U.S. patent application number 16/012293 was filed with the patent office on 2018-10-18 for compositions containing polymeric, ionic compounds comprising imidazolium groups.
The applicant listed for this patent is BASF SE. Invention is credited to Monika HABERECHT, Sebastian KOLTZENBURG, Rupert KONRADI, Erica May Wilson Lauterwasser, Jean-Pierre Berkan Lindner, Jurith Montag, Bernd Muller, Richard Riggs, Claudia Rosenbaum, Michael SIEMER, Bettina SOBOTKA.
Application Number | 20180296459 16/012293 |
Document ID | / |
Family ID | 46877523 |
Filed Date | 2018-10-18 |
United States Patent
Application |
20180296459 |
Kind Code |
A1 |
KONRADI; Rupert ; et
al. |
October 18, 2018 |
COMPOSITIONS CONTAINING POLYMERIC, IONIC COMPOUNDS COMPRISING
IMIDAZOLIUM GROUPS
Abstract
The present invention relates to compositions containing
polymeric, ionic compounds comprising imidazolium groups. In
particular, it relates to the use of polymeric, ionic compounds
comprising imidazolium groups in personal care compositions and/or
in biocide compositions.
Inventors: |
KONRADI; Rupert; (Ladenburg,
DE) ; SIEMER; Michael; (Neuhofen, DE) ;
SOBOTKA; Bettina; (Mannheim, DE) ; KOLTZENBURG;
Sebastian; (Neustadt, DE) ; HABERECHT; Monika;
(Ludwigshafen, DE) ; Lindner; Jean-Pierre Berkan;
(Mannheim, DE) ; Rosenbaum; Claudia; (Einhausen,
DE) ; Muller; Bernd; (Frankenthal, DE) ;
Riggs; Richard; (Mannheim, DE) ; Lauterwasser; Erica
May Wilson; (Mannheim, DE) ; Montag; Jurith;
(Ludwigshafen, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BASF SE |
Ludwigshafen am Rhein |
|
DE |
|
|
Family ID: |
46877523 |
Appl. No.: |
16/012293 |
Filed: |
June 19, 2018 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13427287 |
Mar 22, 2012 |
10016354 |
|
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16012293 |
|
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61466493 |
Mar 23, 2011 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
A61Q 19/00 20130101;
A61P 17/08 20180101; A61K 31/787 20130101; A61Q 17/00 20130101;
A61K 8/84 20130101; A61P 17/10 20180101; A01N 43/50 20130101; A01N
43/50 20130101; A01N 2300/00 20130101; A01N 43/50 20130101; A01N
43/56 20130101; A01N 43/653 20130101; A01N 47/24 20130101 |
International
Class: |
A61K 8/84 20060101
A61K008/84; A61Q 19/00 20060101 A61Q019/00; A61Q 17/00 20060101
A61Q017/00; A61K 31/787 20060101 A61K031/787; A01N 43/50 20060101
A01N043/50; A01N 43/56 20060101 A01N043/56; A01N 43/653 20060101
A01N043/653; A01N 47/24 20060101 A01N047/24 |
Claims
1-43. (canceled)
44. A biocide composition comprising at least one polymeric, ionic
compound comprising imidazolium groups (imidazolium compound),
obtainable by reacting a) at least one .alpha.-dicarbonyl compound,
b) at least one aldehyde, c) at least one amino compound having at
least two primary amino groups, d) optionally an amino compound
having only one primary amino group and e) at least one protic
acid, and optionally subjecting the reaction product to an anion
exchange, where in the components a) and b) the aldehyde carbonyl
groups may also be present as hemiacetal or acetal and the ketone
carbonyl groups may also be present as hemiketal or ketal; where
the main chain of the at least one compound comprising imidazolium
groups does not contain 1,4-bound phenylene rings; where the amino
compound having at least two primary amino groups is not
1,3-diamino-2-hydroxy-propane or
1,3-diamino-2-hydroxy-2-methyl-propane; and where the polymer
comprises at least 8 imidazolium rings; and at least one carrier
and/or at least one auxiliary agent.
Description
BACKGROUND OF THE INVENTION
[0001] The present invention relates to compositions containing
polymeric, ionic compounds comprising imidazolium groups. In
particular, it relates to the use of polymeric, ionic compounds
comprising imidazolium groups in personal care compositions and/or
in biocide compositions and in particular in fungicide
compositions.
DESCRIPTION OF THE RELATED ART
[0002] Cationic polymers are widely used in various technical
fields. They are employed e.g. as the active component of biocide
compositions for diversified applications. They are also widely
used in personal care and household products to perform a function
in the final product, ranging e.g. from thickening to conditioning
of a substrate. Depending on the application, the substrate treated
with a composition of a cationic polymer can be skin, hair,
leather, a textile substrate, the surface of an object, etc.
Cationic polymers can be used in haircare products to provide
conditioning to the hair. In skincare products, the same polymers
can provide conditioning effects to the skin. When incorporated
into detergent and fabric softening formulations, the same polymers
can provide conditioning, softening, and antistatic characteristics
to fabrics. There is a continuing demand for cationic polymers
having an overall good application profile for diverse areas of
use.
[0003] According to German biocide law and the EU Biocidal Products
Directive "biocides" are active substances or mixtures containing
one or more active substances, intended to destroy, deter, render
harmless, prevent the action of, or otherwise exert a controlling
effect on any harmful organism by chemical or biological means.
"Harmful organism" means organisms, including pathogenic agents,
which have an unwanted presence or a detrimental effect on humans,
their activities or the products they use or produce, or on
animals, plants or the environment. According to the classification
of the EU Biocidal Products Directive the classification of
biocides, is broken down into 23 product types (i.e. application
categories). They can be roughly categorised in the following main
groups: general biocidal products, disinfectants, preservatives,
pest control, anti-fouling products.
[0004] It is known to employ cationic oligomers and polymers as
active components of biocide compositions. WO 2006/117382 A1
teaches the use of a cationic polymer selected from polyethylene
imines and polyvinyl amines comprising 0.1 to 22 milliequivalent
cationic groups per gram of polymer as active biocidal
substances.
[0005] JP 04-202305 describes a resin having a polystyrene based
main chain and a graft-chain attached to a benzene ring of the main
chain comprising imidazolinium groups. Those resins are useful
inter alia as antimicrobial agent.
[0006] G. Garg et al. describe in J. Colloid Interface Sci. 344
(2010), 90-96 anion effects on anti-microbial activity of
poly[1-vinyl-3-(2-sulfoethyl imidazolium betaine)]. The employed
polymers have a comb structure with a polyalkylene main chain and
zwitterionic side chains comprising a cationic imidazolium group
and an anionic sulfonate group.
[0007] GB 2271718 A describes polyquaternary ammonium compounds of
the formula:
##STR00001##
where R.sup.1 is hydrogen, alkyl, or aryl, each of R.sup.2 and
R.sup.3 is hydrogen or alkyl of 1 to 4 carbon atoms, R.sup.4 is
hydrogen or methyl, X is hydroxyl or halogen, and n is an integer,
that are useful as antimicrobial agents, especially against fungi
and bacteria.
[0008] WO 98/49898 describes biocidal agents comprising quaternary
cationic surfactants having two imidazolinium groups.
[0009] WO 94/08972 describes inter alia the use of oligomeric
imidazolium salts as swimming pool sanitizers having improved
compatibility with chlorine. The oligomeric imidazolium salts
comprise at the most 7 repeat units and the main chain is
terminated by C.sub.1-C.sub.24-hydrocarbyl groups at both ends. The
anion is especially halide, such as chloride, iodide and in
particular bromide.
[0010] WO 03/000221 describes a composition for the treatment of
acne and further skin problems that are accompanied by a
hyperseborrhoea. The composition comprises at least one polymeric
compound with quaternary ammonium groups in the main chain that are
at least partly derived from imidazolium groups. In the concrete
embodiments the main chain comprises in addition at least one
1,4-bound benzene ring and/or a quaternary ammonium ion derived
from an acyclic amine.
[0011] WO 2010/072571 relates to a method for producing polymeric,
ionic imidazolium compounds, characterized in that an
.alpha.-dicarbonyl compound, an aldehyde, at least one amino
compound having at least two primary amino groups, optionally an
amino compound having only one primary amino group, and a hydracid
are reacted with each other. It is not disclosed to employ the
obtained imidazolium compounds as biocides.
[0012] There is a continuing demand for biocides that
simultaneously meet the complex application requirements of various
different uses.
[0013] In the field of personal care compositions, cationic
polymers are used inter alia in detergent cosmetic compositions
employed for cleansing and caring the hair or the skin. Detergent
compositions may additionally comprise at least one cosmetically
acceptable active ingredient that is beneficial to keratin
materials.
[0014] US 2009/0048132 A1 (EP 2 011 477) describes a detergent and
conditioning composition comprising, in a cosmetically acceptable
aqueous medium, at least one cationic polymer, a mixture of 4
different surfactants and at least one beneficial agent other than
the cationic polymer. The composition is used in particular for
cleansing and caring the hair or the skin.
[0015] US 2009/0074692 A1 teaches to use a combination of at least
one cationic polymer and at least one associative polymer in
cosmetic conditioning compositions.
[0016] FR 2920975 A1 describes a composition for antidandruff
treatment of hair and scalp that comprises selenium disulfide and
one or more cationic polymers obtained by polymerization of a
mixture of monomers comprising one or more vinyl monomers
substituted by amino groups, one or more hydrophobic non-ionic
vinyl monomers and one or more associative vinyl monomers.
[0017] FR 2912908 A1 describes a hair dye composition comprising a
cationic dye and a cationic polymer.
[0018] US 2008/131391 A1 (EP 1 927 344) describes a composition for
treating a keratinous substrate, comprising: a) at least one
quaternary ammonium polymer, b) at least one fatty quaternary
agent, c) at least one nonionic surfactant, and d) optionally, at
least one ceramide.
[0019] FR 2910276 A1 describes a composition for treating a
keratinous substrate, comprising a cationic polymer and
alkoxysilanes with solubilizing functional groups, to avoid any
degradation in hair feel on repeated application of the
composition.
[0020] It has now been found, surprisingly, that polymeric, ionic
compounds comprising imidazolium groups of the type described in WO
2010/072571 can be advantageously employed as biocides. Due to
their unique application properties they are in particular suitable
for a use in this technical field. It was also surprisingly found
that irrespective of their biocidal activity those polymeric, ionic
compounds comprising imidazolium groups can be advantageously
employed as an alternative of known cationic polymers. They have an
overall good application profile for diverse areas of use, e.g. in
personal care compositions, home care compositions, compositions
used for material protection, pharmaceutical compositions, plant
protection compositions, etc. In particular, advantageous
properties are obtained if conventional cationic polymers used in
personal care compositions are replaced completely or partly by at
least one polymeric, ionic compound comprising imidazolium
groups.
SUMMARY OF THE INVENTION
[0021] In a first aspect, the invention provides a biocide
composition, comprising at least one polymeric, ionic compound
comprising imidazolium groups (imidazolium compound), obtainable by
reacting
a) at least one .alpha.-dicarbonyl compound, b) at least one
aldehyde, c) at least one amino compound having at least two
primary amino groups, d) optionally an amino compound having only
one primary amino group and e) at least one protic acid, and
optionally subjecting the reaction product to an anion exchange,
where in the components a) and b) the aldehyde carbonyl groups may
also be present as hemiacetal or acetal and the ketone carbonyl
groups may also be present as hemiketal or ketal; where the main
chain of the at least one compound comprising imidazolium groups
does not contain 1,4-bound phenylene rings and specifically does
not contain phenylene rings; where the amino compound having at
least two primary amino groups is not 1,3-diamino-2-hydroxy-propane
or 1,3-diamino-2-hydroxy-2-methyl-propane; and where the polymer
comprises at least 8, preferably at least 10 imidazolium rings; and
at least one carrier and/or at least one auxiliary agent.
[0022] Especially, the main chain of the at least one imidazolium
compound apart from the nitrogen atoms of the imidazolium groups
does not contain any quaternary nitrogen atoms that bear 4 residues
that are different from hydrogen.
[0023] Especially, the main chain of the at least one imidazolium
compound does not contain quaternary ammonium groups of the formula
--(N.sup.+R.sup.AR.sup.B)--, wherein R.sup.A and R.sup.B may have
the same or different meanings, selected from alkyl,
monohydroxyalkyl and polyhydroxyalkyl.
[0024] In particular, the biocide composition according to the
invention is: [0025] a plant protection composition; especially a
fungicidal composition, or [0026] a personal care composition, or
[0027] a home care composition, or [0028] a composition used for
industrial or institutional or hospital disinfection, [0029] a
material protection composition, or [0030] a pharmaceutical
composition.
[0031] Special embodiments of the personal care composition
according to the invention are: [0032] a cosmetic composition, or
[0033] a hygiene composition.
[0034] In a further aspect, the invention provides an antimicrobial
polymer composition or coating composition, wherein the polymer
composition or the coating comprises an effective antimicrobial
amount of at least one polymeric, ionic compound comprising
imidazolium groups, as defined above and in the following.
[0035] The imidazolium compounds according to the invention show a
rapid effect and a broad range of applications against various
microorganisms. Thus, in a first variant, the imidazolium compound
can be used as disinfectants and general biocidal products, e.g. as
defined in main group 1 of the EU Biocidal Products Directive
(Directive 98/8/EC). The imidazolium compounds according to the
invention can be used advantageously as or in: [0036] Human hygiene
biocidal products [0037] Private area and public health area
disinfectants and other biocidal products [0038] Veterinary hygiene
biocidal products [0039] Food and feed area disinfectants [0040]
Drinking water disinfectants
[0041] The imidazolium compounds according to the invention also
show a microbiostatic effect over a long period of time effect
against various microorganisms. Thus, in a second variant, the
imidazolium compound can be used as preservatives, e.g. as defined
in main group 2 of the EU Biocidal Products Directive (Directive
98/8/EC). The imidazolium compounds according to the invention can
be used advantageously as or in: [0042] In-can preservatives [0043]
Film preservatives [0044] Wood preservatives [0045] Fibre, leather,
rubber and polymerised materials preservatives [0046] Masonry
preservatives [0047] Preservatives for liquid-cooling and
processing systems [0048] Slimicides [0049] Metalworking-fluid
preservatives
[0050] In a further aspect, the invention provides a method for
combating harmful organisms or for protecting human beings,
animals, materials or processes from the effects of these harmful
organisms, wherein the habitat of the harmful organism or the human
being, animal or material to be protected is brought into contact
with a biocide composition or the biocide composition is employed
in said process, wherein the biocide composition comprises at least
one polymeric, ionic compound comprising imidazolium groups, as
defined above and in the following.
[0051] In a further aspect, the invention provides a method for
combating harmful fungi, which method comprises treating the fungi
or materials, plants, parts thereof, the locus where the plants
grow or are to grow or plants' propagation material to be protected
from fungal attack with an effective amount of at least one
polymeric, ionic compound comprising imidazolium groups
(imidazolium compound), obtainable by reacting
a) at least one .alpha.-dicarbonyl compound, b) at least one
aldehyde, c) at least one amino compound having at least two
primary amino groups, d) optionally an amino compound having only
one primary amino group and e) at least one protic acid, and
optionally subjecting the reaction product to an anion exchange,
where in the components a) and b) the aldehyde carbonyl groups may
also be present as hemiacetal or acetal and the ketone carbonyl
groups may also be present as hemiketal or ketal; or with a
composition comprising said polymeric, ionic compound.
[0052] Preferably, the amino compound c) having at least two
primary amino groups is not 1,3-diamino-2-hydroxy-propane or
1,3-diamino-2-hydroxy-2-methyl-propane.
[0053] Alternatively or additionally, the polymer comprises
preferably at least 8, more preferably at least 10 imidazolium
rings
[0054] More preferably, the ionic compound comprising imidazolium
groups is as defined above and in the following.
[0055] In a further aspect, the invention provides the use of at
least one imidazolium compound, as defined above and in the
following, as biocide.
[0056] In a further aspect, the invention provides the use of of at
least one polymeric, ionic compound comprising imidazolium groups
(imidazolium compound), obtainable by reacting
a) at least one .alpha.-dicarbonyl compound, b) at least one
aldehyde, c) at least one amino compound having at least two
primary amino groups, d) optionally an amino compound having only
one primary amino group and e) at least one protic acid, and
optionally subjecting the reaction product to an anion exchange,
where in the components a) and b) the aldehyde carbonyl groups may
also be present as hemiacetal or acetal and the ketone carbonyl
groups may also be present as hemiketal or ketal; for combating
harmful fungi.
[0057] Preferably, the amino compound c) having at least two
primary amino groups is not 1,3-diamino-2-hydroxy-propane or
1,3-diamino-2-hydroxy-2-methyl-propane.
[0058] Alternatively or additionally, the polymer comprises
preferably at least 8, more preferably at least 10 imidazolium
rings
[0059] More preferably, the ionic compound comprising imidazolium
groups is as defined above and in the following.
[0060] In a further aspect, the invention provides a composition,
comprising at least one imidazolium compound, as defined above and
in the following, wherein the imidazolium compound performs a
function in the final product different from the function as
biocide. The imidazolium compound may perform this function as an
alternative to or in addition to the function as biocide.
[0061] A preferred embodiment of a composition, wherein the
imidazolium compound performs a function in the final product
different from the function as biocide, is a personal care
composition, comprising [0062] A) at least one polymeric, ionic
compound comprising imidazolium groups (imidazolium compound),
obtainable by reacting [0063] a) at least one .alpha.-dicarbonyl
compound, [0064] b) at least one aldehyde, [0065] c) at least one
amino compound having at least two primary amino groups, [0066] d)
optionally an amino compound having only one primary amino group
and [0067] e) at least one protic acid, [0068] and optionally
subjecting the reaction product to an anion exchange, [0069] where
the main chain of the at least one compound comprising imidazolium
groups does not contain benzene rings, and [0070] where in the
components a) and b) the aldehyde carbonyl groups may also be
present as hemiacetal or acetal and the ketone carbonyl groups may
also be present as hemiketal or ketal, [0071] C) optionally at
least one cosmetically acceptable active ingredient, and [0072] D)
optionally at least one cosmetically acceptable auxiliary.
[0073] A first special embodiment is a cosmetic composition,
comprising in a cosmetically acceptable medium [0074] at least one
imidazolium compound (=component A), as defined above and in the
following, [0075] at least one surfactant and [0076] at least one
cosmetically acceptable active ingredient that is beneficial to
keratin materials.
[0077] The combination of at least one imidazolium compound
according to the invention, at least one surfactant and at least
one cosmetically acceptable active ingredient that is beneficial to
keratin materials may lead to an increase of the deposition of the
beneficial agent on keratin materials and thereby to an increase in
the efficacy of said beneficial agents or to reduce the amount of
said agent used.
[0078] A second special embodiment is a cosmetic composition,
comprising in a cosmetically acceptable medium [0079] at least one
imidazolium compound (=component A), as defined above and in the
following, and [0080] at least one associative polymer.
[0081] Cosmetic compositions, in particular hair compositions, such
as a shampoo or a conditioner, are most commonly in the form of a
liquid having different viscosities. Products of which the texture
is sufficiently thick to remain on the hair, without running, for a
certain period of time, are desirable. This thickener, or even gel,
texture, should not impair the qualities of the product when used.
The use of conventional thickener polymers having usually very high
molar masses creates problems, such as a relatively unpleasant
texture and poor spreadability of the gels obtained. It was now
surprisingly found that a cosmetic composition comprising at least
one imidazolium compound according to the invention and at least
one associative polymer remedies these drawbacks. The compositions
according to the present invention give hair more mass, more body,
and more sheen compared with compositions comprising an associative
polymer in the absence of at least one imidazolium compound.
[0082] A third special embodiment is an antidandruff composition,
comprising in a cosmetically acceptable medium [0083] at least one
imidazolium compound (=component A), as defined above and in the
following, and [0084] optionally at least one antidandruff agent
different from the imidazolium compound.
[0085] Antidandruff products, which have been proposed in order to
combat the formation of dandruff, which is generally accompanied by
a microbial and/or fungal proliferation, are either products which
inhibit microbial proliferation, or keratolytic products. However,
hair treated with antidandruff agents has a coarse, charged feel.
In addition, the use of cationic polymers from the prior art for
this purpose can present various drawbacks. On account of their
high affinity for the hair, some of these polymers can become
deposited in large amount during repeated use, and give undesirable
effects, such as an unpleasant, charged feel, stiffness of the hair
and an inter-fibre adhesion which affects styling. It has now been
surprisingly found that the imidazolium compounds of the invention
used alone or in combination with conventional antidandruff agents
can allow these drawbacks to be overcome or lessened.
[0086] A fourth special embodiment is a composition for the
treatment of acne and cutaneous disorders linked to
hyperseborrhoea, comprising in a cosmetically acceptable medium at
least one imidazolium compound (=component A), as defined above and
in the following.
[0087] A fifth special embodiment is a hair dye composition,
comprising in a cosmetically acceptable medium [0088] at least one
imidazolium compound (=component A), as defined above and in the
following, and [0089] at least one dye, preferably at least one
cationic dye.
[0090] A sixth special embodiment is a cosmetic composition for
treating a keratinous substrate, comprising in a cosmetically
acceptable medium [0091] at least one imidazolium compound
(=component A), as defined above and in the following, and [0092]
at least one fatty quaternary amine.
[0093] A seventh special embodiment is a cosmetic composition for
treating a keratinous substrate, comprising in a cosmetically
acceptable medium [0094] at least one imidazolium compound
(=component A), as defined above and in the following, and [0095]
at least one alkoxysilane with solubilizing functional groups.
[0096] In a further aspect, the invention provides the use of at
least one imidazolium compound, as defined above and in the
following, as auxiliary in pharmacy, preferably as or in (a)
coating(s) for solid drug forms, as surface-active compound, as or
in (an) adhesive(s) and as or in (a) coating(s) for the textile,
paper, printing and leather industry.
DESCRIPTION OF THE INVENTION
[0097] In the context of the invention, the expression "harmful
organism" comprises organisms which have a detrimental effect on
humans, their activities or the products they use or produce, or on
animals or the environment. This includes pathogenic agents. The
term "harmful organism" also comprises organisms which have an
unwanted presence.
[0098] In the context of the invention, the expression
"unsubstituted or substituted alkyl, alkoxy, alkylthio, cycloalkyl,
cycloalkoxy, cycloalkylthio, aryl, aryloxy, arylthio", represents
unsubstituted or substituted alkyl, unsubstituted or substituted
alkoxy, unsubstituted or substituted alkylthio, unsubstituted or
substituted cycloalkyl, unsubstituted or substituted cycloalkoxy,
unsubstituted or substituted cycloalkylthio, unsubstituted or
substituted aryl, unsubstituted or substituted aryloxy,
unsubstituted or substituted arylthio.
[0099] In the context of the present invention, the expression
"alkyl" comprises straight-chain or branched alkyl groups. Alkyl is
preferably C.sub.1-C.sub.30-alkyl, more preferably
C.sub.1-C.sub.20-alkyl even more preferably C.sub.1-C.sub.12-alkyl
and in particular C.sub.1-C.sub.6-alkyl. Examples of alkyl groups
are especially methyl, ethyl, n-propyl, isopropyl, n-butyl,
isobutyl, sec-butyl, tert-butyl, n-pentyl, neo-pentyl, n-hexyl,
n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl,
n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and
n-eicosyl.
[0100] Examples for C.sub.1-C.sub.6-alkyl are methyl, ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,
n-pentyl, neo-pentyl, n-hexyl, and position isomers thereof.
[0101] Examples for C.sub.1-C.sub.12-alkyl are, apart those
mentioned above for C.sub.1-C.sub.6-alkyl, n-heptyl, n-octyl,
2-ethylhexyl, n-nonyl, n-decyl, 2-propylheptyl, n-undecyl,
n-dodecyl and position isomers thereof.
[0102] Examples for C.sub.1-C.sub.20-alkyl are, apart those
mentioned above for C.sub.1-C.sub.12-alkyl, n-tridecyl,
n-tetradecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl,
n-eicosyl and position isomers thereof.
[0103] Examples for C.sub.1-C.sub.30-alkyl are, apart those
mentioned above for C.sub.1-C.sub.20,-alkyl, n-henicosyl, n-docosy,
n-tricosyl, n-tetracosy, n-pentacosyl, n-hexacosyl, n-octacosy,
n-nonacosyl, n-triacontyl and position isomers thereof.
[0104] The expression alkyl also comprises alkyl radicals whose
carbon chains may be interrupted by one or more nonadjacent groups
which are selected from --O--, --S--, --NR.sup.b--, --C(.dbd.O)--,
--S(.dbd.O)-- and/or --S(.dbd.O).sub.2--. R.sup.b is preferably
hydrogen, alkyl, cycloalkyl aryl or a group CH.sub.2CH.sub.2--O
.sub.y--R.sup.c, wherein y is 1, 2, 3, 4, 5 or 6 and R.sup.c is
hydrogen or C.sub.1-C.sub.4-alkyl. Preferably however, the term
alkyl does not comprise alkyl radicals whose carbon chains may be
interrupted by one or more nonadjacent groups which are selected
from --O--, --S--, --NR.sup.b--, --C(.dbd.O)--, --S(.dbd.O)--
and/or --S(.dbd.O).sub.2-- unless explicitly specified.
[0105] Substituted alkyl groups may, depending on the length of the
alkyl chain, have one or more (e.g. 1, 2, 3, 4, 5 or more than 5)
substituents. These are preferably each independently selected from
cycloalkyl, aryl, fluorine, chlorine, bromine, hydroxyl, mercapto,
cyano, nitro, nitroso, formyl, acyl, COOH, carboxylate,
alkylcarbonyloxy, carbamoyl, SO.sub.3H, sulfonate, sulfamino,
sulfamide, amidino, NE.sup.1E.sup.2, where E.sup.1 and E.sup.2 are
each independently hydrogen, alkyl, cycloalkyl or aryl. Cycloalkyl
and aryl substituents of the alkyl groups may in turn be
unsubstituted or substituted; suitable substituents are the
substituents mentioned below for these groups.
[0106] The above remarks regarding alkyl also apply to the alkyl
moiety in alkoxy (an alkyl radical bound via an oxygen atom to the
remainder of the molecule) and alkylthio (=alkylsulfanyl; an alkyl
radical bound via a sulfur atom to the remainder of the
molecule).
[0107] Examples for C.sub.1-C.sub.6-alkoxy are methoxy, ethoxy,
n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy,
tert-butoxy, n-pentoxy, neo-pentoxy, n-hexoxy, and position isomers
thereof.
[0108] Examples for C.sub.1-C.sub.20-alkoxy are, apart those
mentioned above for C.sub.1-C.sub.6-alkoxy, n-heptoxy, n-octyloxy,
n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, n-tridecyloxy,
n-tetradecyloxy, n-pentadecyloxy, n-hexadecyloxy, n-heptadecyloxy,
n-octadecyloxy, n-nonadecyloxy, n-docosyloxy and position isomers
thereof.
[0109] Examples for C.sub.1-C.sub.6-alkylthio are methylthio,
ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio,
sec-butylthio, tert-butylthio, n-pentylthio, neo-pentylthio,
n-hexylthio, and position isomers thereof.
[0110] Examples for C.sub.1-C.sub.20-alkylthio are, apart those
mentioned above for C.sub.1-C.sub.6-alkyl, n-heptylthio,
n-octylthio, 2-ethylhexylthio, n-nonylthio, n-decylthio,
2-propylheptylthio, n-undecylthio, n-dodecylthio, n-tridecylthio,
n-tetradecylthio, n-hexadecylthio, n-heptadecylthio,
n-octadecylthio, n-nonadecylthio, n-eicosylthio and position
isomers thereof.
[0111] In the context of the present invention, the term
"cycloalkyl" denotes a mono-, bi- or tricyclic hydrocarbon radical
having usually from 3 to 20 ("C.sub.3-C.sub.20-cycloalkyl"),
preferably 3 to 12 ("C.sub.3-C.sub.12-cycloalkyl"), more preferably
3 to 10 ("C.sub.3-C.sub.10-cycloalkyl"), in particular 3 to 8
("C.sub.3-C.sub.8-cycloalkyl"), e.g. 5 to 8
("C.sub.5-C.sub.8-cycloalkyl"), carbon atoms such as cyclopropyl,
cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl,
cyclododecyl, cyclopentadecyl, norbornyl, bicyclo[2.2.2]octyl or
adamantyl.
[0112] Preferably, the term cycloalkyl denotes a monocyclic
hydrocarbon radical.
[0113] Examples for C.sub.3-C.sub.8-cycloalkyl are cyclopropyl,
cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and
cyclooctyl.
[0114] Substituted cycloalkyl groups may, depending on the ring
size, have one or more (e.g. 1, 2, 3, 4, 5 or more than 5)
substituents. These are preferably each independently selected from
alkyl, alkoxy, alkylthio, cycloalkyl, aryl, fluorine, chlorine,
bromine, hydroxyl, mercapto, cyano, nitro, nitroso, formyl, acyl,
COOH, carboxylate, alkylcarbonyloxy, carbamoyl, SO.sub.3H,
sulfonate, sulfamino, sulfamide, amidino, NE.sup.3E.sup.4, where
E.sup.3 and E.sup.4 are each independently hydrogen, alkyl,
cycloalkyl or aryl. In the case of substitution, the cycloalkyl
groups preferably bear one or more, for example one, two, three,
four or five, C.sub.1-C.sub.6-alkyl groups.
[0115] The above remarks regarding cycloalkyl also apply to the
cycloalkyl moiety in cycloalkoxy (a cycloalkyl radical bound via an
oxygen atom to the remainder of the molecule) and cycloalkylthio
(=cycloalkylsulfanyl; a cycloalkyl radical bound via a sulfur atom
to the remainder of the molecule).
[0116] Examples for C.sub.3-C.sub.8-cycloalkoxy are cyclopropoxy,
cyclobutoxy, cyclopentoxy, cyclohexoxy, cycloheptoxy and
cyclooctoxy.
[0117] Examples for C.sub.3-C.sub.8-cycloalkylthio are
cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio,
cycloheptylthio and cyclooctylthio.
[0118] In the context of the present invention, the term "aryl"
refers to mono- or polycyclic aromatic hydrocarbon radicals. Aryl
usually is an aromatic radical having 6 to 24 carbon atoms,
preferably 6 to 20 carbon atoms, especially 6 to 14 carbon atoms as
ring members. Aryl is preferably phenyl, naphthyl, indenyl,
fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl, chrysenyl,
pyrenyl, coronenyl, perylenyl, etc., and more preferably phenyl or
naphthyl. Specifically, aryl is phenyl.
[0119] Substituted aryls may, depending on the number and size of
their ring systems, have one or more (e.g. 1, 2, 3, 4, 5 or more
than 5) substituents. These are preferably each independently
selected from alkyl, alkoxy, alkylthio, cycloalkyl, aryl, fluorine,
chlorine, bromine, hydroxyl, mercapto, cyano, nitro, nitroso,
formyl, acyl, COOH, carboxylate, alkylcarbonyloxy, carbamoyl,
SO.sub.3H, sulfonate, sulfamino, sulfamide, amidino,
NE.sup.5E.sup.6, where E.sup.5 and E.sup.6 are each independently
hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl. The
alkyl, alkoxy, alkylthio, cycloalkyl and aryl substituents on the
aryl may in turn be unsubstituted or substituted. Reference is made
to the substituents mentioned above for these groups. The
substituents on the aryl are preferably selected from alkyl and
alkoxy. Substituted aryl is more preferably substituted phenyl
which generally bears 1, 2, 3, 4 or 5, preferably 1, 2 or 3,
substituents.
[0120] Substituted aryl is preferably aryl substituted by at least
one alkyl group ("alkaryl", also referred to hereinafter as
alkylaryl). Alkaryl groups may, depending on the size of the
aromatic ring system, have one or more (e.g. 1, 2, 3, 4, 5, 6, 7,
8, 9 or more than 9) alkyl substituents. The alkyl substituents may
be unsubstituted or substituted. In this regard, reference is made
to the above statements regarding unsubstituted and substituted
alkyl. In a preferred embodiment, the alkaryl groups have
exclusively unsubstituted alkyl substituents. Alkaryl is preferably
phenyl which bears 1, 2, 3, 4 or 5, preferably 1, 2 or 3, more
preferably 1 or 2, alkyl substituents.
[0121] Aryl which bears one or more radicals is, for example, 2-,
3- and 4-methylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dimethylphenyl,
2,4,6-trimethylphenyl, 2-, 3- and 4-ethylphenyl, 2,4-, 2,5-, 3,5-
and 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-, 3- and
4-propylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dipropylphenyl,
2,4,6-tripropylphenyl, 2-, 3- and 4-isopropylphenyl, 2,4-, 2,5-,
3,5- and 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2-, 3-
and 4-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dibutylphenyl,
2,4,6-tributylphenyl, 2-, 3- and 4-isobutylphenyl, 2,4-, 2,5-, 3,5-
and 2,6-diisobutylphenyl, 2,4,6-triisobutylphenyl, 2-, 3- and
4-sec-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-di-sec-butylphenyl,
2,4,6-tri-sec-butylphenyl, 2-, 3- and 4-tert-butylphenyl, 2,4-,
2,5-, 3,5- and 2,6-di-tert-butylphenyl and
2,4,6-tri-tert-butylphenyl; 2-, 3- and 4-methoxyphenyl, 2,4-, 2,5-,
3,5- and 2,6-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2-, 3- and
4-ethoxyphenyl, 2,4-, 2,5-, 3,5- and 2,6-diethoxyphenyl,
2,4,6-triethoxyphenyl, 2-, 3- and 4-propoxyphenyl, 2,4-, 2,5-, 3,5-
and 2,6-dipropoxyphenyl, 2-, 3- and 4-isopropoxyphenyl, 2,4-, 2,5-,
3,5- and 2,6-diisopropoxyphenyl and 2-, 3- and 4-butoxyphenyl.
[0122] The above remarks regarding aryl also apply to the aryl
moiety in aryloxy (an aryl radical bound via an oxygen atom to the
remainder of the molecule) and arylthio (=arylsulfanyl; an aryl
radical bound via a sulfur atom to the remainder of the
molecule).
[0123] The term alkylene refers to a linear or branched diradical
of an alkane (or, in other words, a divalent alkyl radical).
[0124] C.sub.2-C.sub.3-Alkylene is a linear or branched divalent
alkyl radical having 2 or 3 carbon atoms. Examples are 1,1-ethylene
[CH(CH.sub.3)], 1,2-ethylene (CH.sub.2CH.sub.2), 1,1-propylene
[CH(CH.sub.2CH.sub.3)], 2,2-propylene [--C(CH.sub.3).sub.2--],
1,2-propylene [CH.sub.2CH(CH.sub.3)] or 1,3-propylene
(CH.sub.2CH.sub.2CH.sub.2).
[0125] C.sub.1-C.sub.3-Alkylene is a linear or branched divalent
alkyl radical having 1, 2 or 3 carbon atoms. Examples are, apart
those mentioned above for C.sub.2-C.sub.3-alkylene, also methylene
(CH.sub.2).
[0126] C.sub.2-C.sub.6-Alkylene is a linear or branched divalent
alkyl radical having 2, 3, 4, 5 or 6 carbon atoms. Examples are,
apart those mentioned above for C.sub.2-C.sub.3-alkylene,
n-butylene [(CH.sub.2).sub.4], [(CH.sub.2).sub.3CH(CH.sub.3)],
(CH.sub.2CH(CH.sub.3)CH.sub.2), [CH(CH.sub.2CH.sub.2CH.sub.3)],
[CH.sub.2CH(CH.sub.2CH.sub.3)], [--C(CH.sub.3).sub.2CH.sub.2--],
n-pentylene [(CH.sub.2).sub.5], n-hexylene [hexamethylene;
(CH.sub.2).sub.6] and position isomers thereof.
[0127] C.sub.1-C.sub.6-Alkylene is a linear or branched divalent
alkyl radical having 1, 2, 3, 4, 5 or 6 carbon atoms. Examples are,
apart from the examples mentioned above for
C.sub.2-C.sub.6-alkylene, also methylene (CH.sub.2).
[0128] C.sub.1-C.sub.30-Alkylene is a linear or branched divalent
alkyl radical having 1 to 30 carbon atoms. Examples for
C.sub.1-C.sub.30-alkylene are, apart from the examples mentioned
above for C.sub.1-C.sub.6-alkylene, diradicals (CH.sub.2).sub.x,
wherein x is an integer from 7 to 30, such as heptamethylene,
octamethylene, nonamethylene, decamethylene and the like, and
position isomers thereof.
[0129] C.sub.4-C.sub.12-Alkylene is a linear or branched divalent
alkyl radical having 4 to 12 carbon atoms. Examples for
C.sub.4-C.sub.12-alkylene are n-butylene [(CH.sub.2).sub.4],
[(CH.sub.2).sub.3CH(CH.sub.3)], (CH.sub.2CH(CH.sub.3)CH.sub.2),
[CH(CH.sub.2CH.sub.2CH.sub.3)], [CH.sub.2CH(CH.sub.2CH.sub.3)],
[--C(CH.sub.3).sub.2CH.sub.2--], n-pentylene [(CH.sub.2).sub.5],
n-hexylene [hexamethylene; (CH.sub.2).sub.6], heptamethylene,
octamethylene, nonamethylene, decamethylene, undecamethylene,
dodecamethylene, and position isomers thereof.
[0130] C.sub.4-C.sub.20-Alkylene is a linear or branched divalent
alkyl radical having 4 to 20 carbon atoms. Examples for
C.sub.4-C.sub.20-alkylene are, apart from the examples mentioned
above for C.sub.4-C.sub.12-alkylene, diradicals (CH.sub.2).sub.x,
wherein x is an integer from 13 to 20, and position isomers
thereof.
[0131] C.sub.3-C.sub.20-Alkylene is a linear or branched divalent
alkyl radical having 3 to 20 carbon atoms. Examples for
C.sub.3-C.sub.20-alkylene are, apart from the examples mentioned
above for C.sub.4-C.sub.12-alkylene, 1,1-propylene
[CH(CH.sub.2CH.sub.3)], 2,2-propylene [--C(CH.sub.3).sub.2--],
1,2-propylene [CH.sub.2CH(CH.sub.3)] or 1,3-propylene
(CH.sub.2CH.sub.2CH.sub.2).
[0132] Alkenylene is a linear or branched aliphatic mono- or poly-,
e.g. mono- or di-, olefinically unsaturated divalent radical
having, for example, 2 to 20 or 2 to 10 or 4 to 8 carbon atoms. If
the radical comprises more than one carbon-carbon double bond,
these are preferably not vicinal, i.e. not allenic.
[0133] Alkynylene is a linear or branched aliphatic divalent
radical having, for example, 2 to 20 or 2 to 10 or 4 to 8 carbon
atoms which comprises one or more, e.g. 1 or 2, carbon-carbon
triple bonds.
[0134] C.sub.5-C.sub.8-Cycloalkylene is a divalent monocyclic,
saturated hydrocarbon group having 5 to 8 carbon ring members.
Examples are cyclopentane-1,2-diyl, cyclopentane-1,3-diyl,
cyclohexane-1,2-diyl, cyclohexane-1,3-diyl, cyclohexane-1,4-diyl,
cycloheptane-1,2-diyl, cycloheptane-1,3-diyl,
cycloheptane-1,4-diyl, cyclooctane-1,2-diyl, cyclooctane-1,3-diyl,
cyclooctane-1,4-diyl and cyclooctane-1,5-diyl.
[0135] Carboxylate and sulfonate respectively represent a
derivative of a carboxylic acid function and a sulfonic acid
function, especially a metal carboxylate or sulfonate, a carboxylic
ester or sulfonic ester function or a carboxamide or sulfonamide
function.
[0136] In context of the radical A (see below) being an alkylene
group which may be substituted by a carboxylate group, this term is
limited to a carboxylate anion (COO.sup.-).
[0137] The expression "halogen" denotes in each case fluorine,
bromine, chlorine or iodine, particularly chlorine, bromide or
iodine.
Imidazolium Compound
[0138] The following general definition of the imidazolium
compounds employed according to the invention applies to all
concrete compositions comprising at least one imidazolium compound
mentioned in this application. The following general definition of
the imidazolium compounds also applies to all concrete uses of
those compounds mentioned in this application. Possible differences
(if any) are mentioned for each individual composition or use.
[0139] Suitable imidazolium compounds for the biocide compositions
according to the invention and methods for their production are
described in WO 2010/072571 which is incorporated herein by
reference. Accordingly, the imidazolium compounds can be obtained
by a polycondensation reaction of at least one .alpha.-dicarbonyl
compound, at least one aldehyde, at least one amino compound having
at least two primary amino groups and at least one protic acid as
essential starting materials. In a polycondensation, polymerization
occurs with elimination of a low molecular weight compound, such as
water or alcohol. In the present case, water is eliminated. When
the carbonyl groups of the .alpha.-dicarbonyl compound are present
completely or partly as ketal and/or the aldehyde group of the
aldehyde is present as acetal or hemiacetal, an alcohol is
correspondingly eliminated instead of water.
a) .alpha.-Dicarbonyl Compound
[0140] The .alpha.-dicarbonyl compound is preferably selected from
compounds of the formula (I)
R.sup.1--CO--CO--R.sup.2 (I)
wherein R.sup.1 and R.sup.2 are independently selected from
hydrogen and in each case unsubstituted or substituted alkyl,
alkoxy, alkylthio, cycloalkyl, cycloalkoxy, cycloalkylthio, aryl,
aryloxy, arylthio. Preferably, R.sup.1 and R.sup.2 are
independently selected from hydrogen and in each case unsubstituted
or substituted alkyl, cycloalkyl and aryl and more preferably from
hydrogen and in each case unsubstituted or substituted
C.sub.1-C.sub.20-alkyl, C.sub.3-C.sub.8-cycloalkyl and aryl.
[0141] The .alpha.-dicarbonyl compound a) preferably comprises or
consists of glyoxal. Thus, in particular R.sup.1 and R.sup.2 are
hydrogen.
[0142] The aldehyde or keto group of the compound a) can also be
present as hemiacetal, acetal, hemiketal or ketal, preferably of a
lower alcohol, in particular a C.sub.1-C.sub.10-alkanol. In this
case, the alcohol is eliminated in the condensation reaction
forming the imidazolium compound.
[0143] Preferably, the compound a) is not employed in form of a
hemiacetal, acetal, hemiketal or ketal.
b) Aldehyde
[0144] The aldehyde b) is preferably selected from compounds of the
formula (II)
R.sup.3--CHO (II)
wherein R.sup.3 is selected from hydrogen, alkyl, cycloalkyl and
aryl.
[0145] Preferably, R.sup.3 is selected from hydrogen,
C.sub.1-C.sub.20-alkyl, C.sub.3-C.sub.8-cycloalkyl, optionally
substituted aryl and a radical of the formula --CH.sub.2
O--CH.sub.2CH.sub.2 .sub.x--OR.sup.a, wherein x is 1, 2, 3, 4, 5 or
6 and R.sup.a is hydrogen or C.sub.1-C.sub.4-alkyl, and is more
preferably selected from hydrogen, C.sub.1-C.sub.20-alkyl, a group
--CH.sub.2 O--CH.sub.2CH.sub.2 .sub.x--OR.sup.a, wherein x is 1, 2,
3, 4, 5 or 6 and R.sup.a is hydrogen or C.sub.1-C.sub.4-alkyl and
phenyl which may be substituted by 1, 2, 3, 4 or 5 radicals
selected from C.sub.1-C.sub.20-alkyl, C.sub.1-C.sub.6-haloalkyl,
C.sub.1-C.sub.20-alkoxy, C.sub.1-C.sub.6-haloalkoxy and NR'R'',
where R' and R'R'' are, independently of each other, selected from
hydrogen and C.sub.1-C.sub.6-alkyl.
[0146] Suitable aldehydes are e.g. formaldehyde, acetaldehyde,
propionaldehyde, butanal, pentanal, hexanal, heptanal, octanal,
nonanal, decanal, undecanal, dodecanal, tridecanal, tetradecanal
and the higher homologs with up to 20 carbon atoms, benzaldehyde,
substituted benzaldehydes, such as 2-, 3- or 4-methylbenzaldehyde,
2-, 3- or 4-trifluoromethylbenzaldehyde or 2-, 3- or
4-methoxybenzaldehyde, and aldehydes of formula
CH(.dbd.O)--CH.sub.2 O--CH.sub.2CH.sub.2 .sub.x--OR.sup.a, wherein
x is 1, 2, 3, 4, 5 or 6 and R.sup.a is hydrogen or
C.sub.1-C.sub.4-alkyl, derived from a polyethylene glycol or
polythyleneglycol monoether of formula HOCH.sub.2CH.sub.2
O--CH.sub.2CH.sub.2 .sub.x--OR.sup.a, wherein x is 1, 2, 3, 4, 5 or
6 and R.sup.a is hydrogen or C.sub.1-C.sub.4-alkyl, in which one
CH.sub.2OH group in oxidized to a CHO group.
[0147] The aldehyde group of the aldehyde b) can also be present as
hemiacetal or acetal, preferably as hemiacetal or acetal of a lower
alcohol, in particular a C.sub.1-C.sub.10-alkanol. In this case,
the alcohol is eliminated in the condensation reaction forming the
imidazolium compound.
[0148] The aldehyde group is preferably not present as hemiacetal
or acetal.
[0149] Preferably, component b) comprises or consists of a
formaldehyde source. Thus, in particular R.sup.3 is hydrogen.
Suitable formaldehyde sources are formaldehyde, formaldehyde
oligomers (e.g. trioxane) and polymers of formaldehyde (e.g.
paraformaldehyde). More preferably, component b) comprises or
consists of formaldehyde. In a suitable embodiment, the
formaldehyde is employed as an aqueous solution (formalin
solution).
[0150] Alternatively, the aldehyde is preferably selected from
benzaldehyde and an aldehyde of formula R.sup.3--CHO, where R.sup.3
is C.sub.1-C.sub.20-alkyl, more preferably from acetaldehyde,
propionaldehyde, butanal, pentanal, hexanal, heptanal, octanal,
nonanal, decanal, undecanal, dodecanal, tridecanal, tetradecanal
and the higher homologs with up to 20 carbon atoms, and
benzaldehyde.
[0151] Specifically, the aldehyde is selected from formaldehyde (or
a formaldehyde source), dodecanal and benzaldehyde and is very
specifically formaldehyde (or a formaldehyde source).
c) Amino Compound Having at Least Two Primary Amino Groups
[0152] The amino compound is preferably selected from compounds of
the formula (III)
A(NH.sub.2).sub.m (III)
wherein m is an integer greater than or equal to 2, and A is an
m-valent organic radical.
[0153] In the formula (III), m indicates the number of primary
amino groups bound to the group A. m can assume very large values,
e.g. m can be an integer from 2 to 10 000, in particular from 2 to
5000. Very high values of m are present, e.g. if the compound c) of
the formula (III) comprises a nitrogen-comprising polymer.
[0154] If only amino compounds c) of the formula (III) are
employed, wherein m is 2 (diamines), the obtained imidazolium
compounds are linear.
[0155] If at least one amino compound c) of the formula (III) is
employed, wherein m is greater than 2, the obtained imidazolium
compounds are branched.
[0156] In a preferred embodiment, m is an integer from 2 to 6, in
particular from 2 to 4. More preferably, m is 2 (diamine) or m is 3
(triamine). In particular, m is 2.
[0157] In alternative embodiment, component c) comprises at least
one amino compound having two primary amino groups and at least one
amino compound having three primary amino groups. In this
embodiment, m is a real number in a range of greater than 2 and
less than 3.
[0158] The group A can be, in particular, a hydrocarbon group,
which can be substituted or interrupted by functional groups
comprising heteroatoms.
[0159] In a preferred embodiment, component c) is selected from
[0160] amines of the formula 1
[0160] H.sub.2N-A-NH.sub.2 (1) [0161] wherein [0162] A is a
divalent aliphatic, alicyclic, aliphatic-alicyclic, aromatic or
araliphatic radical, where the aliphatic moieties in the
aforementioned aliphatic, aliphatic-alicyclic or araliphatic
radicals may be interrupted by one or more nonadjacent groups which
are selected from --O--, --S-- and --N(R.sup.b)--, where R.sup.b is
selected from hydrogen, C.sub.1-C.sub.20-alkyl and a group
CH.sub.2CH.sub.2--O .sub.y--R.sup.c, wherein y is 1, 2, 3, 4, 5 or
6 and R.sup.c is hydrogen or C.sub.1-C.sub.4-alkyl; where alicyclic
or aromatic moieties in the aforementioned alicyclic,
aliphatic-alicyclic, aromatic or araliphatic radicals may be
substituted by 1, 2, 3 or 4 radicals selected from
C.sub.1-C.sub.20-alkyl, C.sub.1-C.sub.20-alkoxy, a radical of the
formula --O-- CH.sub.2CH.sub.2O].sub.z--R.sup.d, where R.sup.d is
hydrogen or C.sub.1-C.sub.4-alkyl and z is 1, 2, 3, 4, 5 or 6;
carboxyl and carboxylate, and where the aliphatic moieties in the
aforementioned aliphatic, aliphatic-alicyclic or araliphatic
radicals may be substituted by 1, 2, 3 or 4 radicals selected from
C.sub.1-C.sub.20-alkoxy, a radical of the formula --O
CH.sub.2CH.sub.2O].sub.z--R.sup.d, where R.sup.d is hydrogen or
C.sub.1-C.sub.4-alkyl and z is 1, 2, 3, 4, 5 or 6, carboxyl and
carboxylate; with the proviso that the aromatic or araliphatic
radicals do not contain 1,4-bound phenylene rings; [0163] amines of
the formula 2
##STR00002##
[0163] in which [0164] Y is CR.sup.C, N, C.sub.2-C.sub.6-alkyl or
C.sub.3-C.sub.6-cycloalkyl; [0165] E.sub.1, E.sub.2 and E.sub.3,
independently of each other, are a single bond,
C.sub.1-C.sub.10-alkylene, --NR.sup.D--C.sub.2-C.sub.10-alkylene or
--O--C.sub.1-C.sub.10-alkylene, with the proviso that E.sub.1,
E.sub.2 and E.sub.3 are not a single bond and are not
--NR.sup.D--C.sub.2-C.sub.10-alkylene when Y is N; [0166] R.sup.C
is H, C.sub.2-C.sub.4-hydroxyalkyl or C.sub.1-C.sub.4-alkoxy and is
preferably H, C.sub.1-C.sub.4-alkyl or C.sub.1-C.sub.4-alkoxy; and
[0167] R.sup.B and R.sup.D, independently of each other, are H,
C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.4-hydroxyalkyl or
C.sub.1-C.sub.4-alkoxy and are preferably H, C.sub.1-C.sub.4-alkyl
or C.sub.1-C.sub.4-alkoxy; and [0168] mixtures thereof.
[0169] Divalent aliphatic radicals are those which comprise no
cycloaliphatic, aromatic or heterocyclic constituents. Examples are
alkylene, alkenylene and alkynylene radicals.
[0170] Divalent alicyclic radicals can comprise one or more, e.g.
one or two, alicyclic radicals;
[0171] however, they comprise no aromatic or heterocyclic
constituents. The alicyclic radicals can be substituted by
aliphatic radicals, but bonding sites for the NH.sub.2 groups are
located on the alicyclic radical.
[0172] Divalent aliphatic-alicyclic radicals comprise not only at
least one divalent aliphatic radical but also at least one divalent
alicyclic radical, it being possible for the two bonding sites for
the NH.sub.2 groups to both either be located on the alicyclic
radical(s) or both on the aliphatic radical(s) or one on an
aliphatic radical and the other on an alicyclic radical.
[0173] Divalent aromatic radicals can comprise one or more, e.g.
one or two, aromatic radicals; however, they comprise no alicyclic
or heterocyclic constituents. The aromatic radicals can be
substituted by aliphatic radicals, but both bonding sites for the
NH.sub.2 groups are located on the aromatic radical(s).
[0174] Divalent araliphatic radicals comprise not only at least one
divalent aliphatic radical but also at least one divalent aromatic
radical, it being possible for the two bonding sites for the
NH.sub.2 groups to be located either both on the aromatic
radical(s) or both on the aliphatic radical(s) or one on an
aliphatic radical and the other on an aromatic radical.
[0175] Preferably, the divalent aliphatic radicals A are selected
from linear and branched C.sub.1-C.sub.30-alkylene which may be
interrupted by one or more nonadjacent groups which are selected
from --O--, --S-- and --N(R.sup.b)--, where R.sup.b is selected
from hydrogen, C.sub.1-C.sub.20-alkyl and a group
CH.sub.2CH.sub.2--O .sub.yR.sup.c, wherein y is 1, 2, 3, 4, 5 or 6
and R.sup.c is hydrogen or C.sub.1-C.sub.4-alkyl; and/or may be
substituted by 1, 2, 3 or 4 radicals selected from
C.sub.1-C.sub.20-alkoxy, a radical of the formula --O
CH.sub.2CH.sub.2O].sub.z--R.sup.d, where R.sup.d is hydrogen or
C.sub.1-C.sub.4-alkyl and z is 1, 2, 3, 4, 5 or 6, carboxyl and
carboxylate.
[0176] More preferably, the divalent aliphatic radical A is linear
or branched C.sub.2-C.sub.20-alkylene, even more preferably linear
or branched C.sub.3-C.sub.20-alkylene, particularly preferably
linear or branched C.sub.4-C.sub.20-alkylene and in particular
linear or branched C.sub.4-C.sub.12-alkylene; specifically a linear
C.sub.4-C.sub.12-alkylene. The alkylene chain may carry a carboxyl
or carboxylate group. Preferably, the alkylene biradical is linear.
Examples of suitable amines in which the radical A has this meaning
(C.sub.2-C.sub.20-alkylene) are 1,2-ethylenediamine, 1,2- and
1,3-propylenediamine, 2,2-dimethyl-1,3-propanediamine,
1,4-butylenediamine, 1,5-pentylenediamine, hexamethylenediamine,
heptamethylenediamine, octamethylenediamine, nonamethylenediamine,
decamethylenediamine, undecamethylenediamine,
dodecamethylenediamine, tridecamethylenediamine,
tetradecamethylenediamine, pentadecamethylenediamine,
hexadecamethylenediamine, heptadecamethylenediamine,
octadecamethylenediamine, nonadecamethylenediamine,
eicosamethylenediamine, 2-butyl-2-ethyl-1,5-pentamethylenediamine,
2,2,4- or 2,4,4-trimethyl-1,6-hexamethylenediamine,
1,5-diamino-2-methylpentane, 1,4-diamino-4-methylpentane and the
like. Among these, preference is given to 1,4-butylene diamine,
1,5-pentylene diamine, 1,6-hexylene diamine, 1,8-octylene diamine,
1,12-dodecylenediamine and mixtures thereof. Also preferred are the
carboxyl- or carboxylate-substituted alkylene diamines of formulae
NH.sub.2--CH(COOH)CH.sub.2CH.sub.2CH.sub.2--NH.sub.2 and
NH.sub.2--CH(COO.sup.-)CH.sub.2CH.sub.2CH.sub.2--NH.sub.2.
[0177] In an alternatively more preferred embodiment, the divalent
aliphatic radical A is a group B--X .sub.k--B-- in which each X
independently is --O--, --S-- or --N(R.sup.b)--, where R.sup.b is
selected from hydrogen, C.sub.1-C.sub.20-alkyl and a group
CH.sub.2CH.sub.2--O .sub.y--R.sup.c, wherein y is 1, 2, 3, 4, 5 or
6 and R.sup.c is hydrogen or C.sub.1-C.sub.4-alkyl, preferably O,
each B independently is C.sub.2-C.sub.6-alkylene, preferably
C.sub.2-C.sub.3-alkylene; and k is an integer from 1 to 100,
preferably 1 to 10 and more preferably 2 to 4. Examples of suitable
amines in which the radical A has this meaning are amine-terminated
polyoxyalkylene polyols, for example Jeff-Amines, such as
1,8-diamino-3,6-dioxaoctan, 1,13-diamino-4,7,10-trioxatridecan,
4,9-dioxadodecane-1,12-diamine and
4,7,10-trioxatridecane-1,13-diamine, or else more regular
amine-terminated polyoxyalkylenediols (amine-terminated
polyalkylene glycols; amine-terminated polyalkylene oxides), such
as amine-terminated polyethylene glycols, amine-terminated
polypropylene glycols or amine-terminated polybutylene glycols. The
three last-mentioned amines (amine-terminated polyalkylene glycols)
preferably have a molecular weight of from 100 to 3000 g/mol. Among
these, preference is given to amines
NH.sub.2--[CH.sub.2CH.sub.2O].sub.x--CH.sub.2CH.sub.2--NH.sub.2
with x being 2 or 3, preferably 2, and
NH.sub.2--CH.sub.2CH.sub.2CH.sub.2--[CH.sub.2CH.sub.2O].sub.x--CH.sub.2CH-
.sub.2CH.sub.2--NH.sub.2 with x being 2 or 3, preferably 2.
[0178] Preferably, the divalent alicyclic radicals A are selected
from C.sub.5-C.sub.8-cycloalkylene which may carry 1, 2, 3 or 4
C.sub.1-C.sub.4-alkyl radicals. Examples of suitable amines in
which the radical A has this meaning are cyclopentylenediamine,
such as 1,2-diaminocyclopentane or 1,3-diaminocyclopentane,
cyclohexylenediamine, such as 1,2-diaminocyclohexane,
1,3-diaminocyclohexane or 1,4-diaminocyclohexane,
1-methyl-2,4-diaminocyclohexane, 1-methyl-2,6-diaminocyclohexane,
cycloheptylenediamine, such as 1,2-diaminocycloheptane,
1,3-diaminocycloheptane or 1,4-diaminocycloheptane, and
cyclooctylenediamine, such as 1,2-diaminocyclooctane,
1,3-diaminocyclooctane, 1,4-diaminocyclooctane or
1,5-diaminocyclooctane. The amino groups (NH.sub.2 groups) may be
in the cis or trans position relative to one another.
[0179] Preferably, the divalent aliphatic-alicyclic radicals A are
selected from
C.sub.1-C.sub.4-alkylene-C.sub.5-C.sub.8-cycloalkylene,
C.sub.5-C.sub.8-cycloalkylene-C.sub.1-C.sub.4alkylene-C.sub.5-C.sub.8-cyc-
loalkylene and
C.sub.1-C.sub.4-alkylene-C.sub.5-C.sub.8-cycloalkylene-C.sub.1-C.sub.4-al-
kylene, where the cycloalkylene radicals may carry 1, 2, 3 or 4
C.sub.1-C.sub.4-alkyl radicals. Examples of suitable amines in
which the radical A has this meaning are
diaminodicyclohexylmethane, such as bis(4-aminocyclohexyl)methane
or bis(3-aminocyclohexyl)methane; isophoronediamine,
bis(aminomethyl)cyclohexane, such as
1,1-bis(aminomethyl)cyclohexane, 1,2-bis(aminomethyl)cyclohexane,
1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane,
2-aminopropylcyclohexylamine,
3(4)-aminomethyl-1-methylcyclohexylamine,
2-(2-amino-propyl)-cyclohexylamine and the like. The groups bonded
to the alicyclic radical can in each case assume any desired
position (cis/trans) relative to one another.
[0180] Preferably, the divalent aromatic radicals A are selected
from 1,2-phenylene, 1,3-phenylene, naphthylene and biphenylene,
with the phenylene radicals possibly carrying 1, 2, 3 or 4 radicals
selected from C.sub.1-C.sub.20-alkyl, C.sub.1-C.sub.20-alkoxy and a
radical of the formula --O CH.sub.2CH.sub.2O].sub.x--R.sup.d, where
R.sub.d is hydrogen or C.sub.1-C.sub.4-alkyl and z is 1, 2, 3, 4, 5
or 6. Examples of suitable amines in which the radical A has this
meaning are o-phenylenediamine, m-phenylenediamine,
tolylenediamine, such as o-, m- and p-tolylenediamine,
xylylenediamine, and naphthylenediamine, such as 1,2-, 1,3-, 1,4-,
1,5-, 1,8-, 2,3-, 2,6- and 2,7-naphthylene.
[0181] Preferably, the divalent araliphatic radicals A are selected
from phenylene-C.sub.1-C.sub.4-alkylene,
phenylene-C.sub.1-C.sub.4-alkylene-phenylene and
C.sub.1-C.sub.4-alkylene-phenylene-C.sub.1-C.sub.4-alkylene, with
the phenylene radicals possibly carrying 1, 2, 3 or 4 radicals
selected from C.sub.1-C.sub.20-alkyl, C.sub.1-C.sub.20-alkoxy and a
radical of the formula --O CH.sub.2CH.sub.2O].sub.z--R.sup.d, where
R.sup.d is hydrogen or C.sub.1-C.sub.4-alkyl and z is 1, 2, 3, 4, 5
or 6. Examples of suitable amines in which the radical A has this
meaning are diaminodiphenylmethane, such as 2,2'-, 3,3'- and
4,4'-diaminodiphenylmethane, 3-aminomethyl-benzylamine and the
like.
[0182] Examples for amines 2 are
compounds of the formula (2.A)
##STR00003##
wherein R.sup.5, R.sup.6 and R.sup.7 are each, independently of one
another, a C.sub.1-C.sub.10 alkylene group, particularly preferably
a C.sub.2-C.sub.6-alkylene group; such as
N,N-bis(3-aminopropyl)ethylenediamine,
N,N-bis(3-aminopropyl)propane-1,3-diamine,
N,N-bis(3-aminopropyl)butane-1,4-diamine, tris(2-aminoethyl)amine,
tris(2-aminopropyl)amine, tris(3-aminopropyl)amine,
tris(2-aminobutyl)amine, tris(3-aminobutyl)amine,
tris(4-aminobutyl)amine, tris(5-aminopentyl)amine and
tris(6-aminohexyl)amine. In a preferred embodiment, R.sup.5,
R.sup.6 and R.sup.7 have the same meaning. A preferred compound
(2.A) is tris(2-aminoethyl)amine
(R.sup.5=R.sup.6=R.sup.7=ethylene).
[0183] Further examples of amines 2 are trisaminohexane,
trisaminononane, 4-aminomethyl-1,8-octamethylenediamine and the
like.
[0184] Further examples of amines 2 are the compounds of following
structures (2.B) or (2.C):
##STR00004##
[0185] Further examples of amines 2 are amines of the formula 2,
wherein Y is CR.sup.C, where R.sup.C is H or C.sub.1-C.sub.4-alkyl,
and E.sub.1, E.sub.2 and E.sub.3, independently of each other, are
--O--C.sub.1-C.sub.6-alkylene, preferably
--O--CH.sub.2CH.sub.2CH(CH.sub.3)--. Among these, preference is
given to a compound wherein Y is CR.sup.C, where R.sup.C is ethyl,
and E.sup.1, E.sub.2 and E.sub.3 are
--O--CH.sub.2CH.sub.2CH(CH.sub.3)--.
[0186] Among the above compounds 2, preference is given to the
amine of the formula 2, wherein Y is CR.sup.C, where R.sup.C is
ethyl, and E.sub.1, E.sub.2 and E.sub.3 are
--O--CH.sub.2CH.sub.2CH(CH.sub.3)--.
[0187] In particular, the amine c) is selected from: [0188]
compounds of the formula H.sub.2N--(CH.sub.2).sub.m--NH.sub.2,
wherein m is an integer of 3 to 20, preferably 4 to 20, more
preferably 4 to 12, where a CH.sub.2 group may be substituted by a
carboxyl or carboxylate group, such as 1,3-propylenediamine,
1,4-butylenediamine, 1,5-pentylenediamine, hexamethylenediamine,
heptamethylenediamine, octamethylenediamine, nonamethylenediamine,
decamethylenediamine, undecamethylenediamine,
dodecamethylenediamine, tridecamethylenediamine,
tetradecamethylenediamine, pentadecamethylenediamine,
hexadecamethylenediamine, heptadecamethylenediamine,
octadecamethylenediamine, nonadecamethylenediamine,
eicosamethylenediamine, the carboxyl- or carboxylate-substituted
alkylene diamines of formulae
NH.sub.2--CH(COOH)CH.sub.2CH.sub.2CH.sub.2--NH.sub.2 or
NH.sub.2--CH(COO.sup.-)CH.sub.2CH.sub.2CH.sub.2--NH.sub.2;
especially 1,4-butylene diamine, 1,5-pentylene diamine,
1,6-hexylene diamine, 1,8-octylene diamine, 1,12-dodecylenediamine
and the carboxyl- or carboxylate-substituted alkylene diamines of
formulae NH.sub.2--CH(COOH)CH.sub.2CH.sub.2CH.sub.2--NH.sub.2 or
NH.sub.2--CH(COO.sup.-)CH.sub.2CH.sub.2CH.sub.2--NH.sub.2; [0189]
compounds of the formula NH.sub.2 B--X .sub.k--B--NH.sub.2; in
which each X independently is --O--, --S-- or --N(R.sup.b)--, where
R.sup.b is selected from hydrogen, C.sub.1-C.sub.20-alkyl and a
group CH.sub.2CH.sub.2--O .sub.y--R.sup.c, wherein y is 1, 2, 3, 4,
5 or 6 and R.sup.c is hydrogen or C.sub.1-C.sub.4-alkyl, preferably
O; each B independently is C.sub.2-C.sub.6-alkylene, preferably
C.sub.2-C.sub.3-alkylene; and k is an integer from 1 to 100,
preferably 1 to 10, more preferably 2 to 4, such as
1,8-diamino-3,6-dioxaoctan, 1,13-diamino-4,7,10-trioxatridecan,
4,9-dioxadodecane-1,12-diamine and
4,7,10-trioxatridecane-1,13-diamine, or else more regular
amine-terminated polyoxyalkylenediols (amine-terminated
polyalkylene glycols; amine-terminated polyalkylene oxides), such
as amine-terminated polyethylene glycols, amine-terminated
polypropylene glycols or amine-terminated polybutylene glycols;
especially
NH.sub.2--[CH.sub.2CH.sub.2O].sub.x--CH.sub.2CH.sub.2--NH.sub.2
with x being 2 or 3, preferably 2, and
NH.sub.2--CH.sub.2CH.sub.2CH.sub.2--[CH.sub.2CH.sub.2O].sub.x--CH.sub.2CH-
.sub.2CH.sub.2--NH.sub.2 with x being 2 or 3, preferably 2; [0190]
bis(4-aminocyclohexyl)methane, bis(3-aminocyclohexyl)methane,
isophoronediamine, 1,1-bis(aminomethyl)cyclohexane,
1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane,
1,4-bis(aminomethyl)cyclohexane, 2-aminopropylcyclohexylamine,
3(4)-aminomethyl-1-methylcyclohexylamine,
2-(2-amino-propyl)-cyclohexylamine; especially
bis(4-aminocyclohexyl)methane, bis(3-aminocyclohexyl)methane,
isophoronediamine; 3-aminomethyl-benzylamine; [0191] amines of the
formula 2, wherein Y is CR.sup.C, where R.sup.C is H or
C.sub.1-C.sub.4-alkyl, and E.sub.1, E.sub.2 and E.sub.3,
independently of each other, are --O--C.sub.1-C.sub.6-alkylene,
preferably --O--CH.sub.2CH.sub.2CH(CH.sub.3)--; especially the
amine of the formula 2, wherein Y is CR.sup.C, where R.sup.C is
ethyl, and E.sub.1, E.sub.2 and E.sub.3 are
--O--CH.sub.2CH.sub.2CH(CH.sub.3)--; and [0192] mixtures
thereof.
[0193] It is of course also possible to use in the biocide
compositions of the invention imidazolium compounds that are
obtained from a mixture of two or more than two different amino
compounds c). If an amine of formula 2 is used, it is even
preferred to use it in combination with a diamine A(NH.sub.2).sub.m
with m being 2. In a preferred embodiment, the mixture of amino
compounds c) comprises at least two amino compounds having
different numbers of primary amino groups. The use of diamines
(m=2) in admixture with amino compounds having more than two
primary amino groups (m>2), e.g. triamines, enables the desired
degree of crosslinking or degree of branching to be set via the
proportion of amines with m=2 to amines m>2.
[0194] Preferred mixtures of amino compounds c) are the following:
[0195] tris(2-aminoethyl)amine and ethylene diamine [0196]
tris(2-aminoethyl)amine and 1,3-propylene diamine [0197]
tris(2-aminoethyl)amine and 1,4-butylenediamine [0198]
tris(2-aminoethyl)amine and 1,5-pentylene diamine [0199]
tris(2-aminoethyl)amine and 1,6-hexylene diamine [0200] the amine
of the formula 2, wherein Y is CR.sup.C, where R.sup.C is ethyl,
and E.sub.1, E.sub.2 and E.sub.3 are
--O--CH.sub.2CH.sub.2CH(CH.sub.3)-- and 1,4-butylenediamine.
[0201] In a preferred embodiment, the amino compound c) has a
molecular weight of less than 10 000 g/mol, particularly preferably
less than 5000 g/mol, very particularly preferably less than 1000
g/mol, in particular less than 500 g/mol.
[0202] Possible diamines and triamines are, in particular,
compounds having a molecular weight of from 60 to 500 g/mol or from
60 to 250 g/mol.
[0203] In a further preferred embodiment, component c) is selected
from nitrogen-comprising polymers. Preferably, component c) is
selected from polyvinylamine polymers.
[0204] Suitable polyvinylamine polymers are obtainable by free
radical polymerization of ethylenically unsaturated monomers having
a nitrogen containing group that can be transferred into a primary
amino group. In particular, such monomers are selected from
vinylcarboxamides which comprise amido groups that are capable of
hydrolysis under formation of primary amino groups.
[0205] Suitable polyvinylamine polymers c) are described inter alia
in U.S. Pat. No. 4,421,602, U.S. Pat. No. 5,334,287, EP-A 216 387,
U.S. Pat. No. 5,981,689, WO 00/63295, U.S. Pat. No. 6,121,409 and
U.S. Pat. No. 6,132,558. The teaching of those documents is
incorporated herein by reference. They are prepared in general by
hydrolysis of polymers comprising N-vinylcarboxamide units. These
polymers contain in polymerized form monomers selected from e.g.
N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide,
N-vinyl-N-methyl-acetamide, N-vinyl-N-ethylacetamide,
N-vinylpropionamide and mixtures thereof. It is possible to use
comonomers from different monomer classes. Preferred
polyvinylamines polymers c) are homopolymers of
N-vinylformamide.
[0206] The homo- and copolymers which comprise N-vinylcarboxamide
units incorporated in the form of polymerized units can be partly
or completely hydrolyzed by known methods. The degree of hydrolysis
is generally in a range from 1 to 100 mol %, preferably from 10 to
99 mol %, particularly preferably from 20 to 95 mol % and
especially preferably from 30 to 90 mol %. The degree of hydrolysis
corresponds to the content of primary vinylamine groups in the
polymers, in mol %. The hydrolysis of the polymers described above
is effected by known processes, by the action of acids (e.g.
mineral acids, such as sulfuric acid, hydrochloric acid or
phosphoric acid, carboxylic acids, such as formic acid or acetic
acid, or sulfonic acids or phosphonic acids), bases or enzymes, as
described, for example, in DE-A 31 28 478 and U.S. Pat. No.
6,132,558. With the use of acids as hydrolysis agents, the
vinylamine units of the polymers are present as an ammonium salt,
while the free amino groups form in the hydrolysis with bases.
[0207] Suitable polyvinylamine polymers c) preferably have a number
average molecular weight in a range of from 220 to 1 000 000,
preferably from 440 to 100 000 and in particular 750 to 50 000.
[0208] Suitable poly(alkyleneimines) polymers c) include the
homopolymers of ethyleneimine (aziridine) or its higher homologues,
the copolymers of ethyleneimine or its higher homologues with
further monomers, and also the graft polymers, e.g. of
polyamidoamines or polyvinylamines, with ethyleneimine or its
higher homologues. The poly(alkyleneimines) can be crosslinked or
uncrosslinked. They can be modified, e.g. by reaction with alkylene
oxides, dialkyl or alkylene carbonates or C.sub.1- to
C.sub.4-carboxylic acids or derivatives of C.sub.1- to
C.sub.4-carboxylic acids.
[0209] Suitable poly(alkyleneimines) are obtainable by customary
processes known to the person skilled in the art and are
commercially available. Suitable poly(alkyleneimine)s are all
polymers which are obtainable by cationically initiated
polymerization of alkyleneimines and/or N-substituted
alkyleneimines. Preferred poly(alkyleneimines) are
polyethyleneimines. They are obtainable by cationically initiated
polymerization of ethyleneimine (aziridine) and/or N-substituted
aziridines.
[0210] Poly(alkyleneimines) useful as component c) also include the
polymers of higher homologues of ethyleneimine, such as
propyleneimine (2-methylaziridine), 1- or 2-butyleneimine
(2-ethylaziridine or 2,3-dimethylaziridine). The
poly(alkyleneimines) are preferably homopolymers of
ethyleneimine.
[0211] Catalysts which can be used for the cationic polymerization
of alkyleneimines are, for example, Bronsted acids, such as
sulfuric acid, phosphoric acid, p-toluenesulfonic acid, or
carboxylic acids, such as formic acid, acetic acid or propionic
acid, or Lewis acids, such as halides, for example zinc chloride or
alkyl halides, such as methyl chloride, ethyl chloride, benzyl
chloride or ethylene chloride. Suitable polyethyleneimines can also
be obtained by reaction of ethylene chloride with ammonia and
amines. Polymers of this type are commercial products.
[0212] Useful poly(alkyleneimines) c) also include alkyleneimine
polymers obtainable by grafting polyvinylamines with at least one
alkyleneimine. Preferred are the graft polymers of ethyleneimine.
Suitable polyvinylamines and poly(amidoamines) are mentioned before
and in the following.
[0213] Suitable poly(alkyleneimines) c) preferably have a number
average molecular weight in the range of from 150 to 1 000 000,
more preferably 250 to 10 000.
[0214] Further suitable nitrogen containing polymer c) are
poly(amidoamines). Poly(amidoamines) in the sense of the invention
comprise nitrogen atoms in the form of amide groups and nitrogen
atoms in the form of amine groups. Poly(amidoamines) are
obtainable, for example, by condensing polycarboxylic acids with
polyamines.
[0215] Suitable polycarboxylic acids for the preparation of
poly(amidoamines) are e.g. aliphatic and alicyclic acids. Those
aliphatic and alicyclic acids may have e.g. 2 to 30 carbon atoms.
Preferred are dicarboxylic acids, for example, oxalic acid, malonic
acid, succinic acid, maleic acid, adipic acid, glutaric acid,
suberic acid, sebacic acid, heptanedioic acid, octanedioic acid,
nonanedioic acid, undecane-am-dicarboxylic acid,
dodecane-.alpha.,.omega.-dicarboxylic acid, cis- and
trans-cyclohexane-1,2-dicarboxylic acid, cis and trans
cyclohexane-1,3-dicarboxylic acid, cis and trans
cyclohexane-1,4-dicarboxylic acid, cis and trans
cyclopentane-1,2-dicarboxylic acid, cis and trans
cyclopentane-1,3-dicarboxylic acid.
[0216] In particular, the poly(amidoamines) c) do not contain
aromatic dicarboxylic acids, e.g. phthalic acid, isophthalic acid
or terephthalic acid.
[0217] Suitable tricarboxylic acids or polycarboxylic acids for the
preparation of poly(amidoamines) c) are e.g.
1,2,3-propanetricarboxylic acid or 1,3,5-cyclohexanetricarboxylic
acid.
[0218] The carboxylic acids can also be employed for the
preparation of poly(amidoamines) in the form of derivatives. Such
derivatives are preferably anhydrides, acyl chlorides and esters.
In the polycarboxylic acids all or only a part of the acid groups
may be derivatised. Preferred esters are esters of
C.sub.1-C.sub.8-alcanols, especially the methyl ester or ethyl
ester.
[0219] Suitable polyamines for the preparation of poly(amidoamines)
contain at least two primary or secondary nitrogen atoms capable of
forming amide groups. The total number of basic nitrogen atoms in
the polyamines is preferably in the range of from 3 to 100, more
preferably 3 to 25, e.g. 4 to 10. In the preparation of the
poly(amidoamines), it is possible to use mixtures of two or more
polycarboxylic acids as well as mixtures of two or more polyamines.
Examples of suitable polyamines are diethylenetriamine,
triethylenetetramine, tetraethylene pentamine, dipropylene
triamine, tripropylene tetramine, dihexamethylene triamine,
aminopropylethylenediamine and bisaminopropylethylenediamine.
Suitable polyamines are also polyalkylenepolyamines. The polyamines
can be present in a mixture with diamines. Useful diamines include
for example 1,2-diaminoethane, 1,3-diaminopropane,
1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane,
1,8-diaminooctane, isophoronediamine, 4,4'-diaminodiphenyl-methane,
1,4-bis(3-aminopropyl)piperazine, 4,9-dioxadodecane-1,12-diamine,
4,7,10-trioxatridecane-1,13-diamine or .alpha.,.omega.-diamino
compounds of polyalkylene oxides.
[0220] Lactones or lactams of carboxylic acids having 4 to 8 carbon
atoms may also be used in the condensation for the preparation of
poly(amidoamines).
[0221] Suitable poly(amidoamines) have at least two terminal amino
groups (--NH, --NH.sub.2) or both.
[0222] Suitable as poly(amidoamines) are also poly(amidoamines)
grafted with at least one alkyleneimine, e.g. grafted with
ethyleneimine. Grafted poly(amidoamines) are obtainable from the
above-described poly(amidoamines) by reaction with at least one
alkyleneimine in the presence of Bronsted acids or Lewis acids,
such as sulfuric acid or boron trifluoride etherates. The reaction
temperature is preferably in the range of from 80 to 100.degree. C.
Compounds of this type are described, for example, in U.S. Pat. No.
4,144,123 and DE-B-24 34 816. The teaching of these documents is
incorporated by reference. Suitable poly(amidoamines) grafted with
ethyleneimine have, for example, an average molecular weight of
from 3000 to 1 000 000 daltons. The graft polymers generally
contain from 10 to 90% by weight of polyamidoamines as a grafting
base and from 90 to 10% by weight of alkyleneimine as a graft.
[0223] Suitable poly(amidoamines) c) preferably have a number
average molecular weight in the range of from 150 to 1 000 000,
more preferably 250 to 10 000.
d) Other Starting Materials
[0224] In the process of the invention, it is possible to use
further compounds, e.g. in order to introduce specific end groups
into the polymer or bring about additional crosslinking by means of
further functional groups, to set defined properties or to make
further reactions on the resulting polymer (polymer-analogous
reactions) at a later point in time possible.
[0225] Thus, if desired, it is possible to make concomitant use of,
for example, compounds having only one primary amino group
(=component d)) in order to influence the molecular weight of the
polymeric imidazolium compounds. The compound having only one
primary amino group leads to chain termination and then forms the
end group of the polymer chain concerned. The higher the proportion
of compounds having only one primary amino group, the lower the
molecular weight. Based on 100 mol of amino compounds having at
least two primary amino groups, it is possible, in a preferred
embodiment, to use, for example, from 0 to 10 mol of compounds
having only one primary group.
e) Protic Acid
[0226] The anions of the imidazolium compound are derived from the
anions of the protic acid(s) employed as component e). It is also
possible to subject the imidazolium compound to an anion exchange.
This allows the preparation of imidazolium compounds with anions
for which no corresponding stable protic acid exists. The anion
exchange can be effected by known methods, e.g. transprotonation,
reaction with a metal salt, ion exchange chromatography,
electrolytically or by means of a combination of these
measures.
[0227] The imidazolium compound employed according to the invention
comprises anions that act as counterions to the imidazolium
cations. The anions are selected from anions of the formula
Y.sup.n-, wherein n is the valency of the anion. The corresponding
protic acid can be represented by the formula
Y.sup.n-(H.sup.+).sub.n.
[0228] In a first embodiment, the anions of the formula Y.sup.n-
are selected from anions of inorganic acids and low molecular
weight organic acid. In this embodiment, m is preferably an integer
from 1 to 6, more preferably an integer from 1 to 4, in
particularly 1 or 2. In a special embodiment, n is 1.
[0229] In a second embodiment, the anions of the formula Y.sup.n-
are selected from anions of polymeric protic acids, e.g.
polyacrylic acid. In this embodiment, n can assume very high
values. Suitable polymeric protic acids comprise at least one
ethylenically unsaturated organic acid in polymerized form.
Preferred ethylenically unsaturated organic acid are selected from
acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic
acid, etc. and mixtures thereof. Especially preferred are the homo-
and copolymers of acrylic acid and/or methacrylic acid. Suitable
polymeric protic acids are also the copolymers of at least one
ethylenically unsaturated organic acid, preferably selected from
acrylic acid methacrylic acid, maleic acid, fumaric acid, itaconic
acid with at least one copolymerizable comonomer, e.g. selected
from (meth)acrylates, vinyl esters or aromatic monomers such as
styrene and mixtures thereof.
[0230] The anions of the imidazolium compound (=anions of the
formula Y.sup.n-) and the anions of the corresponding protic acid
(.dbd.Y.sup.n-(H.sup.+).sub.n) are preferably selected from:
the group of halides and halogen-comprising anions of the general
formulae:
F.sup.-, Cl.sup.-, Br.sup.-, I.sup.-, BF.sub.4.sup.-,
PF.sub.6.sup.-, AlCl.sub.4.sup.-, Al.sub.2Cl.sub.7--,
Al.sub.3Cl.sub.10.sup.-, AlBr.sub.4.sup.-, FeCl.sub.4.sup.-,
BCl.sub.4.sup.-, SbF.sub.6.sup.-, AsF.sub.6, --ZnCl.sub.3.sup.-,
SnCl.sub.3.sup.-, CuCl.sub.2;
the group of pseudohalides and other nitrogen-containing anions of
the formulae:
CN.sup.-, SCN.sup.-, OCN.sup.-, NO.sub.2.sup.-, NO.sub.3.sup.-,
N(CN).sup.-;
the group of sulfates, sulfites and sulfonates of the general
formulae:
SO.sub.4.sup.2-, HSO.sub.4.sup.-, SO.sub.3.sup.2-, HSO.sub.3.sup.-,
R.sup.aOSO.sub.3.sup.-, R.sup.2SO.sub.3.sup.-;
the group of phosphates of the general formulae:
PO.sub.4.sup.3-, HPO.sub.4.sup.2-, H.sub.2PO.sub.4.sup.-,
R.sup.aPO.sub.4.sup.2-, HR.sup.aPO.sub.4.sup.-,
R.sup.aR.sup.bPO.sub.4.sup.-;
the group of phosphonates and phosphinates of the general
formulae:
R.sup.aHPO.sub.3.sup.-, R.sup.aR.sup.bPO.sub.2.sup.-,
R.sup.aR.sup.bPO.sub.3.sup.-;
the group of phosphites of the general formulae:
PO.sub.3.sup.3-, HPO.sub.3.sup.2-, H.sub.2PO.sub.3.sup.-,
R.sup.aPO.sub.3.sup.2-, R.sup.aHPO.sub.3.sup.-,
R.sup.aR.sup.bPO.sub.3.sup.-;
the group of phosphonites and phosphinites of the general
formulae:
R.sup.aR.sup.bPO.sub.2.sup.-, R.sup.aHPO.sub.2.sup.-,
R.sup.aR.sup.bPO.sup.-, R.sup.aHPO.sup.-;
the group of carboxylates and polybasic carboxylic acids of the
formulae:
R.sup.aCOO.sup.-; R.sup.e(COO.sup.-).sub.f;
the group of borates of the general formulae:
BO.sub.3.sup.3-, HBO.sub.3.sup.2-, H.sub.2BO.sub.3.sup.-,
R.sup.aR.sup.bBO.sub.3.sup.-, R.sup.aHBO.sub.3.sup.-,
R.sup.aBO.sub.3.sup.2-,
B(OR.sup.a)(OR.sup.b)(OR.sup.c)(OR.sup.d).sup.-,
B(HSO.sub.4).sup.-, B(R.sup.aSO.sub.4).sup.-;
the group of boronates of the general formulae:
R.sup.2BO.sub.2.sup.2-, R.sup.aR.sup.bBO.sup.-;
the group of halogenated hydrocarbons of the general formulae:
CF.sub.3SO.sub.3, (CF.sub.3SO.sub.3).sub.2N.sup.-,
CF.sub.3CO.sub.2, CCl.sub.3CO.sub.2.sup.-;
the group of carbonates and carbonic esters of the general
formulae:
HCO.sub.3.sup.-, CO.sub.3.sup.2-, R.sup.aCO.sub.3.sup.-;
the group of silicates and silicic esters of the general
formulae:
SiO.sub.4.sup.4-, HSiO.sub.4.sup.3-, H.sub.2SiO.sub.4.sup.2-,
H.sub.3SiO.sub.4.sup.-, R.sup.aSiO.sub.4.sup.3-,
R.sup.aR.sup.bSiO.sub.4.sup.2-,
R.sup.aR.sup.bR.sup.cSiO.sub.4.sup.-, HR.sup.aSiO.sub.4.sup.2-,
H.sub.2R.sup.aSiO.sub.4.sup.-, HR.sup.aR.sup.bSiO.sub.4.sup.-;
the group of alkylsilane and arylsilane salts of the general
formulae:
R.sup.aSiO.sub.3.sup.3-, R.sup.aR.sup.bSiO.sub.2.sup.2-,
R.sup.aR.sup.bR.sup.cSiO.sup.-,
R.sup.aR.sup.bR.sup.cSiO.sub.3.sup.-,
R.sup.aR.sup.bR.sup.cSiO.sub.2.sup.-,
R.sup.aR.sup.bSiO.sub.3.sup.2-;
the group of carboximides, bis(sulfonyl)imides and sulfonylimides
of the general formulae:
##STR00005##
the group of methides of the general formula:
##STR00006##
the group of alkoxides and aryloxides of the general formula:
R.sup.aO.sup.-;
the group of halometalates of the general formula:
[M.sub.rHal.sub.t].sup.s-,
where M is a metal and Hal is fluorine, chlorine, bromine or
iodine, r and t are positive integers and indicate the
stoichiometry of the complex and s is a positive integer and
indicates the charge on the complex; the group of sulfides,
hydrogensulfides, polysulfides, hydrogenpolysulfides and thiolates
of the general formulae:
S.sup.2-, HS.sup.-, [S.sub.v].sup.2-, [HS.sub.v].sup.-,
[R.sup.aS].sup.-,
where v is a positive integer from 2 to 10; the group of complex
metal ions such as Fe(CN).sub.6.sup.3-, Fe(CN).sub.6.sup.4-,
MnO.sub.4.sup.-, Fe(CO).sub.4.
[0231] In the above formulae, R.sup.a, R.sup.b, R.sup.c and R.sup.d
are each, independently of one another, nonacidic hydrogen,
C.sub.1-C.sub.30-alkyl and aryl-, heteroaryl-, cycloalkyl-,
halogen-, hydroxy-, amino-, carboxy-, formyl-, --O--, --CO--,
--CO--O-- or --CO--N<substituted derivatives thereof, for
example methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl,
2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl),
1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl,
2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl,
2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl,
4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl,
4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl,
2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3-dimethyl-1-butyl,
2-ethyl-1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl,
heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,
tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,
nonadecyl, icosyl, henicosyl, docosyl, tricosyl, tetracosyl,
pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl,
triacontyl, phenylmethyl (benzyl), diphenylmethyl, triphenylmethyl,
2-phenylethyl, 3-phenylpropyl, cyclopentylmethyl,
2-cyclopentylethyl, 3-cyclopentyl-propyl, cyclohexylmethyl,
2-cyclohexylethyl, 3-cyclohexylpropyl, methoxy, ethoxy, formyl,
acetyl or C.sub.qF.sub.2(q-a)+(1-b)H.sub.2a+b where q.ltoreq.30,
0.ltoreq.a.ltoreq.q and b=0 or 1 (for example CF.sub.3,
C.sub.2F.sub.5, CH.sub.2CH.sub.2--C.sub.(q-2)F.sub.2(q-2)+1,
C.sub.6F.sub.13, C.sub.8F.sub.17, C.sub.10F.sub.21,
C.sub.12F.sub.25);
C.sub.3-C.sub.12-cycloalkyl and aryl-, heteroaryl-, cycloalkyl-,
halogen-, hydroxy-, amino-, carboxy-, formyl-, --O--, --CO-- or
--CO--O-substituted derivatives thereof, for example cyclopentyl,
2-methyl-1-cyclopentyl, 3-methyl-1-cyclopentyl, cyclohexyl,
2-methyl-1-cyclohexyl, 3-methyl-1-cyclohexyl, 4-methyl-1-cyclohexyl
or C.sub.qF.sub.2(q-a)-(1-b)H.sub.2a-b, where q.ltoreq.30,
0.ltoreq.a.ltoreq.q and b=0 or 1; C.sub.2-C.sub.30-alkenyl and
aryl-, heteroaryl-, cycloalkyl-, halogen-, hydroxy-, amino-,
carboxy-, formyl-, --O--, --CO-- or --CO--O-substituted derivatives
thereof, for example 2-propenyl, 3-butenyl, cis-2-butenyl,
trans-2-butenyl or C.sub.qF.sub.2(q-a)-(1-b)H.sub.2a-b where
q.ltoreq.30, 0.ltoreq.a.ltoreq.q and b=0 or 1;
C.sub.3-C.sub.12-cycloalkenyl and aryl-, heteroaryl-, cycloalkyl-,
halogen-, hydroxy-, amino-, carboxy-, formyl-, --O--, --CO-- or
--CO--O-substituted derivatives thereof, for example
3-cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl,
2,5-cyclohexadienyl or C.sub.q F.sub.2(q-a)-3(1-b)H.sub.2a-3b where
q.ltoreq.30, 0.ltoreq.a.ltoreq.q and b=0 or 1; aryl or heteroaryl
having from 2 to 30 carbon atoms and alkyl-, aryl-, heteroaryl-,
cycloalkyl-, halogen-, hydroxy-, amino-, carboxy-, formyl-, --O--,
--CO-- or --CO--O-substituted derivatives thereof, for example
phenyl, 2-methylphenyl (2-tolyl), 3-methyl-henyl (3-tolyl),
4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl,
2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl,
2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl,
4-phenylphenyl, 1-naphthyl, 2-naphthyl, 1-pyrrolyl, 2-pyrrolyl,
3-pyrrolyl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl or
C.sub.6F.sub.(5-a)H.sub.a, where 0.ltoreq.a.ltoreq.5; or two
radicals form an unsaturated, saturated or aromatic ring which may
optionally be substituted by functional groups, aryl, alkyl,
aryloxy, alkyloxy, halogen, heteroatoms and/or heterocycles and may
optionally be interrupted by one or more oxygen and/or sulfur atoms
and/or one or more substituted or unsubstituted imino groups.
[0232] Particular preference is given to R.sup.a, R.sup.b, R.sup.c
and R.sup.d each being, independently of one another, hydrogen and
particularly preferably a C.sub.1-C.sub.10-alkyl group, preferably
a C.sub.1-C.sub.4-alkyl group.
[0233] R.sup.e (see above formula for the polybasic carboxylic
acid) is an organic radical to which a plurality of carboxylic acid
groups are bound. Correspondingly, f is an integer of at least 2.
Preferably, f is an integer of 2 to 100 000, more preferably, 2 to
10 000. Such polybasic carboxylic acids can be, for example, maleic
acid or itaconic acid, phthalic acid, isophthalic acid or
terephthalic acid; other possibilities are polymeric compounds
which can be obtained, for example, by free-radical polymerization
of ethylenically unsaturated compounds using, possibly among
others, monomers having one or two carboxylic acid groups, e.g.
(meth)acrylic acid.
[0234] Particular preference is given to carboxylic acids, i.e.
protic acids of the above carboxylates of the general formulae:
R.sup.aCOO.sup.- and R.sup.e(--COO.sup.-).sub.f
[0235] As such carboxylic acids or carboxylates, particular mention
may be made of organic compounds which have from 1 to 20 carbon
atoms and comprise one or two carboxylate groups, preferably one
carboxylate group.
[0236] The carboxylic acids or carboxylates can be aliphatic or
aromatic compounds. Here, aromatic compounds are compounds
comprising aromatic groups. Particular preference is given to
aliphatic or aromatic compounds which, apart from the oxygen atoms
of the carboxylate group, comprise no further heteroatoms or at
most comprise one or two hydroxyl groups, carbonyl groups or ether
groups. Very particular preference is given to aliphatic or
aromatic compounds which comprise no further heteroatoms in
addition to the oxygen atoms of the carboxylate group.
[0237] As compounds having two carboxylate groups, mention may be
made of, for example, the anions of phthalic acid, of isophthalic
acid, of C.sub.2-C.sub.6-dicarboxylic acids, e.g. oxalic acid,
malonic acid, succinic acid, glutaric acid, adipic acid.
[0238] As compounds having one carboxylate group, mention may be
made of the anions of aliphatic, aromatic, saturated or unsaturated
C.sub.1-C.sub.20-carboxylic acids, in particular alkanecarboxylic
acids, alkenecarboxylic acids, alkynecarboxylic acids,
alkadienecarboxylic acids, alkatrienecarboxylic acids,
hydroxycarboxylic acids or ketonecarboxylic acids or aromatic
carboxylic acids such as benzoic acid or phenylacetic acid.
Suitable alkanecarboxylic acids, alkenecarboxylic acids and
alkadienecarboxylic acids are also known as fatty acids.
[0239] As anions Y.sup.-, mention may be made of, in particular,
the anions of C.sub.1-C.sub.20-alkanecarboxylic acids, which may
optionally be substituted by one or two hydroxy groups, preferably
one hydroxy group.
[0240] Further preferred protic acids or preferred anions of protic
acids are, apart from carboxylic acids (carboxylates), also
sulfonic acid, phosphoric acid or phosphonic acid, with the acid
groups of the sulfonic acid, phosphoric acid or phosphonic acid
being able to be partially esterified.
[0241] As phosphoric acid and esters thereof, mention may be made
of, in particular, compounds of the formula VII
##STR00007##
where R' and R'' are each, independently of one another, hydrogen
or a C.sub.1-C.sub.10-, preferably C.sub.1-C.sub.4-alkyl group.
[0242] As phosphonic acid and esters thereof, mention may be made
of, in particular, compounds of the formula VIII
##STR00008##
where R' and R'' are each, independently of one another, hydrogen
or a C.sub.1-C.sub.10-, preferably C.sub.1-C.sub.4-alkyl group.
[0243] Preferably, the at least one protic acid e) is not a
hydrohalic acid, especially if the composition is a cosmetic or a
personal care composition. Accordingly, the imidazolium compound
employed in the biocide composition according to the invention does
essentially not comprise anions of a hydrohalic acid (F.sup.-,
Cl.sup.-, Br.sup.- and I.sup.-). In the context of the invention,
an imidazolium compound which does essentially not comprise anions
of a hydrohalic acid denotes an imidazolium compound that comprises
at the most 1 mole %, preferably at the most 0.1 mole %, more
preferably at the most 0.01 mole, in particular at the most 0.001
mole %, based on the total anion content anions of a hydrohalic
acid.
[0244] Preferably, the anions are selected from: [0245] the group
of carboxylates and polybasic carboxylic acids [0246] the group of
sulfates, sulfites and sulfonates, [0247] the group of phosphates,
and [0248] the group of halogenated hydrocarbons.
[0249] In particular, the anions are selected from formate,
acetate, propionate, butyrate, pentanoate, hexanoate, heptanoate,
octanoate, glycolate (hydroxyacetate), adipate, succinate,
phthalate, terephthalate, methoxyacetate,
(C.sub.1-C.sub.4-alcoxy)(CH.sub.2CH.sub.2O).sub.xCH.sub.2COO.sup.-
with x being 1-4, benzoate, hydrogenphosphate, sulfate,
hydrogensulfate and methanesulfonate.
[0250] In case that the composition is a plant protection
composition, especially a fungicidal composition, the anions of the
at least one protic acid e) and/or the anions of the imidazolium
compound can additionally be selected from chloride, bromide and
iodide.
[0251] In a preferred embodiment, the biocide composition according
to the invention comprises an imidazolium compound which consists
essentially of repeat units of the general formula (IV), as defined
in the following. Irrespective of the method of their preparation,
imidazolium compound which consists essentially of repeat units of
the general formula (IV), are particularly advantageous as
biocides. Therefore, in a further aspect the invention provides a
biocide composition, comprising at least one polymeric, ionic
compound comprising imidazolium groups (imidazolium compound),
which consists essentially of repeat units of the general formula
(IV)
##STR00009##
wherein [0252] R.sup.1 and R.sup.2 are independently selected from
hydrogen and in each case unsubstituted or substituted alkyl
(preferably C.sub.1-C.sub.20-alkyl), alkoxy (preferably
C.sub.1-C.sub.20-alkoxy), alkylthio (preferably
C.sub.1-C.sub.20-alkylthio), cycloalkyl (preferably
C.sub.3-C.sub.8-cycloalkyl), cycloalkoxy (preferably
C.sub.3-C.sub.8-cycloalkoxy), cycloalkylthio (preferably
C.sub.3-C.sub.8-cycloalkylthio), aryl, aryloxy, arylthio, [0253]
R.sup.3 is selected from hydrogen, alkyl (preferably
C.sub.1-C.sub.20-alkyl), cycloalkyl (preferably
C.sub.3-C.sub.8-cycloalkyl), optionally substituted aryl and a
group --CH.sub.2 O--CH.sub.2CH.sub.2 .sub.x--OR.sup.a, wherein x is
1, 2, 3, 4, 5 or 6 and R.sup.a is hydrogen or
C.sub.1-C.sub.4-alkyl, [0254] each A is independently has one of
the general or preferred meanings given above and does not contain
1,4-bound phenylene units and is not 2-hydroxy-propane-1,3-diyl or
2-hydroxy-2-methyl-propane-1,3-diyl; and is preferably selected
from a C.sub.1-C.sub.30-alkylene group which may be interrupted by
one or more nonadjacent groups which are selected from --O--, --S--
and --N(R.sup.b)--, where R.sup.b is selected from hydrogen,
C.sub.1-C.sub.20-alkyl and a group CH.sub.2CH.sub.2--O
.sub.y--R.sup.c wherein y is 1, 2, 3, 4, 5 or 6 and R.sup.c is
hydrogen or C.sub.1-C.sub.4-alkyl, preferably O; and is more
preferably selected from a group --(CH.sub.2).sub.m-- wherein m is
an integer of 3 to 20, preferably 4 to 20, more preferably 4 to 12,
where one CH.sub.2 group may be substituted by a carboxyl or
carboxylate group, especially 1,4-butylene, 1,5-pentylene,
1,6-hexylene, 1,8-octylene and 1,12-dodecylene; a group -- B--X
.sub.k--B-- in which each X independently is --O--, --S-- or
--N(R.sup.b)--, where R.sup.b is selected from hydrogen,
C.sub.1-C.sub.20-alkyl and a group CH.sub.2CH.sub.2--O
.sub.y--R.sup.c, wherein y is 1, 2, 3, 4, 5 or 6 and R.sup.c is
hydrogen or C.sub.1-C.sub.4-alkyl, preferably O, each B
independently is C.sub.2-C.sub.6-alkylene, preferably
C.sub.2-C.sub.3-alkylene; and k is an integer from 1 to 100,
preferably 1 to 10 and more preferably 2 to 4, especially
--[CH.sub.2CH.sub.2O].sub.x--CH.sub.2CH.sub.2-- with x being 2 or
3, preferably 2, and
--CH.sub.2CH.sub.2CH.sub.2--[CH.sub.2CH.sub.2O].sub.x--CH.sub.2CH.sub.2CH-
.sub.2-- with x being 2 or 3, preferably 2; and a group of one of
the following formulae
[0254] ##STR00010## [0255] where # is the attachment point to the
imidazolium ring; and [0256] Y.sup.n- is an n-valent anion.
[0257] The polymeric, ionic compound preferably contains at least 8
repeating units IV, e.g. 8 to 500, preferably 8 to 300, more
preferably 8 to 200, even more preferably 8 to 150 and in
particular 10 to 150 repeating units IV.
[0258] In the imidazolium compounds the repeat units of the formula
(IV) may have the same or different meanings. Thus, it is e.g.
possible to employ a mixture of different amino compounds c) for
the preparation of imidazolium compounds to obtain repeat units
with different groups A. It is also possible that the imidazolium
compounds comprise different anions Y.sup.n-.
[0259] In the context of the invention, an imidazolium compound
which consists essentially of repeat units of the general formula
(IV) denotes an imidazolium compound that comprises least 60% by
weight, preferably at least 70% by weight, more preferably at least
80% by weight, in particularly at least 90% by weight, especially
at least 95% by weight, of structural units of the formula IV.
[0260] With regard to suitable and preferred meanings of R.sup.1,
R.sup.2, R.sup.3, A and Y.sup.n- reference is made to the
afore-mentioned definitions of those groups.
[0261] In the structural units of the formula IV preferably R.sup.1
and R.sup.2 are hydrogen.
[0262] In the structural units of the formula IV specifically
R.sup.3 is hydrogen, C.sub.1-C.sub.20-alkyl or phenyl and more
specifically hydrogen.
[0263] In a specific embodiment, in the structural units of the
formula IV preferably A is selected from 1,4-butylene,
1,5-pentylene, 1,6-hexylene, 1,8-octylene, 1,12-dodecylene,
3,6-dioxa-1,8-octylene, 4,7,10-trioxa-1,13-tridecylene, a group
B--X .sub.k--B-- in which each X independently is --O--, --S-- or
--N(R.sup.b)--, where R.sup.b is selected from hydrogen,
C.sub.1-C.sub.20-alkyl and a group CH.sub.2CH.sub.2--O
.sub.y--R.sup.c, wherein y is 1, 2, 3, 4, 5 or 6 and R.sup.c is
hydrogen or C.sub.1-C.sub.4-alkyl; preferably O, each B
independently is C.sub.2-C.sub.6-alkylene, preferably
C.sub.2-C.sub.3-alkylene; and k is an integer from 1 to 100,
preferably 1 to 10 and more preferably 2 to 4; and a group of one
of the following formulae
##STR00011##
and mixtures thereof.
[0264] In a further preferred embodiment, the imidazolium compound
comprises repeat units of the formula (IV), wherein A is derived
from a mixture of amino compounds by formal elimination of the
primary amino groups, comprising at least one amine with two
primary amino groups and at least amine with more than two, in
particular three, primary amino groups.
[0265] In the structural units of the formula IV preferably the
anions Y.sup.n- are selected from formate, acetate, propionate,
butyrate, pentanoate, hexanoate, heptanoate, octanoate, glycolate
(hydroxyacetate), adipate, succinate, phthalate, terephthalate,
(C.sub.1-C.sub.4-alcoxy)(CH.sub.2CH.sub.2O).sub.xCH.sub.2COO.sup.-
with x being 1-4, benzoate, sulfate, hydrogensulfate,
methanesulfonate.
[0266] The polymeric ionic compound comprosing imidazolium groups
preferably has a weight average molecular weight M.sub.w
(determined according to the methods described in the examples) of
from 300 bis 500000, more preferably of from 500 to 300000, even
more preferably of from 1000 to 200000, in particular 2000 to
200000 and specifically 4000 to 200000. The dispersity PDI
(M.sub.w/M.sub.n; M.sub.n=number-average molecular weight) is
preferably in the range from 1.1 to 20, more preferably from 1.5 to
15.
[0267] The biocide composition according to the invention can be
employed against a wide variety of harmful organisms, in particular
microorganisms, especially bacteria, fungi (including inter alia
yeasts, slime molds (myxomycetes) and water molds (oomycetes) and
the spores of the fungi), algae, viruses and mycoplasma. Examples
of gram-positive bacteria are Micrococcaceae, Streptococcaceae,
Bacilli, Lactobacillaceae, Actinomycetales, especially
Mycobacterium, Dermatophilus, Nocardiaceae, Streptomyces and
Corynebacterium. Examples of gram-negative microorganisms are
Spirochaetales (e.g. Spirochaetaceae and Leptospiraceae),
Pseudomonadaceae, Legionellaceae, Neisseriaceae,
Enterobacteriaceae, Vibrionaceae, Pasteurellaceae, Bacteroidaceae,
Veillonellaceae, Rickettsiaceae, Bartonellaceae and Chlamydiaceae,
as well as Brucellaceae.
[0268] Examples of yeasts include the families Cryptococcaceae and
Sporobolomycetaceae, in which are found human pathogenic kinds of
Candida, Trichospores as well as Cryptococcus neoformans. Examples
of these are Candida albicans and Saccharomyces cerevisiae.
[0269] An example of a mold within the family zygomycetes is
Mucorales; examples of the family Hypomycetes are Aspergillus and
Penicillium and an example of the family Bodariales is Neurospora.
The representatives of molds most mentioned are, for example,
Alternaria alternata, Aspergillus niger and Penicillium
funiculosum.
[0270] Examples of algae include Scenedesmus obliquus, Euglena
gracillis, Chlorella pyrenoidosa, Chlamydomonas pulsatilla,
Chlorella salina, Phaeodactylum tricornutum, Chlorella sp,
Pleurococcus sp, Nostoc muscorum, Oscillatoria tenuis, Stichococcus
bacillaris and Trentepohlia aurea.
[0271] Mycoplasma denotes a special genus of bacteria that lack a
cell wall. Examples are M. pneumoniae and M. genitalium.
[0272] In a special embodiment, the biocide composition according
to the invention is employed against Staphylococcus aureus and
Pseudomonas aeruginosa.
[0273] The ionic compounds comprising imidazolium groups
(=imidazolium compounds) are in the following also denoted as
component A).
[0274] The content of the imidazolium compounds in the biocide
compositions of the invention can be varied over wide ranges.
Preferably, the biocide composition comprises the at least one
imidazolium compound in an amount of from 0.01 to 100 wt-%, more
preferably 0.1 to 99.9 wt-%, in particular 0.5 to 95 wt-%, based on
the total weight of the composition. Especially, the biocide
composition comprises the at least one imidazolium compound in an
amount of from 0.01 to 10 wt-%, more especially 0.05 to 5 wt-%, in
particular 0.1 to 1 wt-%, based on the total weight of the
composition.
[0275] In addition to at least one imidazolium compound (component
A), the biocide compositions of the invention may comprise at least
one further microbicidal compound different from the compounds of
component (A) (=component B).
[0276] Suitable further microbicidal compounds (B) are selected
from alcohols, including halogenated alcohols, [0277]
isothiazolones, [0278] activated halogen compounds, [0279]
formaldehyde release compounds, [0280] phenolic compounds, [0281]
aldehydes, [0282] acids and esters, [0283] biphenyls, [0284] urea
derivatives, [0285] O-acetals, O-formals, [0286] N-acetals,
N-formals, [0287] benzamidines, [0288] phthalimides, [0289]
pyridine derivatives, [0290] quaternary ammonium and phosphonium
compounds, [0291] amines, [0292] amphoteric compounds, [0293]
dithiocarbamates, [0294] compounds containing active oxygen such as
peroxide, [0295] inorganic salts such as metal oxides, metal
chlorides, metal sulfates, etc., [0296] organic metal salts, such
as Zn-pyrithion, Ag-lactate, etc., [0297] mixtures thereof.
[0298] Examples of alcohol compounds which may serve as the
microbiocidally effective component (B) are
2-bromo-2-nitropropane-1,3-diol and
2-(hydroxymethyl)-2-nitro-1,3-propanediol. Examples of
isothiazolone compounds are 5-chloro-2-methyl-2H-isothiazol-3-one
(CIT), 2-methyl-2H-isothiazol-3-one (MIT),
1,2-benzisothiazol-3(2H)-one, 2-n-octyl-2H-isothiazol-3-one,
4,5-dichloro-2-octyl-2H-isothiazol-3-one and
2-butyl-benzo-[d]isothiazol-3-one and mixtures thereof with one
another, including a mixture of CIT with MIT or mixtures of CIT or
MIT with any of 1,2-benzoisothiazol-3(2H)-one,
2-octyl-2H-isothiazol-3-one,
4,5-dichloro-2-octyl-2H-isothiazol-3-one and
2-butyl-benzo[d]isothiazol-3-one. Examples of other compounds are
dibromodicyanobutane, [beta]-bromo-[beta]-nitrostyrene,
7a-ethyldihydro-1H,3H,5H-oxazolo[3,4-c]oxazole,
tetrahydro-1,3,4,6-tetrakis(hydroxymethyl)-imidazo[4,5-d]-imidazole-2,5(1-
H,3H)-dione, 1,3-dimethyl-5,5-dimethylhydantoin, diazolidinyl ureas
and imidazolidinyl ureas, N'-(3,4-dichlorophenyl)-N,N-dimethyl
urea, 3,3'-methylenebis(5-methyl-oxazolidine),
2-sodiumsulfidopyridine-N-oxide and its metal salts,
dibromonitritopropionamide, tetrakishydroxymethylphosphonium salts,
ortho-phenylphenol and salts of ortho-phenylphenol,
1-(3-chloroallyl)-3,5,7-triaza-1-azodiadamantane salts,
(5-chloro-2,4-dichlorophenoxy)phenol, 3,4,4'-trichlorocarbanilide
(triclocarban), o-benzo-p-chlorophenol, p-hydroxybenzoates,
2-(thiocyanomethylthio) benzothiazole,
3,5-dimethyl-1,3,5-thiadiazinane-2-thione, 2,4-dichlorobenzyl
alcohol, chlorothalonil, methylenebis(thiocyanate), peracetic acid,
4,4-dimethyl-oxazolidine, phenoxyethanol, phenoxypropanol,
2,6-dimethyl-m-dioxan-4-ol-acetate, glutaraldehyde, glyoxal,
ortho-phthalaldehyde, 4-(2-nitrobutyl)-morpholine, triazines such
as 1,3,5-tris-(2-hydroxyethyl)-1,3,5-hexahydrotriazine, quaternary
ammonium compounds such as benzalkoniumchloride,
polyhexamethylenebiguanide salts,
poly(oxyethylene(dimethylimino)ethylene(dimethylimino)-ethylene
dichloride, chlorhexidine gluconate, chloroisocyanurates,
halogenated hydantoins such as
1-bromo-3-chloro-5,5-dimethylhydantoin and polamines such as
polyvinylamine- and polyethylene imine derivatives. Further
examples include IPBC, terbutryn, ziram, zineb, dichlofluanid,
trichlofuanid, folpet, metal dihexa-2,4-dienoate, tebuconazole,
3-benzo(b)thien-2-yl-5,6-dihydro-1,4,2-oxathiazine, 4-oxide,
pyrithiones, thiram, cybutryne, MBT, carbendazim, diuron,
chlorotoluron, fluorometuron, thiabendazole, metazachlor, CuSCN, or
dicopper oxide.
[0299] Preferred components (B) are
2-bromo-2-nitropropane-1,3-diol, 2-methyl-2H-isothiazol-3-one,
1,2-benzisothiazol-3(2H)-one, 2-n-octyl-2H-isothiazol-3-one, a
mixture of 5-chloro-2-methyl-2H-isothiazol-3-one with
2-methyl-2H-isothiazol-3-one, dibromodicyanobutane,
tetrahydro-1,3,4,6-tetrakis(hydroxymethyl)-imidazo[4,5-d]-imidazole-2,5(1-
H,3H)-dione, 3,3'-methylenebis(5-methyl-oxazolidine),
1,3-dimethyl-5,5-dimethylhydantoin,
tetrakishydroxymethylphosphonium salts, ortho-phenylphenol and
salts of ortho-phenylphenol,
1-(3-chloroallyl)-3,5,7-triaza-1-azodiadamantane salts,
(5-chloro-2,4-dichlorophenoxy)phenol, 3,4,4'-trichlorocarbanilide
(triclocarban), p-hydroxybenzoates, 2-(thiocyanomethylthio)
benzothiazole, 3,5-dimethyl-1,3,5-thiadiazinane-2-thione),
iodo-2-propynylbutylcarbamate, 2-sodiumsulfidopyridine-N-oxide and
its metal salts, 2,4-dichlorobenzyl alcohol, chlorothalonil,
methylenebis(thiocyanate), phenoxyethanol, phenoxypropanol,
triazines such as
1,3,5-tris-(2-hydroxyethyl)-1,3,5-hexahydrotriazine, quaternary
ammonium compounds such as benzalkoniumchloride, polyhexamethylene
biguanide salts, poly(oxyethylene(dimethyimino)ethylene
(dimethylimino)ethylene dichloride, chlorhexidine gluconate,
chloroisocyanurates and polyvinylamines, especially the polyamines
disclosed in WO-A-97/32477.
[0300] If the biocide composition according to the invention
comprises components (A) and (B), the amounts of the components (A)
and (B) in the composition are preferably 1 to 99 wt % of (A) and
99 to 1 wt % of (B), more preferably 10 to 90 wt % of (A) and 90 to
10 wt % of (B), especially 20 to 80 wt % of (A) and 80 to 20 wt %
of (B). Preferably, the biocide composition comprises the sum of
compounds (A) and (B) in an amount of from 0.01 to 100 wt %, more
preferably 0.1 to 99.9 wt %, in particular 0.5 to 95 wt %, based on
the total weight of the composition. Especially, the biocide
composition comprises the sum of compounds (A) and (B) in an amount
of from 0.01 to 10 wt %, more especially 0.05 to 5 wt-%, in
particular 0.1 to 1 wt-%, based on the total weight of the
composition.
[0301] The biocide composition according to the invention,
comprising a component (A), optionally (B) and optionally further
components can be made up into the usual formulations and
preparations that are suitable for the desired purpose. The biocide
composition according to the invention can be provided and/or
applied as a solid or as a liquid. This encompasses compositions in
form of aerosols. The biocide composition according to the
invention can be formulated e.g. as powder, granulate, pellets,
pills, agglomerates, solutions, emulsions, suspensions,
dispersions, pastes, in combination with carrier materials,
etc.
[0302] The biocide compositions according to the invention can be
formulated free from solvent or with a suitable solvent. Generally,
the imidazolium compounds used according to the invention are
soluble in most protic solvents, swellable in most aprotic polar
solvents and insoluble in most nonpolar solvents. Suitable solvents
for the biocide compositions according to the invention are
selected from among water, alcohols, such as methanol, ethanol,
n-propanol, isopropanol, n-butanol, tert-butanol, diols and
polyols, such as ethanediol and propanediol, amino alcohols, such
as ethanolamine, diethanolamine and triethanolamine, ethers, e.g.
tetrahydrofuran, diethyl ether, methyl tert-butyl ether and
diethylene glycol monomethyl ether, ketones, such as acetone and
methyl ethyl ketone, esters, e.g. ethyl acetate, formamide,
dimethylformamide (DMF), dimethylacetamide, dimethyl sulfoxide
(DMSO), acetonitrile, aromatic solvents, e.g. benzene, toluene,
ethylbenzene or xylenes, halogenated solvents, e.g.
dichloromethane, chloroform, carbon tetrachloride, dichloroethane
or chlorobenzene, aliphatic solvents, e.g. pentane, hexane,
heptane, octane, ligroin, petroleum ether, cyclohexane and decalin,
and mixtures thereof.
[0303] The solvent is preferably selected from among water,
water-miscible organic solvents and mixtures thereof. The solvent
is particularly preferably selected from among water, methanol,
ethanol, n-propanol, isopropanol, n-butanol, tert-butanol and
mixtures thereof.
[0304] A multitude of different active substances and additives can
be formulated in the biocide compositions according to the
invention.
Fungicidal Composition
[0305] In another aspect, the invention relates to a fungicidal
compositionat least one polymeric, ionic compound comprising
imidazolium groups (imidazolium compound), obtainable by
reacting
a) at least one .alpha.-dicarbonyl compound, b) at least one
aldehyde, c) at least one amino compound having at least two
primary amino groups, d) optionally an amino compound having only
one primary amino group and e) at least one protic acid, and
optionally subjecting the reaction product to an anion exchange,
where in the components a) and b) the aldehyde carbonyl groups may
also be present as hemiacetal or acetal and the ketone carbonyl
groups may also be present as hemiketal or ketal.
[0306] Preferably, the amino compound having at least two primary
amino groups is not 1,3-diamino-2-hydroxy-propane or
1,3-diamino-2-hydroxy-2-methyl-propane; and/or the polymer
comprises at least 8, preferably at least 10 imidazolium rings;
and/or the main chain of the at least one compound comprising
imidazolium groups does not contain 1,4-bound phenylene rings
and/or the main chain of the at least one imidazolium compound
apart from the nitrogen atoms of the imidazolium groups does not
contain any quaternary nitrogen atoms that bear 4 residues that are
different from hydrogen.
[0307] In one preferred embodiment, the amino compound having at
least two primary amino groups is not 1,3-diamino-2-hydroxy-propane
or 1,3-diamino-2-hydroxy-2-methyl-propane.
[0308] In another embodiment, the polymer comprises at least 8,
preferably at least 10 imidazolium rings.
[0309] In another embodiment, the main chain of the at least one
compound comprising imidazolium groups does not contain 1,4-bound
phenylene rings
[0310] In another embodiment, the main chain of the at least one
imidazolium compound apart from the nitrogen atoms of the
imidazolium groups does not contain any quaternary nitrogen atoms
that bear 4 residues that are different from hydrogen.
[0311] In one preferred embodiment, the amino compound having at
least two primary amino groups is not 1,3-diamino-2-hydroxy-propane
or 1,3-diamino-2-hydroxy-2-methyl-propane and the polymer comprises
at least 8, preferably at least 10 imidazolium rings.
[0312] In particular, the polymer has one of the general or
preferred meanings given above in context with the biocidal
composition, and the fungicidal composition has one of the general
or preferred meanings given above for the biocidal composition;
i.e. the above-described biocidal composition is preferably a
fungicidal composition.
[0313] In a particular embodiment, the composition contains at
least one further agrochemically active compound V, e.g. at least
one herbicide, insecticide, growth regulator, fungicide (different
of course from the imidazolium compound) or fertilizer.
[0314] The fungicidal composition containing the polymeric, ionic
compound containing imidazolium rings and at least one further
agrochemically active compound V may be a physical mixture of these
components. Accordingly, the invention also provides a mixture
comprising these components. However, the composition may also be
any combination of these components, it not being required for the
polymeric, ionic compound and compound V to be present together in
the same formulation.
[0315] An example of a composition according to the invention or to
be used according to the invention in which the at least one
polymeric, ionic compound and the at least one compound V are not
present together in the same formulation is a combipack. In a
combipack, two or more components of a combipack are packaged
separately, i.e., not jointly pre-formulated. As such, combipacks
include one or more separate containers such as vials, cans,
bottles, pouches, bags or canisters, each container containing a
separate component for an agrochemical composition. One example is
a two-component combipack. Accordingly the present invention also
relates to a two-component combipack, comprising a first component
which in turn comprises at least one compound polymeric, ionic
compound, a liquid or solid carrier and, if appropriate, at least
one surfactant and/or at least one customary auxiliary, and a
second component which in turn comprises at least one compound V, a
liquid or solid carrier and, if appropriate, at least one
surfactant and/or at least one customary auxiliary. More details,
e.g. as to suitable liquid and solid carriers, surfactants and
customary auxiliaries are described below.
[0316] Practical agricultural experience has shown that the
repeated and exclusive application of an individual active compound
in the control of harmful fungi leads in many cases to a rapid
selection of those fungus strains which have developed natural or
adapted resistance against the active compound in question.
Effective control of these fungi with the active compound in
question is then no longer possible. To reduce the risk of the
selection of resistant fungus strains, mixtures of different active
compounds are nowadays conventionally employed for controlling
harmful fungi. By combining active compounds having different
mechanisms of action, it is possible to ensure successful control
over a relatively long period of time.
[0317] Using the polymeric, ionic compound comprising imidazolium
groups in combination with at least one agrochemically active
compound V results in many cases in an expansion of the fungicidal
spectrum of activity being obtained or in a prevention of fungicide
resistance development. Furthermore, in many cases, synergistic
effects are obtained.
[0318] The following list of active compounds V, in conjunction
with which the polymeric, ionic compounds according to the
invention comprising imidazolium groups can be used, is intended to
illustrate the possible combinations but does not limit them:
[0319] A) Respiration Inhibitors [0320] Inhibitors of complex III
at Q.sub.o site (e.g. strobilurins): azoxystrobin, coumethoxy
strobin, coumoxystrobin, dimoxystrobin, enestroburin,
fenaminstrobin, fenoxy strobin/flufenoxystrobin, fluoxastro bin,
kresoxim-methyl, meto minostrobin, orysastrobin, picoxy strobin,
pyraclostrobin, pyrametostrobin, pyraoxystrobin, trifloxystrobin,
2-[2-(2,5-dimethyl-phenoxymethyl)-phenyl]-3-methoxy-acrylic acid
methyl ester and 2 (2-(3-(2,6-di chlorophenyl)-1-methyl-allylidene
aminooxy methyl)-phenyl)-2-methoxyimino-N methyl-acetamide,
pyribencarb, triclopyricarb/chlorodin carb, famoxadone, fenamidone;
[0321] inhibitors of complex III at Q.sub.i site: cyazofamid,
amisulbrom, [(3S,6S,7R,8R)-8-benz yl-3-[(3-acetoxy-4
methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1,5-di
oxonan-7-yl]2 methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acet
oxymeth oxy)-4-methoxy-pyridine-2
carbonyl]amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl] 2
methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobut
oxycarbonyloxy-4-meth oxy-pyri dine-2
carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl] 2-methylpro
panoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(1,3-ben
zodioxol-5-ylmethoxy)-4-methoxy-pyri dine-2-car
bonyl]amino]-6-methyl-4,9-di oxo-1,5-dioxonan-7-yl]2-methyl
propanoate;
(3S,6S,7R,8R)-3-[[(3-hydroxy-4-methoxy-2-pyridinyl)carbonyl]amino]-6
methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxonan-7-yl
2-methylpropanoate [0322] inhibitors of complex II (e.g.
carboxamides): benodanil, bixafen, boscalid, carboxin, fen furam,
fluopyram, flutolanil, fluxapyroxad, furametpyr, isopyrazam,
mepronil, oxycarboxin, penflufen, penthiopyrad, sedaxane,
tecloftalam, thifluz amide,
N-(4'-trifluoromethylthiobiphenyl-2-yl)-3
difluoromethyl-1-methyl-1H pyr azole-4-carboxamide,
N-(2-(1,3,3-trimethyl-butyl)-phenyl)-1,3-dimethyl-5
fluoro-1H-pyrazole-4 carboxamide,
N-[9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-me
thanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxami-
de, 3
(difluoromethyl)-1-methyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-ca-
rboxamide, 3
(trifluoromethyl)-1-methyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carbox-
amide,
1,3-dimethyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide,
3-(trifluorometh
yl)-1,5-dimethyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide,
3-(difluoro
methyl)-1,5-dimethyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide,
1,3,5-tri
methyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide; [0323]
other respiration inhibitors (e.g. complex I, uncouplers):
diflumetorim, (5,8-difluoro
quinazolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl-
]-ethyl}-amine; nitrophenyl derivates: binapacryl, dinobuton,
dinocap, fluazinam; ferimzone; organometal compounds: fentin salts,
such as fentin-acetate, fentin chloride or fentin hydroxide;
ametoctradin; and silthiofam; [0324] B) Sterol Biosynthesis
Inhibitors (SBI Fungicides) [0325] C14 demethylase inhibitors (DMI
fungicides): triazoles: azaconazole, bitertanol, bromuconazole,
cyproconazole, difenoconazole, diniconazole, diniconazole-M,
epoxiconazole, fenbuconazole, fluquinconazole, flusilazole,
flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole,
myclobutanil, oxpoconazole, paclobutrazole, penconazole,
propiconazole, prothio conazole, simeconazole, tebuconazole,
tetraconazole, triadimefon, triadimenol, triticonazole,
uniconazole, 1-[rel-(2S;3R)-3-(2-chloro
phenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5 thio
cyanato-1H-[1,2,4]triazole,
2-[rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranyl
methyl]-2H [1,2,4]triazole-3-thiol; imidazoles: imazalil,
pefurazoate, prochloraz, triflumizol; pyrimidines, pyridines and
piperazines: fenarimol, nuarimol, pyrifenox, triforine; [0326]
Delta14-reductase inhibitors: aldimorph, dodemorph,
dodemorph-acetate, fenpropimorph, tridemorph, fenpropidin,
piperalin, spiroxamine; [0327] Inhibitors of 3-keto reductase:
fenhexamid; [0328] C) Nucleic Acid Synthesis Inhibitors [0329]
phenylamides or acyl amino acid fungicides: benalaxyl, benalaxyl-M,
kiralaxyl, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl;
[0330] others: hymexazole, octhilinone, oxolinic acid, bupirimate,
5-fluorocytosine, 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine,
5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4 amine; [0331] D)
Inhibitors of Cell Division and Cytoskeleton [0332] tubulin
inhibitors, such as benzimidazoles, thiophanates: benomyl,
carbendazim, fuberidazole, thiabendazole, thiophanate-methyl;
triazolopyrimidines: 5-chloro-7 (4 methyl
piperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]tri azolo[1,5
a]pyrimidine [0333] other cell division inhibitors: diethofencarb,
ethaboxam, pencycuron, fluopicolide, zoxamide, metrafenone,
pyriofenone; [0334] E) Inhibitors of Amino Acid and Protein
Synthesis [0335] methionine synthesis inhibitors
(anilino-pyrimidines): cyprodinil, mepanipyrim, pyrimethanil;
[0336] protein synthesis inhibitors: blasticidin-S, kasugamycin,
kasugamycin hydrochloride-hydrate, mildiomycin, streptomycin,
oxytetracyclin, polyoxine, validamycin A; [0337] F) Signal
Transduction Inhibitors [0338] MAP/histidine kinase inhibitors:
fluoroimid, iprodione, procymidone, vinclozolin, fenpiclonil,
fludioxonil; [0339] G protein inhibitors: quinoxyfen; [0340] G)
Lipid and Membrane Synthesis Inhibitors [0341] Phospholipid
biosynthesis inhibitors: edifenphos, iprobenfos, pyrazophos,
isoprothiolane; [0342] lipid peroxidation: dicloran, quintozene,
tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole;
[0343] phospholipid biosynthesis and cell wall deposition:
dimethomorph, flumorph, mandipropamid, pyrimorph, benthiavalicarb,
iprovalicarb, valifenalate and N-(1-(1-(4-cyano-phenyl)
ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester;
[0344] compounds affecting cell membrane permeability and fatty
acides: propamocarb, propamo carb-hydrochlorid [0345] fatty acid
amide hydrolase inhibitors:
1-[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3
isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1-
H-pyrazol-1 yl]ethanone [0346] H) Inhibitors with Multi Site Action
[0347] inorganic active substances: Bordeaux mixture, copper
acetate, copper hydroxide, copper oxychloride, basic copper
sulfate, sulfur; [0348] thio- and dithiocarbamates: ferbam,
mancozeb, maneb, metam, metiram, propineb, thiram, zineb, ziram;
[0349] organochlorine compounds (e.g. phthalimides, sulfamides,
chloronitriles): anilazine, chlorothalonil, captafol, captan,
folpet, dichlofluanid, dichlorophen, flusulfamide,
hexachlorobenzene, pentachlorphenole and its salts, phthalide,
tolylfluanid,
N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl-benzenesulfonamide;
[0350] guanidines and others: guanidine, dodine, dodine free base,
guazatine, guazatine-acetate, iminoctadine,
iminoctadine-triacetate, iminoctadine-tris(albesilate), dithianon,
2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-te-
traone; [0351] I) Cell Wall Synthesis Inhibitors [0352] inhibitors
of glucan synthesis: validamycin, polyoxin B; melanin synthesis
inhibitors: pyroquilon, tricyclazole, carpropamid, dicyclomet,
fenoxanil; [0353] J) Plant Defence Inducers [0354]
acibenzolar-S-methyl, probenazole, isotianil, tiadinil,
prohexadione-calcium; phosphonates: fosetyl, fosetyl-aluminum,
phosphorous acid and its salts; [0355] K) Unknown Mode of Action
[0356] bronopol, chinomethionat, cyflufenamid, cymoxanil, dazomet,
debacarb, diclo mezine, difenzoquat, difenzoquat-methylsulfate,
diphenylamin, fenpyrazamine, flumetover, flusulfamide, flutianil,
methasulfocarb, nitrapyrin, nitrothal-isopropyl, oxin-copper,
proquinazid, tebufloquin, tecloftalam, triazoxide,
2-butoxy-6-iodo-3 propylchromen-4-one, N-(cyclo
propylmethoxyimino-(6-difluoro-methoxy-2,3 di
fluoro-phenyl)-methyl)-2-phenyl acetamide,
N'-(4-(4-chloro-3-trifluoromethyl-phen
oxy)-2,5-dimethyl-phenyl)-N-ethyl-N methyl formamidine,
N'(4-(4-fluoro-3-trifluoro
methyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine,
N'-(2-methyl-5-trifluoromethyl-4-(3-trimethyl silanyl-prop
oxy)-phenyl)-N-ethyl-N-methyl forma midine, N'-(5-difluoromethyl-2
methyl-4-(3-tri methylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl
formamidine,
2-{1-[2-(5-methyl-3-trifluoromethyl-pyrazole-1-yl)-acetyl]-piperidin-4-yl-
}-thiazole-4 carboxylic acid
methyl-(1,2,3,4-tetrahydro-naphthalen-1 yl)-amide, 2-{1-[2-(5-meth
yl-3-trifluoromethyl-pyrazole-1-yl)-acetyl]-piperidin-4-yl}-thiazole-4-ca-
rboxylic acid methyl-(R)-1,2,3,4-tetrahydro-naphthalen-1-yl-amide,
[0357]
1-[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1--
piperidinyl]- [0358]
2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone,
methoxy-acetic acid [0359]
6-tert-butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester,
N-Methyl-2-{1-[(5-methyl-3-tri fluoro methyl-1H-pyr
azol-1-yl)-acetyl]-piperi din-4-yl}-N-[(1R)-1,2,3,4-tetrahydro
naphthalen-1-yl]-4-thi azolecarboxamide,
3-[5-(4-methylphenyl)-2,3-dimethyl-isoxazolidin-3 yl]-pyridine,
3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine
(pyrisoxazole), N-(6-methoxy-pyridin-3-yl) cyclopropane carboxylic
acid amide, 5-chloro-1
(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1H-ben zoimidazole, [0360]
2-(4-chloro-phenyl)-N-[4-(3,4-dimeth
oxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide; [0361] L)
Antifungal biocontrol agents, plant bioactivators: Ampelomyces
quisqualis (e.g. AQ 10.RTM. from Intrachem Bio GmbH & Co. KG,
Germany), Aspergillus flavus (e.g. AFLAGUARD.RTM. from Syngenta,
CH), Aureobasidium pullulans (e.g. BOTECTOR.RTM. from bio-ferm
GmbH, Germany), Bacillus pumilus (e.g. NRRL Accession No. B 30087
in SONATA.RTM. and BALLAD.RTM. Plus from AgraQuest Inc., USA),
Bacillus subtilis (e.g. isolate NRRL-Nr. B-21661 in RHAPSODY.RTM.,
SERENADE.RTM. MAX and SERENADE.RTM. ASO from AgraQuest Inc., USA),
Bacillus subtilis var. amylolique faciens FZB24 (e.g. TAEGRO.RTM.
from Novozyme Biologicals, Inc., USA), Candida oleophila 1-82 (e.g.
ASPIRE.RTM. from Ecogen Inc., USA), Candida saitoana (e.g.
BIOCURE.RTM. (in mixture with lysozyme) and BIOCOAT.RTM. from Micro
Flo Company, USA (BASF SE) and Arysta), Chitosan (e.g. ARMOUR-ZEN
from BotriZen Ltd., NZ), Clonostachys rosea f. catenulata, also
named Gliocladium catenulatum (e.g. isolate J1446: PRESTOP.RTM.
from Verdera, Finland), Coniothyrium minitans (e.g. CONTANS.RTM.
from Prophyta, Germany), Cryphonectria parasitica (e.g. Endothia
parasitica from CNICM, France), Cryptococcus albidus (e.g. YIELD
PLUS.RTM. from Anchor Bio-Technologies, South Africa), Fusarium
oxysporum (e.g. BIOFOX.RTM. from S.I.A.P.A., Italy, FUSACLEAN.RTM.
from Natural Plant Protection, France), Metschnikowia fructicola
(e.g. SHEMER.RTM. from Agrogreen, Israel), Microdochium dimerum
(e.g. ANTIBOT.RTM. from Agrauxine, France), Phlebiopsis gigantea
(e.g. ROTSOP.RTM. from Verdera, Finland), Pseudozyma flocculosa
(e.g. SPORODEX.RTM. from Plant Products Co. Ltd., Canada), Pythium
oligandrum DV74 (e.g. POLYVERSUM.RTM. from Remeslo SSRO,
Biopreparaty, Czech Rep.), Reynoutria sachlinensis (e.g.
REGALIA.RTM. from Marrone Biolnnovations, USA), Talaromyces flavus
V117b (e.g. PROTUS.RTM. from Prophyta, Germany), Trichoderma
asperellum SKT-1 (e.g. ECO-HOPE.RTM. from Kumiai Chemical Industry
Co., Ltd., Japan), T. atroviride LC52 (e.g. SENTINEL.RTM. from
Agrimm Technologies Ltd, NZ), T. harzianum T-22 (e.g.
PLANTSHIELD.RTM. der Firma BioWorks Inc., USA), T. harzianum TH 35
(e.g. ROOT PRO.RTM. from Mycontrol Ltd., Israel), T. harzianum T-39
(e.g. TRICHODEX.RTM. and TRICHODERMA 20000 from Mycontrol Ltd.,
Israel and Makhteshim Ltd., Israel), T. harzianum and T. viride
(e.g. TRICHOPEL from Agrimm Technologies Ltd, NZ), T. harzianum
ICC012 and T. viride ICC080 (e.g. REMEDIER.RTM. WP from Isagro
Ricerca, Italy), T. polysporum and T. harzianum (e.g. BINAB.RTM.
from BINAB Bio-Innovation AB, Sweden), T. stromaticum (e.g.
TRICOVAB.RTM. from C.E.P.L.A.C., Brazil), T. virens GL-21 (e.g.
SOILGARD.RTM. from Certis LLC, USA), T. viride (e.g. TRIECO.RTM.
from Ecosense Labs. (India) Pvt. Ltd., Indien, BIO-CURE.RTM. F from
T. Stanes & Co. Ltd., Indien), T. viride TV1 (e.g. T. viride
TV1 from Agribiotec srl, Italy), Ulocladium oudemansii HRU3 (e.g.
BOTRY-ZEN.RTM. from Botry-Zen Ltd, NZ); [0362] M) Growth Regulators
[0363] abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine,
brassinolide, butralin, chlormequat (chlormequat chloride), choline
chloride, cyclanilide, daminozide, dike gulac, dimethipin,
2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthi
acet, forchlorfenuron, gibberellic acid, inabenfide,
indole-3-acetic acid, maleic hydrazide, mefluidide, mepiquat
(mepiquat chloride), naphthaleneacetic acid, N 6 benzyladenine,
paclobutrazol, prohexadione (prohexadione-calcium), prohydrojasmon,
thidiazuron, triapenthenol, tributyl phosphorotrithioate, 2,3,5 tri
iodobenzoic acid, trinexapac-ethyl and uniconazole; [0364] N)
Herbicides [0365] acetamides: acetochlor, alachlor, butachlor,
dimethachlor, dimethenamid, flufenacet, mefenacet, metolachlor,
metazachlor, napropamide, naproanilide, pethoxamid, pretilachlor,
propachlor, thenylchlor; [0366] amino acid derivatives: bilanafos,
glyphosate, glufosinate, sulfosate; [0367]
aryloxyphenoxypropionates: clodinafop, cyhalofop-butyl, fenoxaprop,
fluazifop, haloxyfop, metamifop, propaquizafop, quizalofop,
quizalofop-P-tefuryl; [0368] Bipyridyls: diquat, paraquat; [0369]
(thio)carbamates: asulam, butylate, carbetamide, desmedipham,
dimepiperate, eptam (EPTC), esprocarb, molinate, orbencarb,
phenmedipham, prosulfocarb, pyributicarb, thiobencarb, triallate;
[0370] cyclohexanediones: butroxydim, clethodim, cycloxydim,
profoxydim, sethoxydim, tepraloxydim, tralkoxydim; [0371]
dinitroanilines: benfluralin, ethalfluralin, oryzalin,
pendimethalin, prodiamine, trifluralin; [0372] diphenyl ethers:
acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fomesafen,
lactofen, oxyfluorfen; [0373] hydroxybenzonitriles: bomoxynil,
dichlobenil, ioxynil; [0374] imidazolinones: imazamethabenz,
imazamox, imazapic, imazapyr, imazaquin, imazethapyr; [0375]
phenoxy acetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid
(2,4-D), 2,4-DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB, Mecoprop;
[0376] pyrazines: chloridazon, flufenpyr-ethyl, fluthiacet,
norflurazon, pyridate; [0377] pyridines: aminopyralid, clopyralid,
diflufenican, dithiopyr, fluridone, fluroxypyr, picloram,
picolinafen, thiazopyr; [0378] sulfonyl ureas: amidosulfuron,
azimsulfuron, bensulfuron, chlorimuron-ethyl, chlorsulfuron,
cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron,
flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron,
imazosulfuron, iodosulfuron, mesosulfuron, metazosulfuron,
metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron,
prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron,
sulfosulfuron, thifensulfuron, triasulfuron, tribenuron,
trifloxysulfuron, triflusulfuron, tritosulfuron, 1
((2-chloro-6-propyl-imidazo[1,2-b]pyridazin-3-yl)sulfonyl)-3-(4,6-dimetho-
xy-pyrimidin-2-yl)urea;
[0379] triazines: ametryn, atrazine, cyanazine, dimethametryn,
ethiozin, hexazinone, metamitron, metribuzin, prometryn, simazine,
terbuthylazine, terbutryn, triaziflam; [0380] ureas: chlorotoluron,
daimuron, diuron, fluometuron, isoproturon, linuron, metha
benzthiazuron, tebuthiuron; [0381] other acetolactate synthase
inhibitors: bispyribac-sodium, cloransulam-methyl, diclosulam,
florasulam, flucarbazone, flumetsulam, metosulam, ortho-sulfamuron,
penoxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim,
pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac,
pyroxasulfone, pyroxsulam; [0382] others: amicarbazone,
aminotriazole, anilofos, beflubutamid, benazolin, bencarbazone,
benfluresate, benzofenap, bentazone, benzobicyclon, bicyclopyrone,
bromacil, bromobutide, butafenacil, butamifos, cafenstrole,
carfentrazone, cinidon-ethyl, chlorthal, cinmethylin, clomazone,
cumyluron, cyprosulfamide, dicamba, difenzoquat, diflufenzopyr,
Drechslera monoceras, endothal, ethofumesate, etobenzanid,
fenoxasulfone, fentrazamide, flumiclorac-pentyl, flumioxazin,
flupoxam, flurochloridone, flurtamone, indanofan, isoxaben,
isoxaflutole, lenacil, propanil, propyzamide, quinclorac,
quinmerac, mesotrione, methyl arsonic acid, naptalam, oxadiargyl,
oxadiazon, oxaziclomefone, pentoxazone, pinoxaden, pyraclonil,
pyraflufen-ethyl, pyrasulfotole, pyrazoxyfen, pyrazolynate,
quinoclamine, saflufenacil, sulcotrione, sulfentrazone, terbacil,
tefuryltrione, tembotrione, thiencarbazone, topramezone,
(3-[2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydro-
-2H-pyrimidin-1-yl)-phenoxy]-pyridin-2-yloxy)-acetic acid ethyl
ester, 6-amino-5-chloro-2-cyclopropyl-pyrimidine-4-carboxylic acid
methyl ester,
6-chloro-3-(2-cyclopropyl-6-methyl-phenoxy)-pyridazin-4-ol,
4-amino-3-chloro-6-(4-chloro-phenyl)-5-fluoro-pyridine-2-carboxylic
acid,
4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxy-phenyl)-pyridine-2-carbox-
ylic acid methyl ester, and
4-amino-3-chloro-6-(4-chloro-3-dimethylamino-2-fluoro-phenyl)-pyridine-2--
carboxylic acid methyl ester. [0383] O) Insecticides [0384]
organo(thio)phosphates: acephate, azamethiphos, azinphos-methyl,
chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon,
dichlorvos, dicrotophos, dimethoate, disulfoton, ethion,
fenitrothion, fenthion, isoxathion, malathion, methamidophos,
methidathion, methyl-parathion, mevinphos, monocrotophos,
oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone,
phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl,
profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos,
triazophos, trichlorfon; [0385] carbamates: alanycarb, aldicarb,
bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan,
fenoxycarb, furathiocarb, methiocarb, methomyl, oxamyl, pirimicarb,
propoxur, thiodicarb, triazamate; [0386] pyrethroids: allethrin,
bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin,
alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin,
deltamethrin, esfen valerate, etofenprox, fenpropathrin,
fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin,
prallethrin, pyrethrin I and II, resmethrin, silafluofen,
tau-fluvalinate, tefluthrin, tetramethrin, tralomethrin,
transfluthrin, profluthrin, dimefluthrin; [0387] insect growth
regulators: a) chitin synthesis inhibitors: benzoylureas:
chlorfluazuron, cyramazin, diflubenzuron, flucycloxuron,
flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron,
triflumuron; buprofezin, diofenolan, hexythiazox, etox azole,
clofentazine; b) ecdysone antagonists: halofenozide,
methoxyfenozide, tebufenozide, azadirachtin; c) juvenoids:
pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis
inhibitors: spirodiclofen, spiromesifen, spirotetramat; [0388]
nicotinic receptor agonists/antagonists compounds: clothianidin,
dinotefuran, flupyradifurone, imidacloprid, thiamethoxam,
nitenpyram, acetamiprid, thiacloprid, 1
2-chloro-thiazol-5-ylmethyl)-2-nitrimino-3,5-dimethyl-[1,3,5]triazinane;
[0389] GABA antagonist compounds: endosulfan, ethiprole, fipronil,
vaniliprole, pyrafluprole, pyriprole,
5-amino-1-(2,6-dichloro-4-methyl-phenyl)-4-sulfinamoyl-1H
pyrazole-3-carbothioic acid amide; [0390] macrocyclic lactone
insecticides: abamectin, emamectin, milbemectin, lepimectin,
spinosad, spinetoram; [0391] mitochondrial electron transport
inhibitor (METI) I acaricides: fenazaquin, pyridaben, tebufenpyrad,
tolfenpyrad, flufenerim; [0392] METI II and III compounds:
acequinocyl, fluacyprim, hydramethylnon; [0393] Uncouplers:
chlorfenapyr; [0394] oxidative phosphorylation inhibitors:
cyhexatin, diafenthiuron, fenbutatin oxide, propargite; [0395]
moulting disruptor compounds: cryomazine; [0396] mixed function
oxidase inhibitors: piperonyl butoxide; [0397] sodium channel
blockers: indoxacarb, metaflumizone; [0398] others: benclothiaz,
bifenazate, cartap, flonicamid, pyridalyl, pymetrozine, sulfur,
thiocyclam, flubendiamide, chlorantraniliprole, cyazypyr (HGW86),
cyenopyrafen, flupyrazofos, cyflumetofen, amidoflumet, imicyafos,
bistrifluron, and pyrifluquinazon.
[0399] The compounds V, their preparation and their biological
activity e.g. against harmful fungi, pests or weed is known (cf.:
http://www.alanwood.net/pesticides/); these substances are
commercially available and known, for example, from the references
below:
benalaxyl, methyl N-(phenylacetyl)-N-(2,6-xylyl)-DL-alaninate (DE
29 03 612); metalaxyl, methyl
N-(methoxyacetyl)-N-(2,6-xylyl)-DL-alaninate (GB 15 00 581);
ofurace,
(RS)-.alpha.-(2-chloro-N-2,6-xylylacetamido)-.gamma.-butyrolactone
[CAS RN 58810-48-3]; oxadixyl;
N-(2,6-dimethylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)acetamide
(GB 20 58 059); aldimorph, "4-alkyl-2,5(or
2,6)-dimethylmorpholine", comprising 65-75% of
2,6-dimethylmorpholine and 25-35% of 2,5-dimethylmorpholine,
comprising more than 85% of 4-dodecyl-2,5(or
2,6)-dimethylmorpholine, where "alkyl" also includes octyl, decyl,
tetradecyl and hexadecyl, with a cis/trans ratio of 1:1 [CAS RN
91315-15-0]; dodine, 1-dodecylguanidinium acetate (Plant Dis. Rep.,
Vol. 41, p. 1029 (1957)); dodemorph,
4-cyclododecyl-2,6-dimethylmorpholine (DE 1198125); fenpropimorph,
(RS)-cis-4-[3-(4-tert-butylphenyl)-2-methylpropyl]-2,6-dimethylmorpholine
(DE 27 52 096); fenpropidin,
(RS)-1-[3-(4-tert-butylphenyl)-2-methylpropyl]piperidine (DE 27 52
096); guazatine, mixture of the reaction products from the
amidation of technical grade iminodi(octa-methylene)diamine,
comprising various guanidines and polyamines [CAS RN 108173-90-6];
iminoctadine, 1,1'-iminodi(octamethylene)diguanidine (Congr. Plant
Pathol. 1, p. 27 (1968); spiroxamine,
(8-tert-butyl-1,4-dioxaspiro[4.5]dec-2-yl)diethylamine (EP-A 281
842); tridemorph, 2,6-dimethyl-4-tridecylmorpholine (DE 11 64 152);
pyrimethanil, 4,6-dimethylpyrimidin-2-ylphenylamine (DD-A 151 404);
mepanipyrim, (4-methyl-6-prop-1-ynylpyrimidin-2-yl)phenylamine
(EP-A 224 339); cyprodinil,
(4-cyclopropyl-6-methylpyrimidin-2-yl)phenylamine (EP-A 310 550);
cycloheximid,
4-{(2R)-2-[(1S,3S,5S)-3,5-dimethyl-2-oxocyclohexyl]-2-hydroxyethyl}piperi-
dine-2,6-dione [CAS RN 66-81-9]; griseofulvin,
7-chloro-2',4,6-trimethoxy-6'-methylspiro[benzo-furan-2(3H),1'-cyclohex-2-
'-ene]-3,4'-dione [CAS RN 126-07-8]; kasugamycin,
3-O-[2-amino-4-[(carboxyiminomethyl)amino]-2,3,4,6-tetradeoxy-.alpha.-D-a-
rabino-hexopyranosyl]-D-chiro-inositol [CAS RN 6980-18-3];
natamycin,
(8E,14E,16E,18E,20E)-(1R,3S,5R,7R,12R,22R,24S,25R,26S)-22-(3-amino-3,6-di-
deoxy-.beta.-D-mannopyranosyloxy)-1,3,26-trihydroxy-12-methyl-10-oxo-6,11,-
28-trioxatricyclo[22.3.1.05,7]octacosa-8,14,16,18,20-pentaene-25-carboxyli-
c acid [CAS RN 7681-93-8]; polyoxin,
5-(2-amino-5-O-carbamoyl-2-deoxy-L-xylonamido)-1-(5-carboxy-1,2,3,4-tetra-
hydro-2,4-dioxopyrimidin-1-yl)-1,5-dideoxy-.beta.-D-allofuranuronic
acid [CAS RN 22976-86-9]; streptomycin,
1,1'-{1-L-(1,3,5/2,4,6)-4-[5-deoxy-2-O-(2-deoxy-2-methylamino-.alpha.-L-g-
lucopyranosyl)-3-C-formyl-.alpha.-L-lyxofuranosyloxy]-2,5,6-trihydroxycycl-
ohex-1,3-ylene}diguanidine (J. Am. Chem. Soc. 69, p. 1234 (1947));
bitertanol,
.beta.-([1,1'-biphenyl]-4-yloxy)-.alpha.-(1,1-dimethylethyl)-1H-1,2,4-tri-
azole-1-ethanol (DE 23 24 020); bromuconazole,
1-[[4-bromo-2-(2,4-dichlorophenyl)tetrahydro-2-furanyl]methyl]-1H-1,2,4-t-
riazole (Proc. Br. Crop. Prot. Conf. 1990--Pests Dis. Vol. 1, p.
459); cyproconazole,
2-(4-chlorophenyl)-3-cyclopropyl-1-[1,2,4]triazol-1-ylbutan-2-ol
(U.S. Pat. No. 4,664,696); difenoconazole,
1-{2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-[1,3]dioxolan-2-ylmeth-
yl}-1H-[1,2,4]triazole (GB-A 2 098 607); diniconazole,
(.beta.E)-.beta.-[(2,4-dichlorophenyl)methylene]-.alpha.-(1,1-dimethyleth-
yl)-1H-1,2,4-triazole-1-ethanol (Noyaku Kagaku, 1983, Vol. 8, p.
575); enilconazole (imazalil),
1-[2-(2,4-dichlorphenyl)-2-(2-propenyloxy)ethyl]-1H-imidazole
(Fruits 28, p. 545, 1973); epoxiconazole,
(2RS,3SR)-1-[3-(2-chlorophenyl)-2,3-epoxy-2-(4-fluorophenyl)propyl]-1H-1,-
2,4-triazole (EP-A 196 038); fenbuconazole,
.alpha.-[2-(4-chloro-phenyl)ethyl]-.alpha.-phenyl-1H-1,2,4-triazole-1-pro-
panenitrile (Proc. Br. Crop Prot. Conf. 1988--Pests Dis. Vol. 1, p.
33); fluquinconazole,
3-(2,4-dichlorophenyl)-6-fluoro-2-[1,2,4]-triazol-1-yl-3H-quinazolin-4-on-
e (Proc. Br. Crop Prot. Conf.-Pests Dis., 5-3, 411 (1992));
flusilazole,
1-{[bis-(4-fluorophenyl)methylsilanyl]methyl}-1H-[1,2,4]triazole
(Proc. Br. Crop Prot. Conf.-Pests Dis., 1, 413 (1984)); flutriafol,
.alpha.-(2-fluorophenyl)-.alpha.-(4-fluorophenyl)-1H-1,2,4-triazole-1-eth-
anol (EP 15 756); hexaconazole,
2-(2,4-dichlorophenyl)-1-[1,2,4]triazol-1-ylhexan-2-ol (CAS RN
79983-71-4); ipconazole,
2-[(4-chlorophenyl)methyl]-5-(1-methylethyl)-1-(1H-1,2,4-triazol-1-ylmeth-
yl)cyclopentanol (EP 267 778), metconazole,
5-(4-chlorobenzyl)-2,2-dimethyl-1-[1,2,4]triazol-1-ylmethyl-cyclopentanol
(GB 857 383); myclobutanil,
2-(4-chlorophenyl)-2-[1,2,4]triazol-1-yl-methylpentanenitrile (CAS
RN 88671-89-0); penconazole,
1-[2-(2,4-dichlorophenyl)-pentyl]-1H-[1,2,4]triazole (Pesticide
Manual, 12th Ed. (2000), S.712); propiconazole,
1-[[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-tr-
iazole (BE 835 579); prochloraz,
N-(propyl-[2-(2,4,6-trichlorophenoxy)ethyl])imidazole-1-carboxamide
(U.S. Pat. No. 3,991,071); prothioconazole,
2-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydr-
o-[1,2,4]triazole-3-thione (WO 96/16048); simeconazole,
.alpha.-(4-fluorophenyl)-.alpha.-[(trimethylsilyl)methyl]-1H-1,2,4-triazo-
le-1-ethanol [CAS RN 149508-90-7]; tebuconazole,
1-(4-chlorophenyl)-4,4-dimethyl-3-[1,2,4]triazol-1-ylmethylpentan-3-ol
(EP-A 40 345); tetraconazole,
1-[2-(2,4-dichlorophenyl)-3-(1,1,2,2-tetrafluoroethoxy)propyl]-1H-1,2,4-t-
riazole (EP 234 242); triadimefon,
1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone
(BE 793 867); triadimenol,
.beta.-(4-chlorophenoxy)-.alpha.-(1,1-dimethylethyl)-1H-1,2,4-triazole-1--
ethanol (DE 23 24 010); triflumizol,
(4-chloro-2-trifluoromethylphenyl)-(2-propoxy-1-[1,2,4]triazol-1-ylethyli-
den)-amine (JP-A 79/119 462); triticonazole,
(5E)-5-[(4-chlorophenyl)methylene]-2,2-dimethyl-1-(1H-1,2,4-triazol-1-ylm-
ethyl)cyclopentanol (FR 26 41 277); iprodione,
N-isopropyl-3-(3,5-dichlorophenyl)-2,4-dioxoimidazolidine-1-carboxamide
(GB 13 12 536); myclozolin,
(RS)-3-(3,5-dichlorophenyl)-5-methoxymethyl-5-methyl-1,3-oxazolidine-2,4--
dione [CAS RN 54864-61-8]; procymidone,
N-(3,5-dichlorophenyl)-1,2-dimethyl-cyclopropane-1,2-dicarboximide
(U.S. Pat. No. 3,903,090); vinclozolin,
3-(3,5-dichlorophenyl)-5-methyl-5-vinyloxazolidine-2,4-dione (DE-A
22 07 576); ferbam, iron(3+) dimethyldithiocarbamate (U.S. Pat. No.
1,972,961); nabam, disodium ethylenebis-(dithiocarbamate) (U.S.
Pat. No. 2,317,765); maneb, manganese ethylenebis(dithiocarbamate)
(U.S. Pat. No. 2,504,404); mancozeb, manganese
ethylenebis(dithiocarbamate) polymer complex zinc salt (GB 996
264); metam, methyldithiocarbaminic acid (U.S. Pat. No. 2,791,605);
metiram, zinc ammoniate ethylenebis(dithiocarbamate) (U.S. Pat. No.
3,248,400); propineb, zinc propylenebis-(dithiocarbamate) polymer
(BE 611 960); polycarbamate,
bis(dimethylcarbamo-dithioato-S,S')[.mu.-[[1,2-ethanediylbis[carbamodithi-
oato-S,S']](2-)]]di[zinc] [CAS RN 64440-88-6]; thiram,
bis(dimethylthiocarbamoyl) disulfide (DE 642 532); ziram,
dimethyldithiocarbamate [CAS RN 137-30-4]; zineb, zinc
ethylenebis(dithiocarbamate) (U.S. Pat. No. 2,457,674); anilazine,
4,6-dichloro-N-(2-chlorophenyl)-1,3,5-triazine-2-amine (U.S. Pat.
No. 2,720,480); benomyl,
N-butyl-2-acetylaminobenzoimidazole-1-carboxamide (U.S. Pat. No.
3,631,176); boscalid,
2-chloro-N-(4'-chlorobiphenyl-2-yl)nicotinamide (EP-A 545 099);
carbendazim, methyl (1H-benzoimidazol-2-yl)carbamate (U.S. Pat. No.
3,657,443); carboxin,
5,6-dihydro-2-methyl-N-phenyl-1,4-oxathiin-3-carboxamide (U.S. Pat.
No. 3,249,499); oxycarboxin,
5,6-dihydro-2-methyl-1,4-oxathiin-3-carboxanilide 4,4-dioxide (U.S.
Pat. No. 3,399,214); cyazofamid,
4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulfonami-
de (CAS RN 120116-88-3]; dazomet,
3,5-dimethyl-1,3,5-thiadiazinane-2-thione (Bull. Soc. Chim. Fr. 15,
p. 891 (1897)); dithianon,
5,10-dioxo-5,10-dihydronaphtho[2,3-b][1,4]dithiin-2,3-dicarbonitrile
(GB 857 383); famoxadone,
(RS)-3-anilino-5-methyl-5-(4-phenoxyphenyl)-1,3-oxazolidine-2,4-dione
[CAS RN 131807-57-3]; fenamidone,
(S)-1-anilino-4-methyl-2-methylthio-4-phenylimidazolin-5-one [CAS
RN 161326-34-7]; fenarimol,
.alpha.-(2-chlorophenyl)-.alpha.-(4-chlorophenyl)-5-pyrimidinemethanol
(GB 12 18 623); fuberidazole, 2-(2-furanyl)-1H-benzimidazole (DE 12
09 799); flutolanil,
.alpha.,.alpha.,.alpha.-trifluoro-3'-isopropoxy-o-toluanilide (JP
1104514); furametpyr,
5-chloro-N-(1,3-dihydro-1,1,3-trimethyl-4-isobenzofuranyl)-1,3-dimethyl-1-
H-pyrazole-4-carboxamide [CAS RN 123572-88-3]; isoprothiolane,
diisopropyl 1,3-dithiolan-2-ylidenemalonate (Proc. Insectic.
Fungic. Conf. 8. Vol. 2, p. 715 (1975)); mepronil,
3'-isopropoxy-o-toluanilide (U.S. Pat. No. 3,937,840); nuarimol,
.alpha.-(2-chlorophenyl)-.alpha.-(4-fluorophenyl)-5-pyrimidinemethanol
(GB 12 18 623); fluopicolide (picobenzamid),
2,6-dichloro-N-(3-chloro-5-trifluoromethylpyridin-2-ylmethyl)benzamide
(WO 99/42447); probenazole, 3-allyloxy-1,2-benzothiazole
1,1-dioxide (Agric. Biol. Chem. 37, p. 737 (1973)); proquinazid,
6-iodo-2-propoxy-3-propylquinazolin-4(3H)-one (WO 97/48684);
pyrifenox, 2',4'-dichloro-2-(3-pyridyl)acetophenone
(EZ)--O-methyloxime (EP 49 854); pyroquilon,
1,2,5,6-tetrahydropyrrolo[3,2,1-ij]quinolin-4-one (GB 139 43 373)
quinoxyfen, 5,7-dichloro-4-(4-fluorophenoxy)quinoline (U.S. Pat.
No. 5,240,940); silthiofam,
N-allyl-4,5-dimethyl-2-(trimethylsilyl)thiophene-3-carboxamide [CAS
RN 175217-20-6]; thiabendazole, 2-(1,3-thiazol-4-yl)benzimidazole
(U.S. Pat. No. 3,017,415); thifluzamide,
2',6'-dibromo-2-methyl-4'-tri-fluormethoxy-4-trifluormethyl-1,3-thiazole--
5-carboxanilide [CAS RN 130000-40-7]; thiophanate-methyl,
1,2-phenylenebis(iminocarbonothioyl)bis(dimethylcarbamate) (DE-A 19
30 540); tiadinil,
3'-chloro-4,4'-dimethyl-1,2,3-thiadiazole-5-carboxanilide [CAS RN
223580-51-6]; tricyclazole,
5-methyl-1,2,4-triazolo[3,4-b][1,3]benzothiazole [CAS RN
41814-78-2]; triforine,
N,N'-{piperazine-1,4-diylbis[(trichlormethyl)methylene]}diformamide
(DE 19 01 421); Bordeaux mixture, mixture of
CuSO.sub.4.times.3Cu(OH).sub.2.times.3CaSO.sub.4 [CAS RN
8011-63-0]; copper acetate, Cu(OCOCH.sub.3).sub.2 [CAS RN
8011-63-0]; copper oxychloride, Cu.sub.2Cl(OH).sub.3 [CAS RN
1332-40-7]; basic copper sulfate, CuSO.sub.4 [CAS RN 1344-73-6];
binapacryl, (RS)-2-sec-butyl-4,6-dinitrophenyl 3-methylcrotonate
[CAS RN 485-31-4]; dinocap, mixture of
2,6-dinitro-4-octylphenylcrotonate and
2,4-dinitro-6-octylphenylcrotonate, where "octyl" is a mixture of
1-methylheptyl, 1-ethylhexyl and 1-propylpentyl (U.S. Pat. No.
2,526,660); dinobuton, (RS)-2-sec-butyl-4,6-dinitrophenyl isopropyl
carbonate [CAS RN 973-21-7]; nitrothal-isopropyl, diisopropyl
5-nitroisophthalate (Proc. Br. Insectic. Fungic. Conf. 7., Vol. 2,
p. 673 (1973)); fenpiclonil,
4-(2,3-dichloro-phenyl)-1H-pyrrole-3-carbonitrile (Proc. 1988 Br.
Crop Prot. Conf.--Pests Dis., Vol. 1, p. 65); fludioxonil,
4-(2,2-difluorobenzo[1,3]dioxol-4-yl)-1H-pyrrole-3-carbonitrile
(The Pesticide Manual, publ. The British Crop Protection Council,
10th ed. (1995), p. 482); acibenzolar-S-methyl, methyl
1,2,3-benzothiadiazol-7-carbothioate [CAS RN 135158-54-2];
flubenthiavalicarb (benthiavalicarb), isopropyl
{(S)-1-[(1R)-1-(6-fluorobenzo-thiazol-2-yl)-ethylcarbamoyl]-2-methylpropy-
l}carbamate (JP-A 09/323 984); carpropamid,
2,2-dichloro-N-[1-(4-chlorophenyl)ethyl]-1-ethyl-3-methylcyclopropanecarb-
oxamide [CAS RN 104030-54-8]; chlorothalonil,
2,4,5,6-tetrachloroisophthalonitrile (U.S. Pat. No. 3,290,353);
cyflufenamid,
(Z)--N-[.alpha.-(cyclopropylmethoxyimino)-2,3-difluoro-6-(trifluoro-methy-
l)benzyl]-2-phenylacetamide (WO 96/19442); cymoxanil,
1-(2-cyano-2-methoxyiminoacetyl)-3-ethylurea (U.S. Pat. No.
3,957,847); diclomezine,
6-(3,5-dichlorophenyl-p-tolyl)-pyridazin-3(2H)-one (U.S. Pat. No.
4,052,395) diclocymet,
(RS)-2-cyano-N--[(R)-1-(2,4-dichloro-phenyl)ethyl]-3,3-dimethylbutyramide
[CAS RN 139920-32-4]; diethofencarb, isopropyl
3,4-diethoxycarbanilate (EP 78 663); edifenphos, O-ethyl
S,S-diphenyl phosphoro-dithioate (DE 14 93 736) ethaboxam,
N-(cyano-2-thienylmethyl)-4-ethyl-2-(ethylamino)-5-thiazolecarboxamide
(EP-A 639 574); fenhexamid,
N-(2,3-dichloro-4-hydroxyphenyl)-1-methylcyclohexanecarboxamide
(Proc. Br. Crop Prot. Conf.--Pests Dis., 1998, Vol. 2, p. 327);
fentin acetate, triphenyltin (U.S. Pat. No. 3,499,086); fenoxanil,
N-(1-cyano-1,2-di-methylpropyl)-2-(2,4-dichlorophenoxy)propanamide
(EP 262 393); ferimzone, mepanipyrim,
(Z)-2'-methylacetophenone-4,6-dimethylpyrimidin-2-ylhydrazone [CAS
RN 89269-64-7]; fluazinam,
3-chloro-N-[3-chloro-2,6-dinitro-4-(trifluoromethyl)phenyl]-5-(trifluorom-
ethyl)-2-pyridinamine (The Pesticide Manual, publ. The British Crop
Protection Council, 10th ed. (1995), p. 474); fosetyl,
fosetyl-aluminum, ethylphosphonate (FR 22 54 276); iprovalicarb,
isopropyl
[(1S)-2-methyl-1-(1-p-tolylethylcarbamoyl)propyl]-carbamate (EP-A
472 996); hexachlorbenzene (C. R. Seances Acad. Agric. Fr. 31, p.
24, 1945); metrafenon,
3'-bromo-2,3,4,6'-tetramethoxy-2',6-dimethylbenzophenone (U.S. Pat.
No. 5,945,567); pencycuron,
1-(4-chlorobenzyl)-1-cyclopentyl-3-phenylurea (DE 27 32 257);
penthiopyrad,
(RS)--N-[2-(1,3-dimethylbutyl)-3-thienyl]-1-methyl-3-(trifluoromethyl)-1H-
-pyrazole-4-carboxamide (JP 10130268); propamocarb, propyl
3-(dimethyl-amino)propylcarbamate (DE 15 67 169); phthalide (DE 16
43 347); toloclofos-methyl, O-2,6-dichloro-p-tolyl O,O-dimethyl
phosphorothioate (GB 14 67 561); quintozene, pentachlornitrobenzene
(DE 682 048); zoxamide,
(RS)-3,5-dichloro-N-(3-chloro-1-ethyl-1-methyl-2-oxopropyl)-p-toluamide
[CAS RN 156052-68-5]; azoxystrobin, methyl
2-{2-[6-(2-cyano-1-vinylpenta-1,3-dienyloxy)pyrimidin-4-yloxy]phenyl}-3-m-
ethoxyacrylate (EP 382 375), dimoxystrobin,
(E)-2-(methoxyimino)-N-methyl-2-[.alpha.-(2,5-xylyl-oxy)-o-tolyl]acetamid-
e (EP 477 631); enestroburin, methyl
2-{2-[3-(4-chlorophenyl)-1-methylallylideneaminooxymethyl]phenyl}-3-metho-
xyacrylate (EP 936 213); fluoxastrobin,
(E)-{2-[6-(2-chlorophenoxy)-5-fluoropyrimidin-4-yloxy]phenyl}(5,6-dihydro-
-1,4,2-dioxazin-3-yl)methanone O-methyloxime (WO 97/27189);
kresoxim-methyl, methyl
(E)-methoxyimino[.alpha.-(o-tolyloxy)-o-tolyl]acetate (EP 253 213);
metominostrobin,
(E)-2-(methoxyimino)-N-methyl-2-(2-phenoxyphenyl)acetamide (EP 398
692); orysastrobin,
(2E)-2-(methoxyimino)-2-{2-[(3E,5E,6E)-5-(methoxyimino)-4,6-dimethyl-2,8--
dioxa-3,7-diazanona-3,6-dien-1-yl]phenyl}-N-methylacetamide (WO
97/15552); picoxystrobin, methyl
3-methoxy-2-[2-(6-trifluoromethylpyridin-2-yloxy-methyl)phenyl]acrylate
(EP 278 595); pyraclostrobin, methyl
N-{2-[1-(4-chlorophenyl)-1H-pyrazol-3-yloxymethyl]phenyl}(N-methoxy)carba-
mate (WO 96/01256); trifloxystrobin, methyl
(E)-methoxyimino-{(E)-.alpha.-[1-(.alpha.,.alpha.,.alpha.-trifluoro-m-tol-
yl)ethylidene-aminooxy]o-tolyl}acetate (EP 460 575); captafol,
N-(1,1,2,2-tetrachloroethylthio)cyclohex-4-ene-1,2-dicarboximide
(Phytopathology, Vol. 52, p. 754 (1962)); captan,
N-(tri-chloromethylthio)cyclohex-4-ene-1,2-dicarboximide (U.S. Pat.
No. 2,553,770); dichlofluanid,
N-di-chlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfamide (DE 11
93 498); folpet, N-(trichloromethylthio)phthalimide (U.S. Pat. No.
2,553,770); tolylfluanid,
N-dichlorofluoromethyl-thio-N',N'-dimethyl-N-p-tolylsulfamide (DE
11 93 498); dimethomorph,
3-(4-chloro-phenyl)-3-(3,4-dimethoxyphenyl)-1-morpholin-4-yl-propenone
(EP 120 321); flumetover,
2-(3,4-dimethoxyphenyl)-N-ethyl-.alpha.,.alpha.,.alpha.-trifluoro-N-methy-
l-p-toluamide [AGROW no. 243, 22 (1995)]; flumorph,
3-(4-fluorophenyl)-3-(3,4-dimethoxyphenyl)-1-morpholin-4-ylpropenone
(EP 860 438);
5-Amino-2-isopropyl-3-oxo-4-o-tolyl-2,3-dihydro-pyrazole-1-carb-
othioic acid S-allyl ester (CN1939128).
[0400] The compounds described by IUPAC nomenclature, their
preparation and their fungicidal activity are also known (cf. Can.
J. Plant Sci. 48(6), 587-94, 1968; EP-A 141 317; EP-A 152 031; EP-A
226 917; EP-A 243 970; EP-A 256 503; EP-A 428 941; EP-A 532 022;
EP-A 1 028 125; EP-A 1 035 122; EP-A 1 201 648; EP-A 1 122 244, JP
2002316902; DE 19650197; DE 10021412; DE 102005009458; U.S. Pat.
No. 3,296,272; U.S. Pat. No. 3,325,503; WO 98/46608; WO 99/14187;
WO 99/24413; WO 99/27783; WO 00/29404; WO 00/46148; WO 00/65913; WO
01/54501; WO 01/56358; WO 02/22583; WO 02/40431; WO 03/10149; WO
03/11853; WO 03/14103; WO 03/16286; WO 03/53145; WO 03/61388; WO
03/66609; WO 03/74491; WO 04/49804; WO 04/83193; WO 05/120234; WO
05/123689; WO 05/123690; WO 05/63721; WO 05/87772; WO 05/87773; WO
06/15866; WO 06/87325; WO 06/87343; WO 07/82098; WO 07/90624, WO
11/028657).
N-methyl-2-{1-[(5-methyl-3-trifluoromethyl-1H-pyrazol-1-yl)-acetyl]-piper-
idin-4-yl}-N-[(1R)-1,2,3,4-tetrahydronaphthalen-1-yl]-4-thiazolecarboxamid-
e has been described in WO 2007/014290.
[0401] It is preferred that the compositions comprise as compounds
V fungicidal compounds that are independently of each other
selected from the groups of fungicides A), B), C), D), E), F), G),
H), I), J), K) and L).
[0402] Preference is given to mixtures comprising as compound V at
least one active substance selected from group A) and particularly
selected from azoxystrobin, dimoxystrobin, fluoxastrobin,
kresoxim-methyl, orysastrobin, picoxystrobin, pyraclostrobin,
trifloxystrobin; famoxadone, fenamidone; bixafen, boscalid,
fluopyram, fluxapyroxad, isopyrazam, penflufen, penthiopyrad,
sedaxane; ametoctradin, cyazofamid, fluazinam, fentin salts, such
as fentin acetate.
[0403] Preference is also given to mixtures comprising as compound
V at least one active substance selected from group B) and
particularly selected from cyproconazole, difenoconazole,
epoxiconazole, fluquinconazole, flusilazole, flutriafol,
metconazole, myclobutanil, penconazole, propiconazole,
prothioconazole, triadimefon, triadimenol, tebuconazole,
tetraconazole, triticonazole, prochloraz, fenarimol, triforine;
dodemorph, fenpropimorph, tridemorph, fenpropidin, spiroxamine;
fenhexamid.
[0404] Preference is also given to mixtures comprising as compound
V at least one active substance selected from group C) and
particularly selected from metalaxyl, (metalaxyl-M) mefenoxam,
ofurace.
[0405] Preference is also given to mixtures comprising as compound
V at least one active substance selected from group D) and
particularly selected from benomyl, carbendazim,
thiophanate-methyl, ethaboxam, fluopicolide, zoxamide, metrafenone,
pyriofenone.
[0406] Preference is also given to mixtures comprising as compound
V at least one active substance selected from group E) and
particularly selected from cyprodinil, mepanipyrim,
pyrimethanil.
[0407] Preference is also given to mixtures comprising as compound
V at least one active substance selected from group F) and
particularly selected from iprodione, fludioxonil, vinclozolin,
quinoxyfen.
[0408] Preference is also given to mixtures comprising as compound
V at least one active substance selected from group G) and
particularly selected from dimethomorph, flumorph, iprovalicarb,
benthiavalicarb, mandipropamid, propamocarb.
[0409] Preference is also given to mixtures comprising as compound
V at least one active substance selected from group H) and
particularly selected from copper acetate, copper hydroxide, copper
oxychloride, copper sulfate, sulfur, mancozeb, metiram, propineb,
thiram, captafol, folpet, chlorothalonil, dichlofluanid,
dithianon.
[0410] Preference is also given to mixtures comprising as compound
V at least one active substance selected from group I) and
particularly selected from carpropamid and fenoxanil.
[0411] Preference is also given to mixtures comprising as compound
V at least one active substance selected from group J) and
particularly selected from acibenzolar-S-methyl, probenazole,
tiadinil, fosetyl, fosetyl-aluminium, H.sub.3PO.sub.3 and salts
thereof.
[0412] Preference is also given to mixtures comprise as compound V
at least one active substance selected from group K) and
particularly selected from cymoxanil, proquinazid and
N-methyl-2-{1-[(5-methyl-3-trifluoromethyl-1H-pyrazol-1-yl)-acetyl]-piper-
idin-4-yl}-N-[(1R)-1,2,3,4-tetrahydronaphthalen-1-yl]-4-thiazolecarboxamid-
e.
[0413] Preference is also given to mixtures comprising as compound
V at least one active substance selected from group L) and
particularly selected from Bacillus subtilis strain NRRL No.
B-21661, Bacillus pumilus strain NRRL No. B-30087 and Ulocladium
oudemansii.
[0414] More preference is given to following compounds V:
pyraclostrobin, epoxiconazole,
2-[rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranyl
methyl]-2H [1,2,4]triazole-3-thiol and fluxapyroxade.
[0415] Specific compositions contain following fungicides:
[0416] An imidazolium compound F15 or F19 (formulae see in the
examples) and a compound V selected from pyraclostrobin,
epoxiconazole,
2-[rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranyl
methyl]-2H [1,2,4]triazole-3-thiol and fluxapyroxade.
[0417] More specific compositions contain following fungicides:
[0418] An imidazolium compound F15 and a compound V selected from
pyraclostrobin, epoxiconazole,
2-[rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranyl
methyl]-2H [1,2,4]triazole-3-thiol and fluxapyroxade;
an imidazolium compound F19 and a compound V selected from
epoxiconazole and
2-[rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranyl
methyl]-2H [1,2,4]triazole-3-thiol.
[0419] The polymeric, ionic compound comprising imidazolium groups
and the fungicidal compositions according to the invention
containing it are suitable as fungicides. They are distinguished by
an outstanding effectiveness against a broad spectrum of
phytopathogenic fungi, including soil-borne fungi, which derive
especially from the classes of the Plasmodiophoromycetes,
Peronosporomycetes (syn. Oomyce tes), Chytridiomycetes,
Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (syn.
Fungi imperfecti). Some are systemically effective and they can be
used in crop protection as foliar fungicides, fungicides for seed
dressing and soil fungicides. Moreover, they are suitable for
controlling harmful fungi, which inter alia occur in wood or roots
of plants.
[0420] The polymeric, ionic compound comprising imidazolium groups
and the fungicidal compositions according to the invention
containing it are particularly important in the control of a
multitude of phytopathogenic fungi on various cultivated plants,
such as cereals, e.g. wheat, rye, barley, triticale, oats or rice;
beet, e.g. sugar beet or fodder beet; fruits, such as pomes, stone
fruits or soft fruits, e.g. apples, pears, plums, peaches, almonds,
cherries, strawberries, raspberries, blackberries or gooseberries;
leguminous plants, such as lentils, peas, alfalfa or soy beans; oil
plants, such as rape, mustard, olives, sunflowers, coconut, cocoa
beans, castor oil plants, oil palms, ground nuts or soybeans;
cucurbits, such as squashes, cucumber or melons; fiber plants, such
as cotton, flax, hemp or jute; citrus fruit, such as oranges,
lemons, grapefruits or mandarins; vegetables, such as spinach,
lettuce, aspa ragus, cabbages, carrots, onions, tomatoes, potatoes,
cucurbits or paprika; laura ceous plants, such as avocados,
cinnamon or camphor; energy and raw material plants, such as corn,
soybean, rape, sugar cane or oil palm; corn; tobacco; nuts; coffee;
tea; bana nas; vines (table grapes and grape juice grape vines);
hop; turf; natural rubber plants or ornamental and forestry plants,
such as flowers, shrubs, broad-leaved trees or ever greens, e.g.
conifers; and on the plant propagation material, such as seeds, and
the crop material of these plants.
[0421] Preferably the polymeric, ionic compound comprising
imidazolium groups and the fungicidal compositions according to the
invention containing it are used for controlling a multitude of
fungi on field crops, such as potatoes sugar beets, tobacco, wheat,
rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes,
sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or
vegetables, such as cucumbers, tomatoes, beans or squashes.
[0422] The term "plant propagation material" is to be understood to
denote all the genera give parts of the plant such as seeds and
vegetative plant material such as cuttings and tubers (e.g.
potatoes), which can be used for the multiplication of the plant.
This includes seeds, roots, fruits, tubers, bulbs, rhizomes,
shoots, sprouts and other parts of plants, including seedlings and
young plants, which are to be transplan ted after germi nation or
after emergence from soil. These young plants may also be protected
before transplantation by a total or partial treatment by immersion
or pouring.
[0423] Preferably, treatment of plant propagation materials with
the polymeric, ionic compound comprising imidazolium rings and
compositions thereof, respectively, is used for controlling a
multitude of fungi on cereals, such as wheat, rye, barley and oats;
rice, corn, cotton and soybeans.
[0424] The term "cultivated plants" is to be understood as
including plants which have been modified by breeding, mutagenesis
or genetic engineering including but not limiting to agricultural
biotech products on the market or in development (cf.
http://www.bio.org/speeches/pubs/er/agri_products.asp). Genetically
modified plants are plants, which genetic material has been so
modified by the use of recombi nant DNA techniques that under
natural circumstances cannot readily be obtained by cross breeding,
mutations or natural recombination. Typically, one or more genes
have been integrated into the genetic material of a genetically
modified plant in order to improve certain properties of the plant.
Such genetic modifications also include but are not limited to
targeted post-transtional modification of protein(s), oligo- or
polypeptides e.g. by glycosylation or polymer additions such as
prenylated, acetylated or farnesylated moieties or PEG
moieties.
[0425] Plants that have been modified by breeding, mutagenesis or
genetic engineering, e.g. have been rendered tolerant to
applications of specific classes of herbicides, such as
hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors; acetolactate
synthase (ALS) inhibitors, such as sulfonyl ureas (see e.g. U.S.
Pat. No. 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO
98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO
03/13225, WO 03/14356, WO 04/16073) or imidazolinones (see e.g.
U.S. Pat. No. 6,222,100, WO 01/82685, WO 00/026390, WO 97/41218, WO
98/002526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/014357, WO
03/13225, WO 03/14356, WO 04/16073);
enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such
as glyphosate (see e.g. WO 92/00377); glutamine synthetase (GS)
inhibitors, such as glufosinate (see e.g. EP-A 242 236, EP-A 242
246) or oxynil herbicides (see e.g. U.S. Pat. No. 5,559,024) as a
result of conventional methods of breeding or genetic engineering.
Several cultivated plants have been rendered tolerant to herbicides
by conventional methods of breeding (mutagenesis), e.g.
Clearfield.RTM. summer rape (Canola, BASF SE, Germany) being
tolerant to imidazolinones, e.g. imazamox. Genetic engineering
methods have been used to render cultivated plants such as soybean,
cotton, corn, beets and rape, tolerant to herbicides such as glypho
sate and glufosinate, some of which are commercially available
under the trade names RoundupReady.RTM. (glyphosate-tolerant,
Monsanto, U.S.A.) and LibertyLink.RTM. (glufosinate-tolerant, Bayer
CropScience, Germany).
[0426] Furthermore, plants are also covered that are by the use of
recombinant DNA techniques capable to synthesize one or more
insecticidal proteins, especially those known from the bacterial
genus Bacillus, particularly from Bacillus thuringiensis, such as
.delta.-endotoxins, e.g. CryIA(b), CryIA(c), CryIF, CryIF(a2),
CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c; vegetative insecticidal
proteins (VIP), e.g. VIP1, VIP2, VIP3 or VIP3A; insecticidal
proteins of bacteria colonizing nematodes, e.g. Photo irhab idus
spp. or Xenorhabdus spp.; toxins produced by animals, such as
scorpion toxins, arachnid toxins, wasp toxins, or other
insect-specific neurotoxins; toxins produced by fungi, such
Streptomycetes toxins, plant lectins, such as pea or barley
lectins; agglutinins; proteinase inhibitors, such as trypsin
inhibitors, serine protease inhibitors, patatin, cystatin or papain
inhibitors; ribosome-inactivating proteins (RIP), such as ricin,
maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism
enzymes, such as 3-hydroxysteroid oxidase,
ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases,
ecdysone inhibitors or HMG-CoA-reductase; ion channel blockers,
such as blockers of sodium or calcium channels; juvenile hormone
esterase; diuretic hormone receptors (helicokinin receptors);
stilben synthase, bibenzyl synthase, chitinases or glucanases. In
the context of the present invention these insecticidal proteins or
toxins are to be under stood expressly also as pre-toxins, hybrid
proteins, truncated or otherwise modified proteins. Hybrid proteins
are characterized by a new combination of protein domains, (see,
e.g. WO 02/015701). Further examples of such toxins or genetically
modified plants capable of synthesizing such toxins are disclosed,
e.g., in EP A 374 753, WO 93/007278, WO 95/34656, EP A 427 529, EP
A 451 878, WO 03/18810 and WO 03/52073. The methods for producing
such genetically modified plants are generally known to the person
skilled in the art and are described, e.g. in the publications
mentioned above. These insecticidal proteins contained in the
genetically modified plants impart to the plants producing these
proteins tolerance to harmful pests from all taxonomic groups of
athropods, especially to beetles (Coelop tera), two-winged insects
(Diptera), and moths (Lepidoptera) and to nematodes (Nema toda).
Genetically modified plants capable to synthesize one or more
insecticidal pro teins are, e.g., described in the publications
mentioned above, and some of which are commercially available such
as YieldGard.RTM. (corn cultivars producing the Cry1Ab toxin),
YieldGard.RTM. Plus (corn cultivars producing Cry1Ab and Cry3Bb1
toxins), Starlink.RTM. (corn cultivars producing the Cry9c toxin),
Herculex.RTM. RW (corn cultivars producing Cry34Ab1, Cry35Ab1 and
the enzyme Phosphinothricin-N-Acetyltransferase [PAT]); NuCOTN.RTM.
33B (cotton cultivars producing the Cry1Ac toxin), Bollgard.RTM. I
(cotton culti vars producing the Cry1Ac toxin), Bollgard.RTM. II
(cotton cultivars producing Cry1Ac and Cry2Ab2 toxins); VIPCOT.RTM.
(cotton cultivars producing a VIP-toxin); NewLeaf.RTM. (potato
cultivars producing the Cry3A toxin); Bt-Xtra.RTM.,
NatureGard.RTM., KnockOut.RTM., BiteGard.RTM., Protecta.RTM., Bt11
(e.g. Agrisure.RTM. CB) and Bt176 from Syngenta Seeds SAS, France,
(corn cultivars producing the Cry1Ab toxin and PAT enyzme), MIR604
from Syngenta Seeds SAS, France (corn cultivars producing a
modified version of the Cry3A toxin, c.f. WO 03/018810), MON 863
from Monsanto Europe S.A., Belgium (corn cultivars prod ucing the
Cry3Bb1 toxin), IPC 531 from Monsanto Europe S.A., Belgium (cotton
cultivars producing a modified version of the Cry1Ac toxin) and
1507 from Pioneer Overseas Corporation, Belgium (corn cultivars
producing the Cry1F toxin and PAT enzyme).
[0427] Furthermore, plants are also covered that are by the use of
recombinant DNA techniques capable to synthesize one or more
proteins to in crease the resistance or tolerance of those plants
to bacterial, viral or fungal pathogens. Examples of such proteins
are the so-called "pathogenesis-related proteins" (PR proteins,
see, e.g. EP A 392 225), plant disease resistance genes (e.g.
potato culti vars, which express resistance genes acting against
Phytophthora infestans derived from the mexican wild potato Solanum
bulbocastanum) or T4-lyso zym (e.g. potato cultivars capable of
synthesizing these proteins with increased resistance against
bacteria such as Erwinia amylvora). The methods for producing such
genetically modified plants are generally known to the person
skilled in the art and are described, e.g. in the publications
mentioned above.
[0428] Furthermore, plants are also covered that are by the use of
recombinant DNA techniques capable to synthesize one or more
proteins to increase the productivity (e.g. bio mass production,
grain yield, starch content, oil content or protein content),
tolerance to drought, salinity or other growth-limiting environ
mental factors or tolerance to pests and fungal, bacterial or viral
pathogens of those plants.
[0429] Furthermore, plants are also covered that contain by the use
of recombinant DNA techniques a modified amount of substances of
content or new substances of content, specifically to improve human
or animal nutrition, e.g. oil crops that produce health-promoting
long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids
(e.g. Nexera.RTM. rape, DOW Agro Sciences, Canada).
[0430] Furthermore, plants are also covered that contain by the use
of recombinant DNA techniques a modified amount of substances of
content or new substances of content, specifically to improve raw
material production, e.g. potatoes that produce increased amounts
of amylopectin (e.g. Amflora.RTM. potato, BASF SE, Germany).
[0431] The polymeric, ionic compound comprising imidazolium groups
and the fungicidal compositions according to the invention
containing it are particularly suitable for controlling the
following plant diseases: Albugo spp. (white rust) on ornamentals,
vegetables (e.g. A. candida) and sun glowers (e.g. A.
tragopogonis); Alternaria spp. (Alternaria leaf spot) on
vegetables, rape (A. brassicola or brassicae), sugar beets (A.
tenuis), fruits, rice, soybeans, potatoes (e.g. A. solani or A.
alternata), tomatoes (e.g. A. solani or A. alternata) and wheat;
Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on
cereals and vegetables, e.g. A. tritici (anthracnose) on wheat and
A. hordei on barley; Bipolaris and Drechslera spp. (teleomorph:
Cochliobolus spp.) on corn (e.g. D. maydis), cereals (e.g. B.
sorokiniana: spot blotch), rice (e.g. B. oryzae) and turfs;
Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals
(e.g. on wheat or barley); Botrytis cinerea (teleomorph:
Botryotinia fuckeliana: grey mold) on fruits and berries (e.g.
strawberries), vegetables (e.g. lettuce, carrots, celery and
cabbages), rape, flowers, vines, forestry plants and wheat; Bremia
lactucae (downy mildew) on lettuce; Cerato cystis (syn. Ophiostoma)
spp. (rot or wilt) on broad-leaved trees and evergreens, e.g. C.
ulmi (Dutch elm disease) on elms; Cercospora spp. (Cercospora leaf
spots) on corn, rice, sugar beets (e.g. C. beticola), sugar cane,
vegetables, coffee, soybeans (e.g. C. sojina or C. kikuchii) and
rice; Cladosporium spp. on tomatoes (e.g. C. fulvum: leaf mold) and
cereals, e.g. C. herbarum (black ear) on wheat; Claviceps purpurea
(ergot) on cereals; Cochliobolus (anamorph: Helminthosporium of
Bipolaris) spp. (leaf spots) on corn (C. carbonum), cereals (e.g.
C. sativus, anamorph: B. sorokiniana) and rice (e.g. C. miyabeanus,
anamorph: H. oryzae); Colletotrichum (teleomorph: Glomerella) spp.
(anthracnose) on cotton (e.g. C. gossypii), corn (e.g. C.
graminicola), soft fruits, potatoes (e.g. C. coccodes: black dot),
beans (e.g. C. lindemuthianum) and soybeans (e.g. C. truncatum or
C. gloeosporioides); Corticium spp., e.g. C. sasakii (sheath
blight) on rice; Coryne spora cassiicola (leaf spots) on soybeans
and ornamentals; Cycloconium spp., e.g. C. oleaginum on olive
trees; Cylindrocarpon spp. (e.g. fruit tree canker or young vine
decline, teleomorph: Nectria or Neonectria spp.) on fruit trees,
vines (e.g. C. lirio dendri, teleomorph: Neonectria liriodendri:
Black Foot Disease) and ornamentals; Dematophora (teleomorph:
Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe
spp., e.g. D. phaseolorum (damping off) on soybeans; Drechs lera
(syn. Helminthosporium, teleomorph: Pyrenophora) spp. on corn,
cereals, such as barley (e.g. D. teres, net blotch) and wheat (e.g.
D. tritici-repentis: tan spot), rice and turf; Esca (dieback,
apoplexy) on vines, caused by Formitiporia (syn. Phellinus)
punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier
Phaeoacremonium chlamydo sporum), Phaeoacremonium aleophilum and/or
Botryosphaeria obtusa; Elsinoe spp. on pome fruits (E. pyri), soft
fruits (E. veneta: anthracnose) and vines (E. ampelina:
anthracnose); Entyloma oryzae (leaf smut) on rice; Epicoccum spp.
(black mold) on wheat; Erysiphe spp. (powdery mildew) on sugar
beets (E. betae), vegetables (e.g. E. pisi), such as cucurbits
(e.g. E. cichoracearum), cabbages, rape (e.g. E. crucife rarum);
Eutypa lata (Eutypa canker or dieback, anamorph: Cytosporina lata,
syn. Liber tella blepharis) on fruit trees, vines and ornamental
woods; Exserohilum (syn. Helmin thosporium) spp. on corn (e.g. E.
turcicum); Fusarium (teleomorph: Gibberella) spp. (wilt, root or
stem rot) on various plants, such as F. graminearum or F. culmorum
(root rot, scab or head blight) on cereals (e.g. wheat or barley),
F. oxysporum on tomatoes, F. solani on soybeans and F.
verticillioides on corn; Gaeumannomyces graminis (take-all) on
cereals (e.g. wheat or barley) and corn; Gibberella spp. on cereals
(e.g. G. zeae) and rice (e.g. G. fujikuroi: Bakanae disease);
Glomerella cingulata on vines, pome fruits and other plants and G.
gossypii on cotton; Grain staining complex on rice; Guignardia
bidwellii (black rot) on vines; Gymnosporangium spp. on rosaceous
plants and junipers, e.g. G. sabinae (rust) on pears;
Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus)
on corn, cereals and rice; Hemileia spp., e.g. H. vastatrix (coffee
leaf rust) on coffee; Isariopsis clavispora (syn. Cladosporium
vitis) on vines; Macrophomina phaseolina (syn. phaseoli) (root and
stem rot) on soybeans and cotton; Microdochium (syn. Fusarium)
nivale (pink snow mold) on cereals (e.g. wheat or barley);
Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp.,
e.g. M. laxa, M. fructicola and M. fructigena (bloom and twig
blight, brown rot) on stone fruits and other rosaceous plants;
Mycosphaerella spp. on cereals, bananas, soft fruits and ground
nuts, such as e.g. M. graminicola (anamorph: Septoria tritici,
Septoria blotch) on wheat or M. fijiensis (black Sigatoka disease)
on bananas; Peronospora spp. (downy mildew) on cabbage (e.g. P.
brassicae), rape (e.g. P. parasitica), onions (e.g. P. destructor),
tobacco (P. tabacina) and soybeans (e.g. P. manshurica); Phakopsora
pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora
spp. e.g. on vines (e.g. P. tracheiphila and P. tetraspora) and
soybeans (e.g. P. gregata: stem rot); Phoma lingam (root and stem
rot) on rape and cabbage and P. betae (root rot, leaf spot and
damping-off) on sugar beets; Phomopsis spp. on sunflowers, vines
(e.g. P. viticola: can and leaf spot) and soybeans (e.g. stem rot:
P. phaseoli, teleomorph: Diaporthe phaseolorum); Physoderma maydis
(brown spots) on corn; Phytophthora spp. (wilt, root, leaf, fruit
and stem root) on various plants, such as paprika and cucurbits
(e.g. P. capsici), soybeans (e.g. P. megasperma, syn. P. sojae),
potatoes and tomatoes (e.g. P. infestans: late blight) and
broad-leaved trees (e.g. P. ramorum: sudden oak death);
Plasmodiophora brassicae (club root) on cabbage, rape, radish and
other plants; Plasmopara spp., e.g. P. viticola (grapevine downy
mildew) on vines and P. halstedii on sunflowers; Podosphaera spp.
(powdery mildew) on rosa ceous plants, hop, pome and soft fruits,
e.g. P. leucotricha on apples; Polymyxa spp., e.g. on cereals, such
as barley and wheat (P. graminis) and sugar beets (P. betae) and
there by transmitted viral diseases; Pseudocercosporella
herpotrichoides (eyespot, teleo morph: Tapesia yallundae) on
cereals, e.g. wheat or barley; Pseudoperonospora (downy mildew) on
various plants, e.g. P. cubensis on cucurbits or P. humili on hop;
Pseudopezicula tracheiphila (red fire disease or `rotbrenner`,
anamorph: Phialophora) on vines; Puccinia spp. (rusts) on various
plants, e.g. P. triticina (brown or leaf rust), P. strihformis
(stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem
or black rust) or P. recondita (brown or leaf rust) on cereals,
such as e.g. wheat, barley or rye, and asparagus (e.g. P.
asparagi); Pyrenophora (anamorph: Drechslera) tritici-repentis (tan
spot) on wheat or P. teres (net blotch) on barley; Pyricularia
spp., e.g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast)
on rice and P. grisea on turf and cereals; Pythium spp.
(damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers,
soy beans, sugar beets, vegetables and various other plants (e.g.
P. ultimum or P. aphani dermatum); Ramularia spp., e.g. R.
collo-cygni (Ramularia leaf spots, Physiological leaf spots) on
barley and R. beticola on sugar beets; Rhizoctonia spp. on cotton,
rice, potatoes, turf, corn, rape, potatoes, sugar beets, vegetables
and various other plants, e.g. R. solani (root and stem rot) on
soybeans, R. solani (sheath blight) on rice or R. cerealis
(Rhizoctonia spring blight) on wheat or barley; Rhizopus stolonifer
(black mold, soft rot) on strawberries, carrots, cabbage, vines and
tomatoes; Rhynchosporium secalis (scald) on barley, rye and
triticale; Sarocladium oryzae and S. attenuatum (sheath rot) on
rice; Sclerotinia spp. (stem rot or white mold) on vegetables and
field crops, such as rape, sunflowers (e.g. S. sclerotiorum) and
soybeans (e.g. S. rolfsii or S. sclerotiorum); Septoria spp. on
various plants, e.g. S. glycines (brown spot) on soybeans, S.
tritici (Septoria blotch) on wheat and S. (syn. Stagonospora)
nodorum (Stagonospora blotch) on cereals; Uncinula (syn. Erysiphe)
necator (powdery mildew, anamorph: Oidium tuckeri) on vines;
Setospaeria spp. (leaf blight) on corn (e.g. S. turcicum, syn.
Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on
corn, (e.g. S. reiliana: head smut), sorghum and sugar cane;
Sphaerotheca fuliginea (powdery mildew) on cucurbits; Spongospora
subterranea (powdery scab) on potatoes and thereby transmitted
viral diseases; Stagonospora spp. on cereals, e.g. S. nodorum
(Stagonospora blotch, teleomorph: Leptosphaeria [syn.
Phaeosphaeria] nodorum) on wheat; Synchytrium endobioticum on
potatoes (potato wart disease); Taphrina spp., e.g. T. deformans
(leaf curl disease) on peaches and T. pruni (plum pocket) on plums;
Thielaviopsis spp. (black root rot) on tobacco, pome fruits,
vegetables, soybeans and cotton, e.g. T. basicola (syn. Chalara
elegans); Tilletia spp. (common bunt or stinking smut) on cereals,
such as e.g. T. tritici (syn. T. caries, wheat bunt) and T.
controversa (dwarf bunt) on wheat; Typhula incarnata (grey snow
mold) on barley or wheat; Uro cystis spp., e.g. U. occulta (stem
smut) on rye; Uromyces spp. (rust) on vege tables, such as beans
(e.g. U. appendiculatus, syn. U. phaseoli) and sugar beets (e.g. U.
betae); Ustilago spp. (loose smut) on cereals (e.g. U. nuda and U.
avaenae), corn (e.g. U. maydis: corn smut) and sugar cane; Venturia
spp. (scab) on apples (e.g. V. inaequalis) and pears; and
Verticillium spp. (wilt) on various plants, such as fruits and
ornamentals, vines, soft fruits, vegetables and field crops, e.g.
V. dahliae on straw berries, rape, potatoes and tomatoes.
[0432] The inventive mixtures and compositions are also suitable
for controlling harmful fungi in the protection of stored products
or harvest and in the protection of materials. The term "protection
of materials" is to be understood to denote the protection of
technical and non-living materials, such as adhesives, glues, wood,
paper and paperboard, textiles, leather, paint dispersions,
plastics, coiling lubricants, fiber or fabrics, against the
infestation and destruction by harmful microorganisms, such as
fungi and bacteria. As to the protection of wood and other
materials, the particular attention is paid to the following
harmful fungi: Ascomycetes such as Ophiostoma spp., Ceratocystis
spp., Aureobasidium pullu lans, Sclerophoma spp., Chaetomium spp.,
Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes such
as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus
spp., Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp.,
Deutero mycetes such as Aspergillus spp., Cladosporium spp.,
Penicillium spp., Trichorma spp., Alternaria spp., Paecilomyces
spp. and Zygomycetes such as Mucor spp., and in addition in the
protection of stored products and harvest the following yeast fungi
are worthy of note: Candida spp. and Saccharomyces cerevisae. In
particular, the mixtures and compositions of the present invention
are effective against plant pathogens in speciality crops such as
vine, fruits, hop, vegetables and tabacco--see the above list.
[0433] Plant propagation materials may be treated with the
polymeric, ionic compound comprising imidazolium groups and the
fungicidal compositions according to the invention containing it
prophylactically either at or before planting or transplanting. The
invention also relates to agrochemical compositions comprising an
auxiliary and at least one polymeric, ionic compound comprising
imidazolium groups and at least compound V.
[0434] An agrochemical composition comprises a fungicidally
effective amount of the at least one polymeric, ionic compound
comprising imidazolium groups and the at least compound V. The term
"effective amount" denotes an amount of the composition or of the
compounds, which is sufficient for controlling harmful fungi on
cultivated plants or in the protection of materials and which does
not result in a substantial damage to the treated plants. Such an
amount can vary in a broad range and is dependent on various
factors, such as the fungal species to be controlled, the treated
cultivated plant or material, the climatic conditions and the
specific compounds used.
[0435] The polymeric, ionic compound comprising imidazolium groups
can be converted into customary types of agrochemical compositions,
e.g. solutions, emulsions, suspensions, dusts, powders, pastes,
granules, pressings, capsules, and mixtures thereof. Examples for
composition types are suspensions (e.g. SC, OD, FS), emulsifiable
concentrates (e.g. EC), emul sions (e.g. EW, EO, ES, ME), capsules
(e.g. CS, ZC), pastes, pastilles, wettable pow ders or dusts (e.g.
WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g.
WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well
as gel formulations for the treatment of plant propagation
materials such as seeds (e.g. GF). These and further compositions
types are defined in the "Catalogue of pesticide formulation types
and international coding system", Technical Monograph No. 2, 6th
Ed. May 2008, CropLife International.
[0436] The compositions are prepared in a known manner, such as
described by Mollet and Grubemann, Formulation technology, Wiley
VCH, Weinheim, 2001; or Knowles, New developments in crop
protection product formulation, Agrow Reports DS243, T&F
Informa, London, 2005.
[0437] Suitable auxiliaries are solvents, liquid carriers, solid
carriers or fillers, surfactants, dispersants, emulsifiers,
wetters, adjuvants, solubilizers, penetration enhancers, protective
colloids, adhesion agents, thickeners, humectants, repellents,
attractants, feeding stimulants, compatibilizers, bactericides,
anti-freezing agents, anti-foaming agents, colorants, tackifiers
and binders.
[0438] Suitable solvents and liquid carriers are water and organic
solvents, such as mineral oil fractions of medium to high boiling
point, e.g. kerosene, diesel oil; oils of vegetable or animal
origin; aliphatic, cyclic and aromatic hydrocarbons, e.g. toluene,
paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols,
e.g. ethanol, propanol, butanol, benzylalcohol, cyclo hexanol;
glycols; DMSO; ketones, e.g. cyclo hexanone; esters, e.g. lactates,
carbonates, fatty acid esters, gamma-butyrolactone; fatty acids;
phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid
di methylamides; and mixtures thereof.
[0439] Suitable solid carriers or fillers are mineral earths, e.g.
silicates, silica gels, talc, kaolins, limestone, lime, chalk,
clays, dolomite, diatomaceous earth, bentonite, calcium sulfate,
magnesium sulfate, magnesium oxide; polysaccharides, e.g.
cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium
phosphate, ammonium nitrate, ureas; products of vegetable origin,
e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and
mixtures thereof.
[0440] Suitable surfactants are surface-active compounds, such as
anionic, cationic, nonionic and amphoteric surfactants, block
polymers, polyelectrolytes, and mixtures there of. Such surfactants
can be used as emusifier, dispersant, solubilizer, wetter,
penetration enhancer, protective colloid, or adjuvant. Examples of
surfactants are listed in McCutcheon's, Vol. 1: Emulsifiers &
Detergents, McCutcheon's Directories, Glen Rock, USA, 2008
(International Ed. or North American Ed.).
[0441] Suitable anionic surfactants are alkali, alkaline earth or
ammonium salts of sulf onates, sulfates, phosphates, carboxylates,
and mixtures thereof. Examples of sulf onates are
alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates,
lignine sulfonates, sulfonates of fatty acids and oils, sulfonates
of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols,
sulfonates of condensed naphthalenes, sulf onates of dodecyl- and
tridecylbenzenes, sulfonates of naphthalenes and alkyl naphtha
lenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates
are sulfates of fatty acids and oils, of ethoxylated alkylphenols,
of alcohols, of ethoxylated alcohols, or of fatty acid esters.
Examples of phosphates are phosphate esters. Examples of carboxy
lates are alkyl carboxylates, and carboxylated alcohol or
alkylphenol ethoxylates. Suitable nonionic surfactants are
alkoxylates, N-substituted fatty acid amides, amine oxides, esters,
sugar-based surfactants, polymeric surfactants, and mixtures
thereof. Examples of alkoxylates are compounds such as alcohols,
alkylphenols, amines, amides, arylphenols, fatty acids or fatty
acid esters which have been alkoxylated with 1 to 50 equivalents.
Ethylene oxide and/or propylene oxide may be employed for the
alkoxylation, preferably ethylene oxide. Examples of N-substituted
fatty acid amides are fatty acid glucamides or fatty acid
alkanolamides. Examples of esters are fatty acid esters, glycerol
esters or monoglycerides. Examples of sugar-based surfactants are
sorbitans, ethoxylated sorbitans, sucrose and glucose esters or
alkylpolyglucosides. Examples of polymeric surfactants are home- or
copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate.
[0442] Suitable cationic surfactants are quaternary surfactants,
for example quaternary am monium compounds with one or two
hydrophobic groups, or salts of long-chain primary amines. Suitable
amphoteric surfactants are alkylbetains and imidazolines. Suitable
block polymers are block polymers of the A-B or A-B-A type
comprising blocks of poly ethylene oxide and polypropylene oxide,
or of the A-B-C type comprising alkanol, poly ethylene oxide and
polypropylene oxide. Suitable polyelectrolytes are polyacids or
polybases. Examples of polyacids are alkali salts of polyacrylic
acid or polyacid comb polymers. Examples of polybases are
polyvinylamines or polyethyleneamines.
[0443] Suitable adjuvants are compounds which have a neglectable or
even no pesticidal activity themselves, and which improve the
biological performance of the polymeric, ionic compound comprising
imidazolium groups on the target. Examples are surfactants, mineral
or vegetable oils, and other auxilaries. Further examples are
listed by Knowles, Adjuvants and additives, Agrow Reports DS256,
T&F Informa UK, 2006, chapter 5.
[0444] Suitable thickeners are polysaccharides (e.g. xanthan gum,
carboxymethylcellu lose), anorganic clays (organically modified or
unmodified), polycarboxylates, and silicates.
[0445] Suitable bactericides are bronopol and isothiazolinone
derivatives such as alkyliso thiazolinones and
benzisothiazolinones.
[0446] Suitable anti-freezing agents are ethylene glycol, propylene
glycol, urea and glycerin.
[0447] Suitable anti-foaming agents are silicones, long chain
alcohols, and salts of fatty acids.
[0448] Suitable colorants (e.g. in red, blue, or green) are
pigments of low water solubility and water-soluble dyes. Examples
are inorganic colorants (e.g. iron oxide, titan oxide, iron
hexacyanoferrate) and organic colorants (e.g. alizarin-, azo- and
phthalocyanine colorants).
[0449] Suitable tackifiers or binders are polyvinylpyrrolidons,
polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or
synthetic waxes, and cellulose ethers.
[0450] Examples for composition types and their preparation are
(wherein active substances denote at least one polymeric, ionic
compound comprising imidazolium groups and optionally compound
V):
i) Water-Soluble Concentrates (SL, LS)
[0451] 10-60 wt % active substances and 5-15 wt % wetting agent
(e.g. alcohol alkoxylates) are dissolved in water and/or in a
water-soluble solvent (e.g. alcohols) ad 100 wt %. The active
substance dissolves upon dilution with water.
ii) Dispersible Concentrates (DC)
[0452] 5-25 wt % active substances and 1-10 wt % dispersant (e.g.
polyvinylpyrrolidone) are dissolved in organic solvent (e.g.
cyclohexanone) ad 100 wt %. Dilution with water gives a
dispersion.
iii) Emulsifiable Concentrates (EC)
[0453] 15-70 wt % active substances and 5-10 wt % emulsifiers (e.g.
calcium dodecylben zenesulfonate and castor oil ethoxylate) are
dissolved in water-insoluble organic sol vent (e.g. aromatic
hydrocarbon) ad 100 wt %. Dilution with water gives an
emulsion.
iv) Emulsions (EW, EO, ES)
[0454] 5-40 wt % active substances and 1-10 wt % emulsifiers (e.g.
calcium dodecylben zenesulfonate and castor oil ethoxylate) are
dissolved in 20-40 wt % water-insoluble organic solvent (e.g.
aromatic hydrocarbon). This mixture is introduced into water ad 100
wt % by means of an emulsifying machine and made into a homogeneous
emul sion. Dilution with water gives an emulsion.
v) Suspensions (SC, OD, FS)
[0455] In an agitated ball mill, 20-60 wt % active substances are
comminuted with addition of 2-10 wt % dispersants and wetting
agents (e.g. sodium lignosulfonate and alcohol ethoxylate), 0.1-2
wt % thickener (e.g. xanthan gum) and ad water ad 100 wt % to give
a fine active substance suspension. Dilution with water gives a
stable suspension of the active substance. For FS type composition
up to 40 wt % binder (e.g. polyvinylalcohol) is added.
vi) Water-Dispersible Granules and Water-Soluble Granules (WG,
SG)
[0456] 50-80 wt % active substances are ground finely with addition
of dispersants and wetting agents (e.g. sodium lignosulfonate and
alcohol ethoxylate) ad 100 wt % and prepared as water-dispersible
or water-soluble granules by means of technical appliances (e.g.
extrusion, spray tower, fluidized bed). Dilution with water gives a
stable dispersion or solution of the active substance.
vii) Water-Dispersible Powders and Water-Soluble Powders (WP, SP,
WS)
[0457] 50-80 wt % active substances are ground in a rotor-stator
mill with addition of 1-5 wt % dispersants (e.g. sodium
lignosulfonate), 1-3 wt % wetting agents (e.g. alcohol ethoxylate)
and solid carrier (e.g. silica gel) ad 100 wt %. Dilution with
water gives a stable dispersion or solution of the active
substance.
viii) Gel (GW, GF)
[0458] In an agitated ball mill, 5-25 wt % active substances are
comminuted with addition of 3-10 wt % dispersants (e.g. sodium
lignosulfonate), 1-5 wt % thickener (e.g. carboxy methylcellulose)
and water ad 100 wt % to give a fine suspension of the active
substance. Dilution with water gives a stable suspension of the
active substance.
iv) Microemulsion (ME)
[0459] 5-20 wt % active substances are added to 5-30 wt % organic
solvent blend (e.g. fatty acid dimethylamide and cyclohexanone),
10-25 wt % surfactant blend (e.g. alcohol ethoxylate and arylphenol
ethoxylate), and water ad 100 wt %. This mixture is stirred for 1 h
to produce spontaneously a thermodynamically stable
microemulsion.
iv) Microcapsules (CS)
[0460] An oil phase comprising 5-50 wt % active substances, 0-40 wt
% water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15
wt % acrylic monomers (e.g. methylmethac rylate, methacrylic acid
and a di- or triacrylate) are dispersed into an aqueous solu tion
of a protective colloid (e.g. polyvinyl alcohol). Radical
polymerization initiated by a radi cal initiator results in the
formation of poly(meth)acrylate microcapsules. Alternatively, an
oil phase comprising 5-50 wt % of an active compound, 0-40 wt %
water insoluble organic solvent (e.g. aromatic hydrocarbon), and an
isocyanate monomer (e.g. diphenylmethene-4,4'-diisocyanatae) are
dispersed into an aqueous solution of a protective colloid (e.g.
polyvinyl alcohol). The addition of a polyamine (e.g.
hexamethylenediamine) results in the formation of polyurea
microcapsules. The mono mers amount to 1-10 wt %. The wt % relate
to the total CS composition.
ix) Dustable Powders (DP, DS)
[0461] 1-10 wt % active substances are ground finely and mixed
intimately with solid carrier (e.g. finely divided kaolin) ad 100
wt %.
x) Granules (GR, FG)
[0462] 0.5-30 wt % active substances are ground finely and
associated with solid carrier (e.g. silicate) ad 100 wt %.
Granulation is achieved by extrusion, spray-drying or fluidized
bed.
xi) Ultra-Low Volume Liquids (UL)
[0463] 1-50 wt % active substances are dissolved in organic solvent
(e.g. aromatic hydro carbon) ad 100 wt %.
[0464] The compositions types i) to xi) may optionally comprise
further auxiliaries, such as 0.1-1 wt % bactericides, 5-15 wt %
anti-freezing agents, 0.1-1 wt % anti-foaming agents, and 0.1-1 wt
% colorants.
[0465] The agrochemical compositions generally comprise between
0.01 and 95%, preferably between 0.1 and 90%, and in particular
between 0.5 and 75%, by weight of active substance(s). The active
substances are employed in a purity of from 90% to 100%, preferably
from 95% to 100% (according to NMR spectrum).
[0466] Solutions for seed treatment (LS), suspoemulsions (SE),
flowable concentrates (FS), powders for dry treatment (DS),
water-dispersible powders for slurry treatment (WS), water-soluble
powders (SS), emulsions (ES), emulsifiable concentrates (EC) and
gels (GF) are usually employed for the purposes of treatment of
plant propagation materials, particularly seeds. The compositions
in question give, after two-to-tenfold dilution, active substance
concentrations of from 0.01 to 60% by weight, preferably from 0.1
to 40%, in the ready-to-use preparations. Application can be
carried out before or during sowing. Methods for applying or
treating the polymeric, ionic compound comprising imidazolium
groups and the optional compound V and compositions thereof,
respectively, on to plant propagation material, especially seeds
include dressing, coating, pelleting, dusting, soaking and
in-furrow application methods of the propagation material.
Preferably, the active compound(s) or the compositions thereof,
respectively, are applied on to the plant propagation material by a
method such that germination is not induced, e.g. by seed dressing,
pelleting, coating and dusting.
[0467] When employed in plant protection, the amounts of active
substances applied are, depending on the kind of effect desired,
from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha,
more preferably from 0.05 to 0.9 kg per ha, in particular from 0.1
to 0.75 kg per ha.
[0468] In treatment of plant propagation materials such as seeds,
e.g. by dusting, coating or drenching seed, amounts of active
substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more
preferably from 1 to 100 g and most preferably from 5 to 100 g, per
100 kilogram of plant propagation material (preferably seed) are
generally required. When used in the protection of materials or
stored products, the amount of active substance applied depends on
the kind of application area and on the desired effect. Amounts
customarily applied in the protection of materials are 0.001 g to 2
kg, preferably 0.005 g to 1 kg, of active substance per cubic meter
of treated material. Various types of oils, wetters, adjuvants,
fertilizer, or micronutrients, and further pesticides (e.g.
herbicides, insecticides, fungicides, growth regulators, safeners)
may be added to the active substances or the compositions
comprising them as premix or, if appropriate not until immediately
prior to use (tank mix). These agents can be admixed with the
compositions according to the invention in a weight ratio of 1:100
to 100:1, preferably 1:10 to 10:1.
[0469] The user applies the composition according to the invention
usually from a predosage device, a knapsack sprayer, a spray tank,
a spray plane, or an irrigation system. Usually, the agrochemical
composition is made up with water, buffer, and/or further
auxiliaries to the desired application concentration and the
ready-to-use spray liquor or the agrochemical composition according
to the invention is thus obtained. Usually, 20 to 2000 liters,
preferably 50 to 400 liters, of the ready-to-use spray liquor are
applied per hectare of agricultural useful area.
[0470] According to one embodiment, individual components of the
composition according to the invention such as parts of a kit or
parts of a binary or ternary mixture may be mixed by the user
himself in a spray tank and further auxiliaries may be added, if
appropriate.
[0471] In the compositions according to the invention containing at
least one compound V, the total weight ratio of polymeric, ionic
compound(s) comprising imidazolium groups and compound(s) V
generally depends from the properties of the active substances
used, usually it is in the range of from 1:100 to 100:1, regularly
in the range of from 1:80 to 80:1, preferably in the range of from
1:50 to 50:1, more preferably in the range of from 1:20 to 20:1,
even more preferably in the range of from 1:10 to 10:1 and in
particular in the range of from 1:4 to 4:1.
[0472] According to further embodiments of the compositions
according to the invention containing at least one compound V, the
total weight ratio of polymeric, ionic compound(s) comprising
imidazolium groups and compound(s) V usually is in the range of
from 100:1 to 1:1, regularly in the range of from 80:1 to 1:1,
preferably in the range of from 50:1 to 1:1, more preferably in the
range of from 20:1 to 1:1, even more preferably in the range of
from 10:1 to 1:1 and in particular in the range of from 4:1 to
1:1.
[0473] According to further embodiments of the compositions
according to the invention containing at least one compound V, the
total weight ratio of polymeric, ionic compound(s) comprising
imidazolium groups and compound(s) V usually is in the range of
from 1:1 to 1:100, regularly in the range of from 1:1 to 1:80,
preferably in the range of from 1:1 to 1:50, more preferably in the
range of from 1:1 to 1:20, even more preferably in the range of
from 1:1 to 1:10 and in particular in the range of from 1:1 to
1:4.
[0474] Any further active components are, if desired, added in a
ratio of from 20:1 to 1:20 to the polymeric, ionic compound(s)
comprising imidazolium groups.
[0475] In the mixtures and compositions, the compound ratios (e.g.
polymeric, ionic compound(s) comprising imidazolium groups/compound
V ratio) are advantageously chosen so as to produce a synergistic
effect, i.e. in the fungicidal composition, the fungicidal use and
method of the present invention the composition preferably contains
the at least one imidazolium compound and the at least one compound
V in synergistically effective amounts. This means that the
relative amount, i.e. the weight ratio of the at least one
imidazolium compound A and the at least one compound V in the
composition, provides for an increased fungicidal efficacy on at
least one harmful fungus which exceeds the additive fungicidal
efficacy of the compounds of the composition as calculated from the
fungicidal efficacy of the individual compounds at a given
application rate. The calculation of the additive efficacies can be
performed e.g. by Colby's formula (Colby, S. R. "Calculating
synergistic and antagonistic responses of herbicide Combinations",
Weeds, 15, 20-22, 1967). Synergism is present if the observed
efficacy is greater than the calculated efficacy.
[0476] The term "synergistic effect" is also understood to refer to
that defined by application of the Tammes method, (Tammes, P. M.
L., "Isoboles, a graphic representation of synergism in
pesticides", Netherl. J. Plant Pathol. 70, 1964).
[0477] To ensure synergism, the at least one imidazolium compound
and the at least one compound V are preferably present in the
compositions of the present invention in a total weight ratio as
already indicated above, i.e. of from 100:1 to 1:100, more
preferably from 80:1 to 1:80, even more preferably from 50:1 to
1:50, and in particular from 20:1 to 1:20.
[0478] The components can be used individually or already partially
or completely mixed with one another to prepare the composition
according to the invention. It is also possible for them to be
packaged and used as combination such as a kit of parts.
[0479] The fungicidal action of the compositions according to the
invention can be shown by the tests described below.
[0480] The active compounds, separately or jointly, are prepared as
a stock solution comprising 25 mg of active compound which is made
up to 10 ml using a mixture of acetone and/or DMSO and the
emulsifier Uniperol.RTM. EL (wetting agent having an emulsifying
and dispersing action based on ethoxylated alkylphenols) in a ratio
by volume of solvent/emulsifier of 99:1. The mixture is then made
up to 100 ml with water. This stock solution is diluted with the
solvent/emulsifier/water mixture described to give the
concentration of active compound stated below.
[0481] The visually determined percentages of infected leaf areas
are converted into efficacies in % of the untreated control.
[0482] The efficacy (E) is calculated as follows using Abbot's
formula:
E=(1-.alpha./.beta.)100
.alpha. corresponds to the fungicidal infection of the treated
plants in % and .beta. corresponds to the fungicidal infection of
the untreated (control) plants in %
[0483] An efficacy of 0 means that the infection level of the
treated plants corresponds to that of the untreated control plants;
an efficacy of 100 means that the treated plants were not
infected.
[0484] The expected efficacies of active compound combinations were
determined using Colby's formula (Colby, S. R. "Calculating
synergistic and antagonistic responses of herbicide combinations",
Weeds, 15, pp. 20-22, 1967) and compared with the observed
efficacies.
E=x+y-xy/100 Colby's formula: [0485] E expected efficacy, expressed
in % of the untreated control, when using the mixture of the active
compounds A and B at the concentrations a and b [0486] x efficacy,
expressed in % of the untreated control, when using the active
compound A at the concentration a [0487] y efficacy, expressed in %
of the untreated control, when using the active compound B at the
concentration b.
[0488] In another aspect, the invention relates to a method for
combating harmful fungi, which method comprises treating the fungi
or materials, plants, parts thereof, the locus where the plants
grow or are to grow or plants' propagation material to be protected
from fungal attack with an effective amount of at least one
polymeric, ionic compound comprising imidazolium groups
(imidazolium compound), obtainable by reacting
a) at least one .alpha.-dicarbonyl compound, b) at least one
aldehyde, c) at least one amino compound having at least two
primary amino groups, d) optionally an amino compound having only
one primary amino group and e) at least one protic acid, and
optionally subjecting the reaction product to an anion exchange,
where in the components a) and b) the aldehyde carbonyl groups may
also be present as hemiacetal or acetal and the ketone carbonyl
groups may also be present as hemiketal or ketal.
[0489] In another aspect, the invention relates to the use of at
least one polymeric, ionic compound comprising imidazolium groups
(imidazolium compound), obtainable by reacting
a) at least one .alpha.-dicarbonyl compound, b) at least one
aldehyde, c) at least one amino compound having at least two
primary amino groups, d) optionally an amino compound having only
one primary amino group and e) at least one protic acid, and
optionally subjecting the reaction product to an anion exchange,
where in the components a) and b) the aldehyde carbonyl groups may
also be present as hemiacetal or acetal and the ketone carbonyl
groups may also be present as hemiketal or ketal; for combating
harmful fungi.
[0490] Preferably, the main chain of the at least one compound
comprising imidazolium groups does not contain 1,4-bound phenylene
rings; and/or the main chain of the at least one imidazolium
compound apart from the nitrogen atoms of the imidazolium groups
does not contain any quaternary nitrogen atoms that bear 4 residues
that are different from hydrogen; and/or the amino compound having
at least two primary amino groups is not
1,3-diamino-2-hydroxy-propane or
1,3-diamino-2-hydroxy-2-methyl-propane; and/or the polymer
comprises at least 8 imidazolium rings.
[0491] In one preferred embodiment, the amino compound having at
least two primary amino groups is not 1,3-diamino-2-hydroxy-propane
or 1,3-diamino-2-hydroxy-2-methyl-propane.
[0492] In another embodiment, the polymer comprises at least 8,
preferably at least 10 imidazolium rings.
[0493] In another embodiment, the main chain of the at least one
compound comprising imidazolium groups does not contain 1,4-bound
phenylene rings
[0494] In another embodiment, the main chain of the at least one
imidazolium compound apart from the nitrogen atoms of the
imidazolium groups does not contain any quaternary nitrogen atoms
that bear 4 residues that are different from hydrogen.
[0495] In one preferred embodiment, the amino compound having at
least two primary amino groups is not 1,3-diamino-2-hydroxy-propane
or 1,3-diamino-2-hydroxy-2-methyl-propane and the polymer comprises
at least 8, preferably at least 10 imidazolium rings.
[0496] In particular, the polymer has one of the general or
preferred meanings given above in context with the biocidal
composition, and the fungicidal composition has one of the general
or preferred meanings given above for the biocidal composition;
i.e. the above-described biocidal composition is preferably a
fungicidal composition.
[0497] In a specific embodiment, the composition contains at least
one further agrochemically active compound V.
[0498] As regards suitable and preferred polymers, compositions,
compounds V, fungi, plants and ways of using the polymers and
compositions, reference is made to what has been said above.
Personal Care Composition
[0499] A further aspect of the invention is a personal care
composition, comprising [0500] A) at least one polymeric, ionic
compound comprising imidazolium groups (imidazolium compound),
obtainable by reacting [0501] a) at least one .alpha.-dicarbonyl
compound, [0502] b) at least one aldehyde, [0503] c) at least one
amino compound having at least two primary amino groups, [0504] d)
optionally an amino compound having only one primary amino group
and [0505] e) at least one protic acid, [0506] and optionally
subjecting the reaction product to an anion exchange, [0507] where
the main chain of the at least one compound comprising imidazolium
groups does not contain 1,4-bound benzene rings, specifically does
not contain benzene rings, and [0508] where in the components a)
and b) the aldehyde carbonyl groups may also be present as
hemiacetal or acetal and the ketone carbonyl groups may also be
present as hemiketal or ketal, [0509] C) optionally at least one
cosmetically acceptable active ingredient, and [0510] D) optionally
at least one cosmetically acceptable auxiliary.
[0511] Preferably, the main chain of the at least one imidazolium
compound apart from the nitrogen atoms of the imidazolium groups
does not contain any quaternary nitrogen atoms that bear 4 residues
that are different from hydrogen, either.
[0512] Suitable personal care compositions are cosmetic
compositions and hygiene compositions. With regard to suitable and
preferred embodiments of the imidazolium compound A), reference is
made to the general definition of the imidazolium compound as
defined above. Suitable and preferred embodiments of the compounds
B) and C) are mentioned in the following.
--Personal Care Composition Containing Imidazolium Compounds as
Microbiocide
[0513] The personal care composition according to the invention can
be a composition that is effective against various microorganisms.
Thus, in a first variant, the personal care composition comprises
at least one imidazolium compound as microbiocide. The personal
care compositions according this variant contains at least one
imidazolium compound A), alone or in combination with at least one
further microbicidal compound B), present at a concentration
effective to confer an antimicrobial effect on a person to whom it
is applied. According to this variant, the imidazolium compound
itself (=component A) may also act as cosmetically active
ingredient. Accordingly, in such a composition the use of a further
cosmetically acceptable active ingredient C) is only optional.
[0514] In a special embodiment, the invention relates to a personal
care composition comprising [0515] A) at least one imidazolium
compound as defined above, [0516] B) optionally at least one
further microbicidal compound different from the compounds of
component (A), [0517] C) optionally at least one cosmetically
acceptable active ingredient, and [0518] D) optionally at least one
cosmetically acceptable auxiliary, wherein the composition contains
components A) and optionally B) in an antimicrobicidal effective
amount.
[0519] An antimicrobicidal effective amount denotes an amount that
is sufficient to reduce the cell population of an unwanted
microorganism or several unwanted microorganisms under a
predetermined threshold value.
[0520] The personal care composition may comprise at least one
imidazolium compound A) as the sole antimicrobicidal effective
component. Then, the personal care composition preferably comprises
the at least one imidazolium compound A) in an amount of from 0.01
to 10 wt %, more preferably 0.05 to 5 wt %, in particular 0.1 to 1
wt %, based on the total weight of the composition. The personal
care composition may also comprise at least one imidazolium
compound A) and at least one further microbicidal compound B)
different from the compounds A) as the antimicrobicidal effective
components. Then, the personal care composition preferably
comprises the sum of components A) and B) in an amount of from 0.01
to 10 wt %, more especially 0.05 to 5 wt %, in particular 0.1 to 1
wt %, based on the total weight of the composition.
--Personal Care Composition Containing Imidazolium Compounds as
Preservative
[0521] In a second variant, the personal care composition comprises
at least one imidazolium compound as preservative. The personal
care composition according to this variant contains at least one
imidazolium compound A), alone or in combination with at least one
further microbicidal compound B), present at a concentration
effective to preserve the composition against microbes. Such
compositions are usually non-toxic, cost-effective and shelf-stable
over prolonged periods. In such a composition the imidazolium
compound itself (=component A) usually does not act as cosmetically
active ingredient. Thus, in the personal care composition according
to this second variant the use of a further cosmetically acceptable
active ingredient C) is usually mandatory.
[0522] A further aspect of the invention is a personal care
composition comprising [0523] A) at least one imidazolium compound
as defined above, [0524] B) optionally at least one further
microbicidal compound different from the compounds of component
(A), [0525] C) optionally at least one cosmetically acceptable
active ingredient, and [0526] D) optionally at least one
cosmetically acceptable auxiliary, wherein the composition contains
components A) and optionally B) in a preservative effective
amount.
[0527] A preservative effective amount denotes an amount that is
sufficient to reduce the cell population of an unwanted
microorganism under a predetermined threshold value to obtain
shelf-stability over a certain period of time. Thus, a
"preservative-effective amount" can be e.g. defined as an amount
sufficient to reduce the cell population by three log orders of the
five following microorganisms: Staphylococcus aureus, Pseudomonas
aeruginosa, Eschrechia coli, Candida albicans and Aspergillus
niger.
[0528] The personal care composition may comprise at least one
imidazolium compound A) as the sole preservative effective
component. Then, the personal care composition preferably comprises
the at least one imidazolium compound A) in an amount of from
0.00001 to 10 wt %, more preferably 0.0001 to 5 wt %, in particular
0.001 to 1 wt %, based on the total weight of the composition. The
personal care composition may also comprise at least one
imidazolium compound A) and at least one further microbicidal
compound B) different from the compounds A) as the preservative
effective components. Then, the personal care composition
preferably comprises the sum of components A) and B) in an amount
of from 0.01 to 10 wt %, more especially 0.05 to 5 wt %, in
particular 0.1 to 1 wt %, based on the total weight of the
composition.
--Personal Care Composition Containing Imidazolium Compounds to
Perform a Function in the Final Product Different from the Function
as Microbiocide or Preservative
[0529] The imidazolium compounds according to the invention can
also be advantageously employed to perform a function in the final
product different from the function as microbiocide or
preservative. The imidazolium compounds may perform this function
as an alternative to or in addition to the function as microbiocide
or preservative.
[0530] Suitable personal care compositions are: [0531] skin-care
preparations, e.g. skin-washing and cleansing preparations in the
form of tablets, liquid soaps, bar soaps, syndets, washing gels,
soapless detergents or washing pastes, [0532] bath preparations,
e.g. liquid (foam baths, milks, oils, shower preparations) or solid
bath preparations, e.g. bath cubes and bath salts; [0533] skin-care
preparations, e.g. skin emulsions, multi-emulsions, powders, sprays
or skin oils; [0534] cosmetic personal care preparations, e.g.
facial make-up in the form of day creams or powder creams, face
powder (loose or pressed), rouge or cream make-up, eye-care
preparations, e.g. eyeshadow preparations, mascara, eyeliner, eye
creams or eye-fix creams; lip-care preparations, e.g. lipsticks,
lip gloss, lip contour pencils, nail-care preparations, such as
nail varnish, nail varnish removers, nail hardeners or cuticle
removers; [0535] foot-care preparations, e.g. foot baths, foot
powders, foot creams or foot balsams, special deodorants and
antiperspirants or callus-removing preparations; [0536]
light-protective preparations, such as sun milks, lotions, creams
or oils, sunblocks or tropicals, pre-tanning preparations or
after-sun preparations; [0537] skin-tanning preparations, e.g.
self-tanning creams; [0538] depigmenting preparations, e.g.
preparations for bleaching the skin or skin-lightening
preparations; [0539] insect-repellents, e.g. insect-repellent oils,
lotions, sprays or sticks; [0540] deodorants, such as deodorant
sprays, deodorant aerosols, pump-action sprays, deodorant gels,
sticks or roll-ons, also water-free deodorant aerosols or sticks;
[0541] antiperspirants, e.g. antiperspirant sticks, creams or
roll-ons, also water-free antiperspirant aerosols and water-free
antiperspirant sticks; [0542] preparations for cleansing and caring
for blemished skin, e.g. synthetic detergents (solid or liquid),
peeling or scrub preparations or peeling masks; [0543] hair-removal
preparations in chemical form (depilation), e.g. hair-removing
powders, liquid hair-removing preparations, cream- or paste-form
hair-removing preparations, hair-removing preparations in gel form
or aerosol foams; [0544] shaving preparations, e.g. shaving soap,
foaming shaving creams, non-foaming shaving creams, foams and gels,
pre-shave preparations for dry shaving, aftershaves or aftershave
lotions; [0545] fragrance preparations, e.g. fragrances (eau de
Cologne, eau de toilette, eau de parfum, parfum de toilette,
perfume), perfume oils or perfume creams; [0546] cosmetic
hair-treatment preparations, e.g. hair-washing preparations in the
form of shampoos and conditioners, hair-care preparations, e.g.
pretreatment preparations, hair tonics, styling creams, styling
gels, pomades, hair rinses, treatment packs, intensive hair
treatments, hair-structuring preparations, e.g. hair-waving
preparations for permanent waves (hot wave, mild wave, cold wave),
hair-straightening preparations, liquid hairsetting preparations,
hair foams, hairsprays, bleaching preparations, e.g. hydrogen
peroxide solutions, lightening shampoos, bleaching creams,
bleaching powders, bleaching pastes or oils, temporary,
semi-permanent or permanent hair colorants, preparations containing
self-oxidising dyes, or natural hair colorants, such as henna or
camomile. [0547] antidandruff preparations in the form of shampoos,
conditioners, hair tonics, styling creams or gels or treatments
packs, [0548] oral care preparations such as pastes, gels, powders,
mouth washes and sprays.
[0549] A preferred embodiment is a personal care composition,
comprising [0550] A) at least one polymeric, ionic compound
comprising imidazolium groups (imidazolium compound), obtainable by
reacting [0551] a) at least one .alpha.-dicarbonyl compound, [0552]
b) at least one aldehyde, [0553] c) at least one amino compound
having at least two primary amino groups, [0554] d) optionally an
amino compound having only one primary amino group and [0555] e) at
least one protic acid, [0556] and optionally subjecting the
reaction product to an anion exchange, [0557] where the main chain
of the at least one compound comprising imidazolium groups does not
contain 1,4-bound benzene rings; specifically does not contain
benzene rings, and [0558] where in the components a) and b) the
aldehyde carbonyl groups may also be present as hemiacetal or
acetal and the ketone carbonyl groups may also be present as
hemiketal or ketal, [0559] C) optionally at least one cosmetically
acceptable active ingredient, and [0560] D) optionally at least one
cosmetically acceptable auxiliary.
[0561] Preferably, the main chain of the at least one imidazolium
compound apart from the nitrogen atoms of the imidazolium groups
does not contain any quaternary nitrogen atoms that bear 4 residues
that are different from hydrogen, either.
[0562] With regard to suitable and preferred embodiments of
component A), reference is made to the afore-mentioned general
definition of the imidazolium compounds employed according to the
invention. With regard to suitable and preferred embodiments of
cosmetically acceptable components C) and D), reference is made to
the following general definition of those components.
[0563] Some appropriate personal care compositions include
deodorants, antiperspirants, skin care products for facial, foot,
hand and whole body uses, sun protection products, personal
cleaning products, hair care products, feminine hygiene products,
oral care products and decorative cosmetics such as lipsticks,
mascara, facial makeup cremes and rouge.
[0564] Suitable cosmetic compositions may exist in a wide variety
of forms, for example: [0565] in the form of liquid preparations as
a W/O, O/W, O/W/O, W/O/W or PIT emulsion and all kinds of
microemulsions, [0566] in the form of a gel, [0567] in the form of
an oil, a cream, milk or lotion, [0568] in the form of a powder, a
lacquer, a tablet or make-up, [0569] in the form of a stick, [0570]
in the form of a spray (spray with propellant gas or pump-action
spray) or an aerosol, [0571] in the form of a foam, or [0572] in
the form of a paste.
[0573] The cosmetic compositions may be, for example, creams, gels,
lotions, alcoholic and aqueous/alcoholic solutions, emulsions,
wax/fat compositions, stick preparations, powders or ointments.
[0574] As water- and oil-containing emulsions (e.g. W/O, O/W, O/W/O
and W/O/W emulsions or microemulsions) the preparations contain,
for example, from 0.1 to 30% by weight, preferably from 0.1 to 15%
by weight and especially from 0.5 to 10% by weight, based on the
total weight of the composition, of one or more UV absorbers, from
1 to 60% by weight, especially from 5 to 50% by weight and
preferably from 10 to 35% by weight, based on the total weight of
the composition, of at least one oil component, from 0 to 30% by
weight, especially from 1 to 30% by weight and preferably from 4 to
20% by weight, based on the total weight of the composition, of at
least one emulsifier, from 10 to 90% by weight, especially from 30
to 90% by weight, based on the total weight of the composition, of
water, and from 0 to 88.9% by weight, especially from 1 to 50% by
weight, of further cosmetically acceptable adjuvants.
[0575] The cosmetic composition may also contain one or one more
additional components C) and/or D), as described below.
[0576] Of special importance are cosmetic preparations for the
hair, especially with the purpose of antidandruff treatment are the
above-mentioned preparations for hair treatment, especially
hair-washing preparations in the form of shampoos, hair
conditioners, hair-care preparations, e.g. pre-treatment
preparations, hair tonics, styling creams, styling gels, pomades,
hair rinses, treatment packs, intensive hair treatments,
hair-straightening preparations, liquid hair-setting preparations,
hair foams and hairsprays. Of special interest are hair-washing
preparations in the form of shampoos.
[0577] A shampoo has, for example, the following composition:
from 0.01 to 5% by weight of the at least one component A), 12.0%
by weight of sodium laureth-2-sulfate, 4.0% by weight of
cocamidopropyl betaine, 3.0% by weight of sodium chloride, and
water ad 100%.
[0578] For example, especially the following hair-cosmetic
formulations may be used: [0579] a1) spontaneously emulsifying
stock formulation, consisting of the antibacterial composition
according to the above disclosure, PEG-6-C.sub.10oxoalcohol and
sorbitan sesquioleate, to which water and any desired quaternary
ammonium compound, for example 4% minkamidopropyl
dimethyl-2-hydroxyethylammonium chloride or Quaternium 80 is added;
[0580] a2) spontaneously emulsifying stock formulation consisting
of the antibacterial composition according to the above disclosure,
tributyl citrate and PEG-20-sorbitan monooleate, to which water and
any desired quaternary ammonium compound, for example 4%
minkamidopropyl dimethyl-2-hydroxyethylammonium chloride or
Quaternium 80 is added; [0581] b) quat-doped solutions of the
antibacterial composition as disclosed above in butyl triglycol and
tributyl citrate; [0582] c) mixtures or solutions of the
antibacterial composition as disclosed above with
n-alkylpyrrolidone.
[0583] As used herein "cosmetically acceptable medium" means a
medium which is non-toxic, non-irritating and otherwise suitable
for contact with the surfaces of a human or other vertebrate body.
Such surfaces include the hair, skin, mouth, anal, urethral and
vaginal surfaces. Whether a composition is physiologically
acceptable can be determined by tests well known to those of skill
in the art.
[0584] A further aspect of the invention is a method of using the
present personal care composition. The methods include contacting
the personal care compositions with a part of the human body. In
general, the method comprises applying the personal care
composition to a body surface or part to be treated.
[0585] The term "applying" includes an appropriate action on the
part of the user to contact the personal care composition to the
body part. Applying includes, in some embodiments, spreading,
spraying, squirting, wiping and brushing. The particular type of
application depends on the body part to which the personal care
composition is to be applied.
[0586] "Body part" means a part of body including the mouth and
other epithelial surfaces of the body. Thus the term body part
includes hair, skin and mouth, anus, urethra and vagina. In the
case of the skin, the body part is often more specific. For
example, in some embodiments the body part is the skin of the face,
hand or foot. In other embodiments, the body part is the whole
body. In other embodiments, for example where the personal care
compositions are deodorants or antiperspirants, body part can be
the underarms.
[0587] Preferably, the cosmetic composition comprises the
components A) and, if present, B) in a fraction of from about 0.001
to 50% by weight, particularly preferably 0.01 to 30% by weight, in
particular 0.05 to 20% by weight, based on the total weight of the
composition.
Cosmetically Acceptable Components C) and D) (General
Definition)
[0588] The components C) and D) of the cosmetic composition are
preferably chosen from cosmetically acceptable carriers,
emulsifiers, surfactants, perfume oils, rheology modifiers
(thickeners), hair polymers, hair and skin conditioners,
water-soluble or dispersible silicone-comprising polymers,
bleachers, gelling agents, care agents, colorants, tinting agents,
tanning agents, dyes, pigments, antidandruff agents, sunscreen
agents, deodorizing active substances, vitamins, plant extracts,
bodying agents, humectants, refatting agents, collagen, protein
hydrolysates, lipids, antioxidants, antifoaming agents, antistatic
agents, emollients, softeners, etc.
[0589] A comprehensive description of cosmetic auxiliaries is found
in H. P. Fiedler, Lexikon der Hilfsstoffe fur Pharmazie, Kosmetik
and angrenzende Gebiete [Encyclopedia of Auxiliaries for
Pharmaceuticals, Cosmetics and Related Fields], 4th edition,
Aulendorff: ECV-Editio-Cantor-Verlag, 1996. A comprehensive
description of cosmetic raw materials, auxiliaries and active
substances, and also suitable formulations, are additionally found
in K. Schrader, Grundlagen and Rezepturen der Kosmetika
[Fundamental Principles and Formulations of Cosmetics], 2nd
edition, Huthig-Verlag, Heidelberg (1989).
[0590] A cosmetically acceptable medium comprises at least one
cosmetically acceptable carrier. The cosmetic compositions
preferably have a carrier component D) which is chosen from water,
hydrophilic components, hydrophobic components and mixtures
thereof.
[0591] Suitable hydrophilic carriers D) are, for example, mono-,
di- or polyhydric alcohols having preferably 1 to 8 carbon atoms,
such as ethanol, n-propanol, isopropanol, propylene glycol,
glycerol, sorbitol, etc.
[0592] Suitable hydrophobic carriers D) are preferably chosen
from
i) oils, fats, waxes, ii) esters of C.sub.6-C.sub.30-monocarboxylic
acids with mono-, di- or trihydric alcohols which are different
from iii), iii) saturated acyclic and cyclic hydrocarbons, iv)
fatty acids, v) fatty alcohols, vi) propellant gases, and mixtures
thereof.
[0593] Suitable silicone oils D) are volatile and non-volatile
silicone oils. The term "volatile oil" means an oil capable of
evaporating from the skin or the lips in less than one hour, and
especially having a vapor pressure, at room temperature and
atmospheric pressure, ranging from 10.sup.-3 to 300 mm Hg (0.13 Pa
to 40,000 Pa).
[0594] Suitable silicone oils D) are for example, linear
polydimethylsiloxanes, poly(methylphenylsiloxanes), optionally
substituted with aliphatic and/or aromatic groups, which are
optionally fluorinated, or with functional groups, such as
hydroxyl, thiol and/or amine groups. Suitable silicone oils D) are
also cyclic siloxanes. The number-average molecular weight of the
polydimethylsiloxanes and poly(methylphenylsiloxanes) is preferably
in a range from about 1000 to 150 000 g/mol. Preferred cyclic
siloxanes have 4- to 8-membered rings. Suitable cyclic siloxanes
are commercially available, for example, under the name
cyclomethicone.
[0595] As volatile silicone oils that may be used in the invention,
mention may be made of linear or cyclic silicones containing from 2
to 7 silicon atoms, these silicones optionally comprising alkyl or
alkoxy groups containing from 1 to 10 carbon atoms. Mention may be
made in particular of octamethylcyclotetrasiloxane,
decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane,
heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane,
octamethyltrisiloxane and decamethyltetrasiloxane, and mixtures
thereof. Among the non-volatile silicone oils that may be mentioned
are non-volatile polydialkylsiloxanes, such as non-volatile
polydimethylsiloxanes (PDMS); polydimethylsiloxanes comprising
alkyl, alkoxy or phenyl groups, which are pendent or at the end of
a silicone chain, these groups containing from 2 to 24 carbon
atoms; phenyl silicones, for instance phenyl trimethicones, phenyl
dimethicones, phenyl trimethyl-siloxy diphenylsiloxanes, diphenyl
dimethicones, diphenyl methyldiphenyltrisiloxanes and
polymethylphenylsiloxanes; polysiloxanes modified with fatty acids
(especially of C.sub.8-C.sub.20), fatty alcohols (especially of
C.sub.8-C.sub.20) or polyoxyalkylenes (especially polyoxy-ethylene
and/or polyoxypropylene); amino polysiloxanes; polysiloxanes
containing hydroxyl groups; fluoro poly-siloxanes comprising a
fluorinated group that is pendent or at the end of a silicone
chain, containing from 1 to 12 carbon atoms, all or some of the
hydrogen atoms of which are replaced with fluorine atoms; and
mixtures thereof.
[0596] Preferred oil and fat components D) are chosen from paraffin
and paraffin oils; vaseline; natural fats and oils, such as castor
oil, soya oil, peanut oil, olive oil, sunflower oil, sesame oil,
avocado oil, cocoa butter, almond oil, peach kernel oil, ricinus
oil, cod-liver oil, pig fat, spermaceti, spermaceti oil, sperm oil,
wheatgerm oil, macadamia nut oil, evening primrose oil, jojoba oil;
fatty alcohols, such as lauryl alcohol, myristyl alcohol, cetyl
alcohol, stearyl alcohol, oleyl alcohol, cetyl alcohol; fatty
acids, such as myristic acid, stearic acid, palmitic acid, oleic
acid, linoleic acid, linolenic acid and saturated, unsaturated and
substituted fatty acids different therefrom; waxes, such as
beeswax, carnauba wax, candililla wax, spermaceti, and mixtures of
the abovementioned oil and fat components.
[0597] Suitable cosmetically and pharmaceutically compatible oil
and fat components D) are described in Karl-Heinz Schrader,
Grundlagen and Rezepturen der Kosmetika [Fundamentals and
formulations of cosmetics], 2nd edition, Verlag Huthig, Heidelberg,
pp. 319-355, which is hereby incorporated by reference.
[0598] Suitable cosmetically active substances C) are, for example,
skin and hair pigmentation agents, tanning agents, bleaches,
keratin-hardening substances, antimicrobial active substances,
photofilter active substances, repellent active substances,
hyperemic substances, keratolytic and keratoplastic substances,
antidandruff active substances, antiphlogistics, keratinizing
substances, active substances which act as antioxidants and/or as
free-radical scavengers, skin moisturizing or humectant substances,
refatting active substances, deodorizing active substances,
sebostatic active substances, plant extracts, antierythimatous or
antiallergic active substances and mixtures thereof.
[0599] Artificially skin-tanning active substances C) which are
suitable for tanning the skin without natural or artificial
irradiation with UV rays are, for example, dihydroxyacetone,
alloxan and walnut shell extract. Suitable keratin-hardening
substances are generally active substances as are also used in
antiperspirants, such as, for example, potassium aluminum sulfate,
aluminum hydroxychloride, aluminum lactate, etc. Antimicrobial
active substances are used in order to destroy microorganisms
and/or to inhibit their growth and thus serve both as preservatives
and also as deodorizing substance which reduces the formation or
the intensity of body odor. These include, for example, customary
preservatives known to the person skilled in the art, such as
p-hydroxybenzoates, imidazolidinylurea, formaldehyde, sorbic acid,
benzoic acid, salicylic acid, etc. Such deodorizing substances are,
for example, zinc ricinoleate, triclosan, undecylenic acid
alkylolamides, triethyl citrate, chlorhexidine etc. Suitable
photofilter active substances are substances which absorb UV rays
in the UV-B and/or UV-A region. Suitable UV filters are those
specified above. Also suitable are p-aminobenzoic esters, cinnamic
esters, benzophenones, camphor derivatives, and pigments which stop
UV rays, such as titanium dioxide, talc and zinc oxide. Suitable
repellent active substances are compounds which are able to keep or
drive certain animals, in particular insects, away from people.
These include, for example, 2-ethyl-1,3-hexanediol,
N,N-diethyl-m-toluamide, etc. Suitable hyperemic substances which
stimulate blood flow in the skin are, for example, essential oils,
such as dwarf-pine, lavender, rosemary, juniper berry, horse
chestnut extract, birch leaf extract, hay flower extract, ethyl
acetate, camphor, menthol, peppermint oil, rosemary extract,
eucalyptus oil, etc. Suitable keratolytic and keratoplastic
substances are, for example, salicylic acid, calcium thioglycolate,
thioglycolic acid and its salts, sulfur, etc. Suitable antidandruff
active substances are, for example, sulfur, sulfur polyethylene
glycol sorbitan monooleate, sulfur ricinol polyethoxylate, zinc
pyrithione, aluminum pyrithione, etc. Suitable antiphlogistics,
which counteract skin irritations, are, for example, allantoin,
bisabolol, dragosantol, camomile extract, panthenol, etc.
[0600] The compositions according to the invention can comprise, as
active substance C) at least one polymer. These include, very
generally, anionic, cationic, amphoteric and neutral polymers.
[0601] Suitable anionic polymers C) for the personal care
compositions according to the invention are generally all anionic
polymers known for this application. The composition according to
the invention preferably comprises at least one soluble or
dispersed anionic polymer. The anionic polymers that may be
employed include, but are not limited to, polymers comprising
groups derived from carboxylic acids, sulfonic acids or phosphoric
acids. Preferably, the anionic polymers have a number-average
molecular mass in a range from 500 to 5 000 000.
[0602] The anionic polymers C) used in the personal care
compositions according to the invention are preferably selected
from:
A) Homo- or copolymers of acrylic or methacrylic acid or salts
thereof. Examples are the products sold under the names
VERSICOL.RTM. E or K by the company Allied Colloid and
ULTRAHOLD.RTM. by BASF SE. Further preferred anionic polymers C)
are the copolymers of acrylic acid and acrylamide and salts
thereof. Examples are the products sold in the form of their sodium
salt under the names RETEN.RTM. 421, 423 or 425 by the company
Hercules. Further preferred anionic polymers C) are the sodium
salts of polyhydroxycarboxylic acids; B) Copolymers of acrylic or
methacrylic acids with a monoethylenic monomer, such as ethylene,
styrene, vinyl esters and acrylic or methacrylic acid esters,
optionally grafted onto a polyalkylene glycol, such as polyethylene
glycol and optionally crosslinked. Such polymers are described, for
example, in French patent 1 222 944 and German patent application
No. 2 330 956. Suitable are also copolymers whose polymer chain
comprises acrylamide units that are optionally N-alkylated and/or
hydroxyalkylated. Examples are the polymers described, e.g. in the
Luxembourg patent applications 75370 and 75371 or sold under the
name QUADRAMER.RTM. by the company American Cyanamid. Suitable are
also copolymers of acrylic acid and at least one
(C.sub.1-C.sub.4)alkyl methacrylate, the copolymer of methacrylic
acid and ethyl acrylate sold under the name LUVIMER.RTM. MAE.RTM.
by BASF SE; the terpolymer of tert-butyl acrylate, ethyl acrylate
and methacrylic acid sold under the name LUVIMER.RTM. 100 P
LUVIMER.RTM. 36 D and LUVIMER.RTM. 30 E by BASF SE, the copolymer
of N-tert.-butylacrylamide, ethyl acrylate, acrylic acid (Ultrahold
strong); C) Copolymers derived from crotonic acid, such as those
whose chain comprises vinyl acetate or propionate units and
optionally other monomers, such as allylic or methallylic esters,
vinyl ether or vinyl ester of a saturated, linear or branched
carboxylic acid comprising a long hydrocarbon-based chain, such as
those comprising at least 5 carbon atoms, it being possible for
these polymers to be grafted and/or crosslinked, or alternatively a
vinyl, allylic or methallylic ester of an [alpha]- or [beta]-cyclic
carboxylic acid. Preferred copolymers of vinyl acetate, crotonic
acid and optionally at least one further vinyl ester are the
Luviset.RTM. trademarks of BASF SE. Such polymers are also
described, inter alia, in French patents 1 222 944, 1 580 545, 2
265 782, 2 265 781, 1 564 110 and 2 439 798. Further commercial
products falling within this category are the resins 28-29-30,
26-13-14 and 28-13-10 sold by National Starch; D) Polymers derived
from maleic, fumaric or itaconic acids or anhydrides with vinyl
esters, vinyl ethers, vinyl halides, phenylvinyl derivatives or
acrylic acid and its esters. The polymers of this category may be
esterified. Such polymers are described e.g. in U.S. Pat. Nos.
2,047,398, 2,723,248, and 2,102,113 and GB patent 839 805. Suitable
commercially available products are e.g. polymers sold under the
names GANTREZ.RTM. AN or ES by the company ISP. Polymers also
falling within this category are the copolymers of maleic,
citraconic or itaconic anhydrides and of an allylic or methallylic
ester optionally comprising an acrylamide or methacrylamide group,
an [alpha]-olefin, acrylic or methacrylic esters, acrylic or
methacrylic acid or vinylpyrrolidone in their chain, the anhydride
functions being monoesterified or monoamidated. These polymers are
described, for example, in French patents 2 350 384 and 2 357 241
by the applicant; E) Polyacrylamides comprising carboxylate groups;
F) Polymers comprising sulfonic groups are polymers comprising
vinylsulfonic, styrenesulfonic, naphthalenesulfonic or
acrylamidoalkylsulfonic units. These polymers can be chosen, for
example, from: polyvinylsulfonic acid salts with a molecular weight
in a range from 1000 to 100 000, and also copolymers with an
unsaturated comonomer, such as acrylic or methacrylic acids and
esters thereof, and also acrylamide or derivatives thereof, vinyl
ethers and vinylpyrrolidone; polystyrenesulfonic acid salts, the
sodium salts having a molecular weight in a range from 500 000 to
100 000, sold, respectively, under the names FLEXAN.RTM. 500 and
FLEXAN.RTM. 130 by National Starch. These compounds are described
in patent FR 2 198 719; and polyacrylamidesulfonic acid salts, such
as those mentioned in U.S. Pat. No. 4,128,631 and, for example,
polyacrylamidoethylpropanesulfonic acid sold under the name
COSMEDIA POLYMER.RTM. HSP 1180 by Henkel.
[0603] Preferred examples of anionic polymers C) are homopolymers
and copolymers of acrylic acid and methacrylic acid or salts
thereof, copolymers of acrylic acid and acrylamide and salts
thereof; sodium salts of polyhydroxycarboxylic acids, water-soluble
or water-dispersible polyesters, polyurethanes, e.g. Luviset
PUR.RTM. from BASF, and polyureas. Particularly suitable polymers
are copolymers of t-butyl acrylate, ethyl acrylate, methacrylic
acid (e.g. Luvimer.RTM. 100P), copolymers of ethyl acrylate and
methacrylic acid (e.g. Luvimer.RTM. MAE), copolymers of
N-tert-butylacrylamide, ethyl acrylate, acrylic acid
(Ultrahold.RTM. 8, strong), copolymers of vinyl acetate, crotonic
acid and if appropriate further vinyl esters (e.g. Luviset.RTM.
grades), maleic anhydride copolymers, if appropriate reacted with
alcohol, anionic polysiloxanes, e.g. carboxyfunctional ones,
t-butyl acrylate, methacrylic acid (e.g. Luviskol.RTM. VBM),
copolymers of acrylic acid and methacrylic acid with hydrophobic
monomers, such as, for example, C.sub.4-C.sub.30-alkyl esters of
(meth)acrylic acid, C.sub.4-C.sub.30-alkylvinyl esters,
C.sub.4-C.sub.30-alkyl vinyl ethers and hyaluronic acid. Examples
of anionic polymers are also vinyl acetate/crotonic acid
copolymers, as are sold, for example, under the names Resyn.RTM.
(National Starch) and Gafset.RTM. (GAF), and vinylpyrrolidone/vinyl
acrylate copolymers obtainable, for example, under the trade name
Luviflex.RTM. (BASF). Further suitable polymers are the
vinylpyrrolidone/acrylate terpolymer obtainable under the name
Luviflex.RTM. VBM-35 (BASF) and polyamides containing sodium
sulfonate or polyesters containing sodium sulfonate. Also suitable
are vinylpyrrolidone/ethyl methacrylate/methacrylic acid
copolymers, as are sold by Stepan under the names Stepanhold-Extra
and -R1, and the Carboset.RTM. grades from BF Goodrich. A further
preferred example of an anionic polymer C) is a methyl
methacrylate/methacrylic acid/acrylic acid/urethane acrylate
copolymer. Those polymers are commercially available as Luviset
Shape.RTM. (INCI Name: Polyacrylate-22) from BASF SE. Luviset Shape
is designed e.g. for aqueous hair sprays to provide a fast-drying,
non-tacky, long-lasting hold.
[0604] Suitable cationic polymers C) are polymers different from
the imidazolium compounds according to the invention (=component
A). The cationic polymer C) may be chosen in principle from all
cationic polymers known to a person skilled in the art as suitable
for cosmetic compositions. Cationic polymers for compositions for
improving the cosmetic properties of the hair are for example those
described in patent applications EP-A-0 337 354 FR-A-2 270 846,
FR-2 383 660, FR-2 598 611, FR-2 470 596 and FR-2 519 863. For the
purposes of the present invention, the term "cationic polymer"
denotes any polymer comprising at least one cationic group or at
least one cationogenic group that may be ionized into a cationic
group. The at least one cationic polymer may be chosen from those
containing units comprising primary, secondary, tertiary, and/or
quaternary amine groups that either may form part of the main
polymer chain or may be borne by a side substituent directly
attached thereto.
[0605] Suitable cationic polymers C) are, for example:
[0606] (1) Homopolymers or copolymers derived from acrylic or
methacrylic esters or amides and comprising at least one of the
units of the following formulae:
##STR00012##
wherein: R3, which may be identical or different, is chosen from a
hydrogen atom and a CH.sub.3 radical; A, which may be identical or
different, is chosen from linear or branched alkyl groups
comprising from 1 to 6 carbon atoms, for example from 2 to 3 carbon
atoms, and hydroxyalkyl groups comprising from 1 to 4 carbon atoms;
R.sub.4, R.sub.5 and R.sub.6, which may be identical or different,
are chosen from alkyl groups comprising from 1 to 18 carbon atoms
and a benzyl radical, and in at least one embodiment, R.sub.4,
R.sub.5 and R.sub.6, which may be identical or different, are
chosen from alkyl groups comprising from 1 to 6 carbon atoms;
R.sub.1 and R2, which may be identical or different, are chosen
from hydrogen and alkyl groups comprising from 1 to 6 carbon atoms,
for example methyl or ethyl; and X.sup.- is chosen from anions
derived from a mineral or organic acid, such as a methosulfate
anion, and halides, such as chloride or bromide.
[0607] The copolymers of group (1) may also comprise at least one
unit derived from comonomers that may be chosen from the family of
acrylamides, methacrylamides, diacetone acrylamides, acrylamides,
and methacrylamides substituted on the nitrogen with lower
(C.sub.1-C.sub.4)alkyls, acrylic or methacrylic acids or esters
thereof, vinyllactams, such as vinylpyrrolidone or
vinylcaprolactam, and vinyl esters.
[0608] Suitable members of group (1) are:
Copolymers of acrylamide and of dimethylaminoethyl methacrylate
quaternized with dimethyl sulfate or with a dimethyl halide, the
copolymers of acrylamide and of
methacryloyloxyethyltrimethylammonium chloride described, for
example, in EP-A-0 080 976, the copolymers of acrylamide and of
methacryloyloxyethyltrimethylammonium methosulfate, quaternized or
nonquaternized vinylpyrrolidone/dialkylaminoalkyl acrylate or
methacrylate copolymers, such as those described in FR patents 2
077 143 and 2 393 573, dimethylaminoethyl
methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymers,
vinylpyrrolidone/methacrylamidopropyldimethylamine copolymers, and
quaternized vinylpyrrolidone/dimethylaminopropylmethacrylamide
copolymers.
[0609] (2) Cationic polysaccharides, for example non-limiting
mention may be made of cationic celluloses and cationic
galactomannan gums. In at least one embodiment, the cationic
polysaccharides are cellulose ether derivatives comprising
quaternary ammonium groups, cationic cellulose copolymers or
cellulose derivatives grafted with a water-soluble quaternary
ammonium monomer and cationic galactomannan gums.
[0610] (3) Polymers comprising piperazinyl units and divalent
alkylene or hydroxyalkylene radicals comprising straight or
branched chains, optionally interrupted by oxygen, sulfur or
nitrogen atoms or by aromatic or heterocyclic rings, and also the
oxidation and/or quaternization products of these polymers.
[0611] (4) Water-soluble polyamino amides prepared, as non-limiting
example, by polycondensation of an acidic compound with a
polyamine; these polyamino amides can be crosslinked with an
epihalohydrin, a diepoxide, a dianhydride, an unsaturated
dianhydride, a bis-unsaturated derivative, a bis-halohydrin, a
bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide or
alternatively with an oligomer resulting from the reaction of a
difunctional compound which is reactive with a bis-halohydrin, a
bis-azetidinium, a bis-haloacyidiamine, a bis-alkyl halide, an
epihalohydrin, a diepoxide or a bis-unsaturated derivative; the
crosslinking agent being used in proportions ranging from 0.025 to
0.35 mol per amine group of the polyamino amide; these polyamino
amides can be alkylated or, if they contain at least one tertiary
amine function, they can be quaternized.
[0612] (5) Polyaminoamide derivatives resulting from the
condensation of polyalkylene polyamines with polycarboxylic acids
followed by alkylation with difunctional agents. Non-limiting
mention may be made, for example, of adipic
acid/dialkylamino-hydroxyalkyldialkylenetriamine polymers wherein
the alkyl radical comprises from 1 to 4 carbon atoms, such as
methyl, ethyl or propyl. Among these derivatives, non-limiting
mention may be made of the adipic
acid/dimethylaminohydroxypropyl/diethylenetriamine polymers.
[0613] (6) Polymers obtained by reaction of a polyalkylene
polyamine comprising two primary amine groups and at least one
secondary amine group with a dicarboxylic acid chosen from
diglycolic acid and saturated aliphatic dicarboxylic acids
comprising from 3 to 8 carbon atoms.
[0614] (7) Cyclopolymers of alkyldiallylamine or of
dialkyldiallylammonium, such as the homopolymers or copolymers
comprising, as main constituent of the chain, units corresponding
to formula
##STR00013##
wherein k and t are equal to 0 or 1, the sum k+t being equal to 1;
R.sub.12 is chosen from a hydrogen atom and a methyl radical;
R.sub.10 and R.sub.11, which may be identical or different, are
chosen from alkyl groups comprising from 1 to 6 carbon atoms,
hydroxyalkyl groups wherein the alkyl group, for example, comprises
from 1 to 5 carbon atoms, and lower (C.sub.1-C.sub.4)amidoalkyl
groups, or R.sub.10 and R.sub.11, together with the nitrogen atom
to which they are attached, are chosen from heterocyclic groups
such as piperidyl or morpholinyl; and Y.sup.- is an anion such as
bromide, chloride, acetate, borate, citrate, tartrate, bisulfate,
bisulfite, sulfate or phosphate.
[0615] Such polymers (7) are described, for example, in FR patent 2
080 759 and in its Certificate of Addition 2 190 406.
[0616] In at least one embodiment, R.sub.10 and R.sub.11, which may
be identical or different, are chosen from alkyl groups comprising
from 1 to 4 carbon atoms.
[0617] Among the polymers defined above, non-limiting mention may
be made, for example, of the dimethyldiallylammonium chloride
homopolymers sold under the name MERQUAT.RTM. 100 by the company
Nalco (and its homologs of low weight-average molar mass) and
copolymers of diallyldimethylammonium chloride and of
acrylamide.
[0618] (8) Quaternary diammonium polymers containing repeating
units corresponding to the formula (6):
##STR00014##
wherein: R.sub.13, R.sub.14, R.sub.15 and R.sub.16, which may be
identical or different, are chosen from aliphatic, alicyclic or
arylaliphatic radicals comprising from 1 to 20 carbon atoms, and
lower hydroxyalkylaliphatic radicals such as hydroxyethyl, or
R.sub.13, R.sub.14, R.sub.15 and R.sub.16, together or separately,
constitute, with the nitrogen atoms to which they are attached,
heterocycles optionally comprising a second heteroatom other than
nitrogen, or R.sub.13, R.sub.14, R.sub.15 and R.sub.16 are chosen
from a linear or branched (C.sub.1-C.sub.6)alkyl radical
substituted with a nitrile, ester, acyl, or amide group, and a
group --CO--O--R.sub.17-D or --CO--NH--R.sub.17-D, wherein R.sub.17
is an alkylene and D is a quaternary ammonium group; A.sub.1 and
B.sub.1 are chosen from polymethylene groups comprising from 2 to
20 carbon atoms, wherein the polymethylene groups may be linear or
branched, saturated or unsaturated, and wherein the polymethylene
groups may comprise, linked to or intercalated in the main chain,
at least one aromatic ring, at least one oxygen or sulfur atom, or
sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl,
quaternary ammonium, ureido, amide or ester groups, and X.sup.- is
an anion derived from a mineral or organic acid; or A.sub.1,
R.sub.13 and R.sub.15 can form, with the two nitrogen atoms to
which they are attached, a piperazine ring; in addition, if A.sub.1
is chosen from a linear or branched, saturated or unsaturated
alkylene or hydroxyalkylene radical, B.sub.1 is chosen from
polymethylene groups comprising from 2 to 20 carbon atoms, wherein
the polymethylene groups may be linear or branched, saturated or
unsaturated, and wherein the polymethylene groups may comprise,
linked to or intercalated in the main chain, at least one aromatic
ring, at least one oxygen or sulfur atom, sulfoxide, sulfone,
disulfide, amino, alkylamino, hydroxyl, quaternary ammonium,
ureido, amide or ester groups, and a group
(CH.sub.2).sub.n--CO-D-OC--(CH.sub.2).sub.n--; wherein D is chosen
from: a) a glycol residue of formula: --O--Z--O--, wherein Z is
chosen from a linear or branched hydrocarbon-based radical, and a
group corresponding to one of the following formulae:
--(CH.sub.2--CH.sub.2--O).sub.x--CH.sub.2--CH.sub.2-- or
--[CH.sub.2--CH(CH.sub.3)--O].sub.y--CH.sub.2--CH(CH.sub.3)--
wherein x and y are integers ranging from 1 to 4, which is a
defined and unique degree of polymerization or an average degree of
polymerization; b) a bis-secondary diamine residue, such as a
piperazine derivative; c) a bis-primary diamine residue of formula:
--NH--Y--NH--, wherein Y is chosen from a linear or branched
hydrocarbon-based-radical, and the divalent radical
--CH.sub.2--CH.sub.2--S--S--CH.sub.2--CH.sub.2--; and
d) a ureylene group of formula: --NH--CO--NH--; and n is an integer
ranging from 1 to 20, for example from 1 to 10.
[0619] In at least one embodiment, X.sup.- is an anion such as
chloride or bromide.
[0620] These polymers can have a number-average molar mass in a
range from 1000 to 100 000.
[0621] In at least one embodiment, polymers that consist of
repeating units corresponding to formula (a) are used:
##STR00015##
wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4, which may be
identical or different, are chosen from alkyl and hydroxyalkyl
radicals comprising from 1 to 4 carbon atoms, n and p are integers
ranging from 2 to 20, and X.sup.- is an anion derived from a
mineral or organic acid.
[0622] In at least one embodiment, R.sub.1, R.sub.2, R.sub.3 and
R.sub.4 are chosen from a methyl radical and n=3, p=6 and X=Cl.
Such a polymer is known as hexadimethrine chloride according to the
INCI (CTFA) nomenclature.
[0623] (9) Polyquaternary ammonium polymers comprised of units of
formula (7):
##STR00016##
wherein: R.sub.18, R.sub.19, R.sub.20 and R.sub.21, which may be
identical or different, are chosen from a hydrogen atom, and
methyl, ethyl, propyl, [beta]-hydroxyethyl, [beta]-hydroxypropyl
and --CH.sub.2CH.sub.2(OCH.sub.2CH.sub.2).sub.pOH radicals, wherein
p is equal to 0 or to an integer ranging from 1 to 6, with the
proviso that R.sub.18, R.sub.19, R.sub.20 and R.sub.21 do not
simultaneously represent a hydrogen atom, r and s, which may be
identical or different, are integers ranging from 1 to 6, q is an
integer ranging from 1 to 34, X.sup.- is an anion such as a halide,
A is chosen from a dihalide radical and
--CH.sub.2--CH.sub.2--O--CH.sub.2--CH.sub.2--. In at least one
embodiment, A is --CH.sub.2--CH.sub.2--O--CH.sub.2--CH.sub.2--.
[0624] Non-limiting examples of such compounds are described in
patent application EP-A-122 324.
[0625] Non-limiting examples include the products MIRAPOL.RTM. A15,
MIRAPOL.RTM. (R) AD1, MIRAPOL.RTM. AZ1 and MIRAPOL.RTM. 175 sold by
the company Miranol.
[0626] (10) Quaternary polymers of vinyllactam (vinylpyrrolidone
and/or vinylcaprolactam) and of vinylimidazole.
[0627] (11) Crosslinked polymers of
methacryloyloxy(C.sub.1-C.sub.4)alkyltri(C.sub.1-C.sub.4)alkyl-ammonium
salts, such as the polymers obtained by homopolymerization of
dimethylaminoethyl methacrylate quaternized with methyl chloride,
or by copolymerization of acrylamide with dimethylaminoethyl
methacrylate quaternized with methyl chloride, the homo- or
copolymerization being followed by crosslinking with a compound
containing olefinic unsaturation, for example
methylenebisacrylamide.
[0628] Other cationic polymers C) that can be used in the context
of the disclosure are cationic proteins or cationic protein
hydrolysates, polyalkyleneimines, for example non-limiting mention
may be made of polyethyleneimines, polymers containing
vinylpyridine or vinylpyridinium units, condensates of polyamines
and of epichlorohydrin, quaternary polyureylenes and chitin
derivatives.
[0629] Preferred cationic polymers C) are polymers with the INCI
name Polyquaternium, e.g. copolymers of
vinylpyrrolidone/N-vinylimidazolium salts (Luviquat.RTM. FC,
Luviquat.RTM. HM, Luviquat.RTM. MS, Luviset Clear.RTM., Luviquat
Supreme.RTM., Luviquat.RTM. Care), copolymers of
N-vinylpyrrolidone/dimethylaminoethyl methacrylate, quaternized
with diethyl sulfate (Luviquat.RTM. PQ 11), copolymers of
N-vinylcaprolactam/N-vinylpyrrolidone/N-vinylimidazolium salts
(Luviquat.RTM. Hold); cationic cellulose derivatives
(Polyquaternium-4 and -10), acrylamido copolymers
(Polyquaternium-7) and chitosan. Suitable cationic (quaternized)
polymers are also Merquat.RTM. (polymer based on
dimethyldiallylammonium chloride), Gafquat.RTM. (quaternary
polymers which are formed by reacting polyvinylpyrrolidone with
quaternary ammonium compounds), Polymer JR (hydroxyethylcellulose
with cationic groups) and cationic polymers based on plants, e.g.
guar polymers, such as the Jaguar.RTM. grades from Rhodia.
[0630] Suitable neutral polymers C) are e.g. polyvinylpyrrolidones,
copolymers of N-vinylpyrrolidone and vinyl acetate and/or vinyl
propionate, polysiloxanes, polyvinylcaprolactam and other
copolymers with N-vinylpyrrolidone, polyethyleneimines and salts
thereof, polyvinylamines and salts thereof, cellulose derivatives,
polyaspartic acid salts and derivatives. These include, for
example, Luviflex.RTM. Swing (partially saponified copolymer of
polyvinyl acetate and polyethylene glycol, BASF).
[0631] Suitable polymers C) are also nonionic, water-soluble or
water-dispersible polymers or oligomers, such as
polyvinylcaprolactam, e.g. Luviskol.RTM. Plus (BASF), or
polyvinylpyrrolidone and copolymers thereof, in particular with
vinyl esters, such as vinyl acetate, e.g. Luviskol.RTM. VA 37
(BASF); polyamides, e.g. based on itaconic acid and aliphatic
diamines, as are described, for example, in DE-A-43 33 238.
[0632] Suitable polymers C) are also amphoteric or zwitterionic
polymers, such as the octylacrylamide/methyl
methacrylate/tert-butylaminoethyl methacrylate/2-hydroxypropyl
methacrylate copolymers obtainable under the names Amphomer.RTM.
(National Starch), and zwitterionic polymers, as are disclosed, for
example, in the German patent applications DE 39 29 973, DE 21 50
557, DE 28 17 369 and DE 37 08 451.
Acrylamidopropyltrimethylammonium chloride/acrylic acid or
methacrylic acid copolymers and alkali metal and ammonium salts
thereof are preferred zwitterionic polymers. Further suitable
zwitterionic polymers are methacroylethylbetaine/methacrylate
copolymers, which are commercially available under the name
Amersette.RTM. (AMERCHOL), and copolymers of hydroxyethyl
methacrylate, methyl methacrylate, N,N-dimethylaminoethyl
methacrylate and acrylic acid (Jordapon.RTM.).
[0633] Suitable polymers C) are also nonionic, anionic, cationic or
amphoteric siloxane-containing, polymers. Suitable are in principle
organomodified and non-organomodified silicones. Siloxane
containing polymers are typical cosmetically acceptable agents that
are beneficial to keratin material. The silicones that can be used
in accordance with the invention may be soluble or insoluble in the
composition. They may be in the form of oils, waxes, resins or
gums. Non-limiting examples of the organopolysiloxanes are defined
in greater detail in Walter Noll's "Chemistry and Technology of
Silicones" (1968) Academic Press. They can be volatile or
nonvolatile. With regard to volatile silicones, reference is made
to the volatile silicone oils mentioned above. Volatile silicones
are preferably chosen from those having a boiling point in a range
from 60.degree. C. to 260.degree. C.
[0634] Examples of volatile silicones are:
(i) Cyclic silicones comprising from 3 to 7 and for example from 4
to 5 silicon atoms. These are, for example, but not limited to,
octamethylcyclotetrasiloxane sold under the name Volatile Silicone
7207 by Union Carbide or SILBIONE.RTM. 70045 V 2 by Rhodia,
decamethylcyclopentasiloxane sold under the name Volatile Silicone
7158 by Union Carbide, and SILBIONE.RTM. 70045 V 5 by Rhodia, and
mixtures thereof.
[0635] Suitable are also cyclocopolymers of the
dimethylsiloxane/methylalkylsiloxane type, such as Volatile
Silicone FZ 3109 sold by the company Union Carbide, having the
general chemical structure:
##STR00017##
with
##STR00018##
[0636] Suitable are also mixtures of cyclic silicones with
organosilicone compounds, such as the mixture of
octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol
(50/50) and the mixture of octamethylcyclotetrasiloxane and
oxy-1,1'-bis(2,2,2',2',3,3'-hexa-trimethylsilyloxy)neopentane;
(ii) Linear volatile silicones comprising from 2 to 9 silicon atoms
and having a viscosity of less than or equal to 5.times.10.sup.-6
m.sup.2/s at 25.degree. C. A non-limiting example is
decamethyltetrasiloxane sold under the name SH 200 by the company
Toray Silicone. Silicones belonging to this category are also
described in Todd & Byers "Volatile Silicone Fluids for
Cosmetics", Cosmetics and Toiletries, Vol. 91, Jan. 76, pp.
27-32.
[0637] Further examples of nonvolatile silicones that are suitable
as component C) include polyalkylsiloxanes, polyarylsiloxanes,
polyalkylarylsiloxanes, silicone gums and resins,
polyorganosiloxanes modified with organofunctional groups, and also
mixtures thereof.
[0638] Organomodified silicones that can be used in accordance with
the invention are silicones as defined above and comprising in
their structure at least one organofunctional group attached via a
hydrocarbon-based group.
[0639] Examples of organomodified silicones are polyorganosiloxanes
comprising:
Polyethyleneoxy and/or polypropyleneoxy groups optionally
comprising (C.sub.6-C.sub.24)alkyl groups. Such polyorganosiloxanes
are commercially available, such as the products known as
dimethicone copolyol sold by the company Dow Corning under the name
DC 1248, SILWET.RTM. L 722, L 7500, L 77 and L 711 by the company
Union Carbide, and the (C.sub.12alkyl)methicone copolyol sold by
the company Dow Corning under the name Q2 5200; suitable nonionic
siloxane-containing polymers C) are also polyether siloxanes, such
as the Tegopren.RTM. trademarks (Goldschmidt) or Belsil.RTM.
trademarks (Wacker); substituted or unsubstituted amine groups.
Such polyorganosiloxanes with substituted or unsubstituted amine
groups are commercially available, such as the products sold under
the name GP 4 Silicone Fluid and GP 7100 by the company Genesee, or
the products sold under the names Q2 8220 and Dow Corning 929 or
939 by the company Dow Corning. The substituted amine groups are,
for example, (C.sub.1-C.sub.4)aminoalkyl groups; thiol groups. Such
polyorganosiloxanes with thiol groups are commercially available,
e.g. the products sold under the names GP 72 A and GP 71 from
Genesee; alkoxylated groups. Such polyorganosiloxanes with
alkoxylated groups are commercially available, such as the product
sold under the name Silicone Copolymer F-755 by SWS Silicones and
ABIL WAX.RTM. 2428, 2434 and 2440 by the company Goldschmidt;
hydroxylated groups. Such polyorganosiloxanes with alkoxylated
groups are commercially available, e.g. the polyorganosiloxanes
comprising a hydroxyalkyl function, described in French patent
application FR-A-85/16334; acyloxyalkyl groups. Such
polyorganosiloxanes with acyloxyalkyl groups are commercially
available, e.g. the polyorganosiloxanes described in U.S. Pat. No.
4,957,732; anionic groups of the carboxylic acid type. Such
polyorganosiloxanes with anionic groups of the carboxylic acid type
are commercially available, e.g. the products described in patent
EP 186 507 from the company Chisso Corporation; anionic groups of
the alkylcarboxylic type. Such polyorganosiloxanes with anionic
groups of the alkylcarboxylic type are commercially available, e.g.
those present in the product X-22-3701E from the company Shin-Etsu;
2-hydroxyalkyl sulfonate groups; 2-hydroxyalkyl thiosulfate groups.
Such polyorganosiloxanes with 2-hydroxyalkyl thiosulfate are
commercially available, e.g. such as the products sold by the
company Goldschmidt under the names ABIL.RTM. S201 and ABIL.RTM.
S255; and hydroxyacylamino groups. Such polyorganosiloxanes with
2-hydroxyalkyl thiosulfate are commercially available, e.g. the
polyorganosiloxanes described in patent application EP 342 834.
Non-limiting mention may be made, for example, of the product
Q2-8413 from the company Dow Corning.
[0640] The personal care compositions according to the invention
may comprise as component C) at least one polyisobutene or
poly(.alpha.-olefin), chosen from those that are well known in the
art. A preferred product is Luvitol Lite (INCI Name: Hydrogenated
Polyisobutene) from BASF SE. Polyisobutenes and
poly(.alpha.-olefins) can be used advantageously as a hair and skin
conditioner. E.g. Luvitol Lite provides on the skin a pleasant soft
feeling without being oily. Polyisobutenes and
poly(.alpha.-olefins) can also be used as a conditioner in hair
products, such as shampoos and body washes, hair styling and
conditioning applications. They contribute to properties, such as
manageability, wet and dry comb, and shine. Finally, below is a
simple example of Luvitol Lite's use in a shampoo type formula with
more than 60% oil, which, I suspect, does not foam very much.
[0641] In addition to the abovementioned constituents, the personal
care compositions according to the invention can also comprise at
least one surface-active substance as component D). The
surface-active substances include surfactants, dispersing agents
and wetting agents.
[0642] Suitable are anionic, cationic, nonionic and amphoteric
surfactants, including polymer surfactants and surfactants with
heteroatoms in the hydrophobic group.
[0643] The following list of suitable and preferred surfactants is
not limited to the application in personal care compositions but is
applicable to all biocide compositions according to the
invention.
[0644] Non-limiting examples of anionic surfactants useful in
embodiments of the compositions of the present invention are
disclosed in McCutcheon's, Detergents and Emulsifiers, North
American edition (1990), published by The Manufacturing
Confectioner Publishing Co.; McCutcheon's, Functional Materials,
North American Edition (1992); and U.S. Pat. No. 3,929,678, to
Laughlin et al., issued Dec. 30, 1975, all of which are
incorporated herein by reference.
[0645] Non-limiting examples of anionic surfactants useful in
embodiments of the compositions of the present invention are
disclosed in McCutcheon's, Detergents and Emulsifiers, North
American edition (1990), published by The Manufacturing
Confectioner Publishing Co.; McCutcheon's, Functional Materials,
North American Edition (1992); and U.S. Pat. No. 3,929,678, to
Laughlin et al., issued Dec. 30, 1975, all of which are
incorporated herein by reference.
[0646] Nonlimiting examples of anionic surfactants include alkyl
and alkyl ether sulfates; sulfated monoglycerides; sulfonated
olefins; alkyl aryl sulfonates; primary or secondary alkane
sulfonates; alkyl sulfosuccinates; acyl taurates; acyl
isethionates; alkyl glycerylether sulfonate; sulfonated methyl
esters; sulfonated fatty acids; alkyl phosphates; acyl glutamates;
acyl sarcosinates; alkyl sulfoacetates; acylated peptides; alkyl
ether carboxylates; acyl lactylates; anionic fluorosurfactants; and
mixtures thereof. Mixtures of anionic surfactants can be used
effectively in some embodiments of the present disclosure.
[0647] Suitable anionic surfactants for use in personal care
compositions according to the invention include alkyl sulfates and
alkyl ether sulfates. Suitable components have the general formulae
R.sup.11--O--SO.sub.3-M and
R.sup.11--(CH.sub.2H.sub.4--O).sub.x--O--SO.sub.3-M, wherein
R.sup.11 is a saturated or unsaturated, branched or unbranched
alkyl group from about 8 to about 24 carbon atoms, x is 1 to 10,
and M is a water-soluble cation such as ammonium, sodium,
potassium, magnesium, triethanolamine, diethanolamine and
monoethanolamine. The alkyl sulfates are typically made by the
sulfation of monohydric alcohols (having from about 8 to about 24
carbon atoms) using sulfur trioxide or other known sulfation
technique. The alkyl ether sulfates are typically made as
condensation products of ethylene oxide and monohydric alcohols
(having from about 8 to about 24 carbon atoms) and then sulfated.
These alcohols can be derived from fats, for example, coconut oil
or tallow, or can be synthetic. Specific examples of alkyl sulfates
which are useful in some embodiments of inventive cleanser
compositions are sodium, ammonium, potassium, magnesium, or TEA
salts of lauryl or myristyl sulfate. Examples of alkyl ether
sulfates include ammonium, sodium, magnesium, or TEA laureth-3
sulfate.
[0648] Another suitable class of anionic surfactants are sulfated
monoglycerides of the general formula
R.sup.12--CO--O--CH.sub.2--C(OH)H--CH.sub.2--O--SO.sub.3-M, wherein
R.sup.12 is a saturated or unsaturated, branched or unbranched
alkyl group from about 8 to about 24 carbon atoms, and M is a
water-soluble cation such as ammonium, sodium, potassium,
magnesium, triethanolamine, diethanolamine and monoethanolamine.
These are typically made by the reaction of glycerin with fatty
acids (having from about 8 to about 24 carbon atoms) to form a
monoglyceride and the subsequent sulfation of this monoglyceride
with sulfur trioxide. An example of a sulfated monoglyceride is
sodium cocomonoglyceride sulfate.
[0649] Other suitable anionic surfactants include olefin sulfonates
of the general formula R.sup.13SO.sub.3-M, wherein R.sup.13 is a
mono-olefin having from about 12 to about 24 carbon atoms, and M is
a water-soluble cation, such as ammonium, sodium, potassium,
magnesium, triethanolamine, diethanolamine and monoethanolamine.
These compounds can be produced by the sulfonation of -olefins by
means of uncomplexed sulfur trioxide, followed by neutralization of
the acid reaction mixture in conditions, such that any sulfones
which have been formed in the reaction are hydrolyzed to give the
corresponding hydroxyalkanesulfonate. An example of a sulfonated
olefin is sodium C14/C16-olefin sulfonate.
[0650] Other suitable anionic surfactants are the linear
alkylbenzene sulfonates of the general formula
R.sup.14--C.sub.6H.sub.4--SO.sub.3-M, wherein R.sup.14 is a
saturated or unsaturated, branched or unbranched alkyl group from
about 8 to about 24 carbon atoms, and M is a water-soluble cation
such as ammonium, sodium, potassium, magnesium, triethanolamine,
diethanolamine and monoethanolamine. These are formed by the
sulfonation of linear alkyl benzene with sulfur trioxide. An
example of this anionic surfactant is sodium dodecylbenzene
sulfonate.
[0651] Further suitable anionic surfactants (in particular for the
cleansing compositions) include primary or secondary alkane
sulfonates of the form R.sup.15--SO.sub.3-M, wherein R.sup.15 is a
saturated or unsaturated, branched or unbranched alkyl chain from
about 8 to about 24 carbon atoms, and M is a water-soluble cation
such as ammonium, sodium, potassium, magnesium, triethanolamine,
diethanolamine and monoethanolamine. These are commonly formed by
the sulfonation of paraffins using sulfur dioxide in the presence
of chlorine and ultraviolet light or another known sulfonation
method. The sulfonation can occur in either the secondary or
primary positions of the alkyl chain. An example of an alkane
sulfonate useful herein is alkali metal or ammonium
C.sub.13-C.sub.17 paraffin sulfonates.
[0652] Further suitable anionic surfactants are alkyl
sulfosuccinates, which include disodium
N-octadecylsulfosuccinamate; diammonium lauryl sulfosuccinate;
tetrasodium N-(1,2-dicarboxyethyl)-N-octadecylsulfosuccinate;
diamyl ester of sodium sulfosuccinic acid; dihexyl ester of sodium
sulfosuccinic acid; and dioctyl esters of sodium sulfosuccinic
acid.
[0653] Also useful are taurates which are based on taurine, which
is also known as 2-aminoethanesulfonic acid. Examples of taurates
include N-alkyltaurines, such as the one prepared by reacting
dodecylamine with sodium isethionate, according to the teaching of
U.S. Pat. No. 2,658,072 which is incorporated herein by reference
in its entirety. Other examples of taurine derivatives that are
useful in embodiments of the disclosure include the acyl taurines
formed by the reaction of n-methyl taurine with fatty acids (having
from about 8 to about 24 carbon atoms).
[0654] Further suitable anionic surfactants are acyl isethionates.
The acyl isethionates typically have the formula
R.sup.16--CO--O--CH.sub.2--CH.sub.2SO.sub.3-M, wherein R.sup.16 is
a saturated or unsaturated, branched or unbranched alkyl group
having from about 10 to about 30 carbon atoms, and M is a cation.
These are typically formed by the reaction of fatty acids (having
from about 8 to about 30 carbon atoms) with an alkali metal
isethionate. Nonlimiting examples of these acyl isethionates
include ammonium cocoyl isethionate, sodium cocoyl isethionate,
sodium lauroyl isethionate, and mixtures thereof.
[0655] Further suitable anionic surfactants are alkylglyceryl ether
sulfonates of the form
R.sup.17--OCH.sub.2--C(OH)H--CH.sub.2--SO.sub.3-M, wherein R.sup.17
is a saturated or unsaturated, branched or unbranched alkyl group
from about 8 to about 24 carbon atoms, and M is a water-soluble
cation, such as ammonium, sodium, potassium, magnesium,
triethanolamine, diethanolamine and monoethanolamine. These can be
formed by the reaction of epichlorohydrin and sodium bisulfite with
fatty alcohols (having from about 8 to about 24 carbon atoms) or
other known methods. One example is sodium cocoglyceryl ether
sulfonate.
[0656] Further suitable anionic surfactants are sulfonated fatty
acids of the general formula R.sub.18--CH(SO.sub.4)--COOH and
sulfonated methyl esters of the general formula
R.sup.18--CH(SO.sub.4)--CO--O--CH.sub.3, where R.sup.18 is a
saturated or unsaturated, branched or unbranched alkyl group from
about 8 to about 24 carbon atoms. These surfactants are generally
formed by the sulfonation of fatty acids or alkyl methyl esters
(having from about 8 to about 24 carbon atoms) with sulfur trioxide
or by other known sulfonation techniques. Examples include alpha
sulfonated coconut fatty acid and lauryl methyl ester.
[0657] Further suitable anionic surfactants are phosphates, such as
monoalkyl-, dialkyl-, and trialkylphosphate salts formed by the
reaction of phosphorous pentoxide with monohydric branched or
unbranched alcohols having from about 8 to about 24 carbon atoms.
In some embodiments, these anionic materials are also be formed by
other known phosphation methods. An example from this class of
surfactants is sodium mono or dilaurylphosphate.
[0658] Further suitable anionic surfactants are acyl glutamates
corresponding to the formula
R.sup.19--CO--N(COOH)--CH.sub.2CH.sub.2--CO.sub.2-M, wherein
R.sup.19 is a saturated or unsaturated, branched or unbranched
alkyl or alkenyl group of about 8 to about 24 carbon atoms, and M
is a water 46 soluble cation. Nonlimiting examples of which include
sodium lauroyl glutamate and sodium cocoyl glutamate.
[0659] Further suitable anionic surfactants are alkanoyl
sarcosinates corresponding to the formula
R.sup.20--CON(CH.sub.3)--CH.sub.2CH.sub.2--CO.sub.2-M, wherein
R.sup.20 is a saturated or unsaturated, branched or unbranched
alkyl or alkenyl group of about 10 to about 20 carbon atoms, and M
is a watersoluble cation. Nonlimiting examples of which include
sodium lauroyl sarcosinate, sodium cocoyl sarcosinate, and ammonium
lauroyl sarcosinate. Other anionic materials include alkyl ether
carboxylates corresponding to the formula
R.sup.21--(OCH.sub.2CH.sub.2).sub.x--OCH.sub.2--CO.sub.2-M, wherein
R.sup.21 is a saturated or unsaturated, branched or unbranched
alkyl or alkenyl group of about 8 to about 24 carbon atoms, x is 1
to 10, and M is a water-soluble cation. Nonlimiting examples of
which include sodium laureth carboxylate. Other anionic materials
include acyl lactylates corresponding to the formula
R.sup.22--CO--[O--CH(CH.sub.3)--CO].sub.x--CO.sub.2-M, wherein
R.sup.22 is a saturated or unsaturated, branched or unbranched
alkyl or alkenyl group of about 8 to about 24 carbon atoms, x is 3,
and M is a water-soluble cation, nonlimiting examples of which
include sodium cocoyl lactylate. Other anionic materials include
the carboxylates, nonlimiting examples of which include sodium
lauroyl carboxylate, sodium cocoyl carboxylate, and ammonium
lauroyl carboxylate. Anionic fluorosurfactants can also be used. A
counter cation, M, counterbalances the negative charge of the
anionic surfactant. Some especially suitable counter cations are
sodium, potassium, ammonium, monoethanolamine, diethanolamine, and
triethanolamine. An especially suitable counter cation is
ammonium.
[0660] Suitable non-ionic surfactants for use in personal care
compositions according to the invention are condensation products
of ethylene oxide with various reactive hydrogen-containing
compounds reactive therewith having long hydrophobic chains (for
example aliphatic chains of about 12-20 carbon atoms) which
condensation products ("ethoxamers") contain hydrophilic
polyoxyethylene moieties, such as condensation products of
poly(ethyleneoxide) with fatty acids, fatty alcohols, fatty amides,
polyhydric alcohols (for example sorbitan monostearate) and
polypropylene oxide (for example Pluronic a materials). Polyoxamers
include for example block copolymers of polyoxyethylene and
polyoxypropylene having an average molecular weight from about 3000
to 5000 and a preferred average molecular weight from about 3500 to
4000 and containing about 10 to 80% hydrophilic polyoxyethylene
groups, by weight, of the block copolymer (for example Pluronic
F127). Other non-ionic surfactants are for example alkyl
polyglucosids, alcanolamides, ethers of e.g. fatty acids with
ethylene oxid or polyethylenglycol, amine oxids e.g.
cocamidopropyla amine oxid.
[0661] Suitable amphoteric surfactants for use in personal care
compositions according to the invention are secondary or tertiary
aliphatic amine derivatives, where the aliphatic chain can be
linear or branched and contains at least 8 to 22 carbon atoms and
one anionic group, such as carboxylate, sulfonate, sulfate,
phosphate or phosphonate. Suitable amphoteric surfactants are also
acyl/dialkyl ethylenediamines, such as acylamphoacetate, disodium
acylamphodipropionate, sodium acylamphohydroxypropylsulfonate,
disodium acylamphodiacetate, sodium acylamphopropionate, where acyl
represents either an alkyl or alkenyl, mono- or polyunsaturated
residue containing 5 to 29 carbon atoms. Suitable amphoteric
surfactants are also N-alkyl amino acids or imino acids, such as
aminopropyl alkylglutamide, alkylaminopropionic acid, sodium
alkylimino propionate, alkyl glycinates and carboxyglycinates, e.g.
sodium cocoglycinate. Suitable amphoteric surfactants are also
C.sub.8-C.sub.18-betains, C.sub.8-C.sub.18-sulfobetains,
C.sub.8-C.sub.24-alkylamido-C.sub.1-C.sub.4-alkylene betains,
imidazoline carboxylates, alkylamphocarboxycarbonic acids,
alkylamphocarbonic acid (for example lauroamphoglycinate) and
N-alkyl-.beta.-aminopropionate or
N-alkyl-.beta.-iminodi-propionate. Preferably, the amphoteric
surfactant comprises
C.sub.10-C.sub.20-alkylamido-C.sub.1-C.sub.4-alkylenbetaine and/or
coco fatty acid amide propylbetaine.
[0662] Suitable thickening polymers useful herein as rheology
modifier D) include anionic polymers, cationic polymers, amphoteric
polymers and nonionic polymers. The thickening polymers useful
herein include, for example, acrylic polymers, polyalkylene glycol
polymers having a molecular weight of more than about 10 000,
celluloses and derivatives thereof, such as hydroxyethyl cellulose,
polyvinylpyrrolidone, polyvinyl alcohol, gums, such as guar gum and
xanthan gum, carragenan, pectin, agar, quince seed (Cydonia oblonga
Mill), starch (rice, corn, potato, wheat), algae colloids (algae
extract), dextran, succinoglucan, pulleran, carboxymethyl starch,
methylhydroxypropyl starch, sodium alginate, and alginic acid
propylene glycol esters. Neutralizing agents may be included to
neutralize the anionic thickening agents described hereinabove.
Nonlimiting examples of such neutralizing agents include sodium
hydroxide, potassium hydroxide, ammonium hydroxide,
monoethanolamine, diethanolamine, triethanolamine,
diisopropanolamine, aminomethylpropanol, trimethamine,
tetrahydroxypropyl ethylenediamine, and mixtures thereof.
[0663] Preferred thickening polymers useful herein as rheology
modifier D) include acrylic polymers. Acrylic polymers useful
herein include those comprising monomers selected from the group
consisting of acrylic acid, salts of acrylic acid, derivatives of
acrylic acid, methacrylic acid, salts of methacrylic acid,
derivatives of methacrylic acid, and mixtures thereof. The
derivatives include, for example, alkyl acrylate, acrylamide, alkyl
methacrylate, and methacrylamide. Such acrylic polymers include,
for example, cross linked acrylic acid polymers with the CTFA name
Carbomer, sodium polyacrylate, polyethylacrylate, polyacrylamide,
and acrylic acid/alkyl acrylate copolymers with the CTFA name
Acrylates/C.sub.10-30 Alkyl Acrylate Crosspolymer. Commercially
available acrylic polymers highly useful herein include, for
example, polyacrylamide with tradename Sepigel 305 available SEPPIC
Inc., and Acrylates/C.sub.10-30 Alkyl Acrylate Crosspolymer having
tradenames Pemulen TR-I, Pemulen TR-2, Carbopol 1342, Carbopol
1382, and Carbopol ETD 2020, all available from B.F. Goodrich
Company.
[0664] Suitable thickening polymers useful herein as rheology
modifier D) include also so called associative polymers. Suitable
associative polymers are mentioned in the following.
[0665] Preferred thickening polymers useful herein as rheology
modifier D) are also the following products that are commercially
available from BASF SE and Cognis corporation:
Rheocare TTA (2-methyl-2-propenoic acid polymer with butyl
2-propenoate and ethyl 2-propenoate, CAS-No. 31069-81-5),
LUVIGEL.RTM. grades, inter alia LUVIGEL.RTM. advance (cross-linked
cationic rheology modifier), LUVIGEL.RTM. EM (milky emulsion of
sodium acrylates copolymer in caprylic/capric triglyceride and
water) and LUVIGEL.RTM. STAR (non-ionic, electrolyte tolerant,
polyurethane-based associative rheology modifier).
[0666] A cationic-compatible liquid rheology modifier that is
especially suitable as component D) for the personal care
compositions of the invention is a cationic polymer with the INCI
name polyacrylate-1 crosspolymer. They are commercially available
under the trade mark Carbopol Aqua CC from Noveon Inc. The
Polyacrylate-1 Crosspolymer is the product of the polymerization of
a mixture of monomers comprising (or constituted of): [0667] a
di(C.sub.1-C.sub.4 alkyl)amino(C.sub.1-C.sub.6 alkyl)methacrylate,
[0668] at least one (meth)acrylic acid C.sub.1-C.sub.30 alkyl
ester, [0669] a polyethoxylated C.sub.10-C.sub.30 alkyl
methacrylate (20-25 mol of ethylene oxide unit), [0670] a
polyethylene glycol/polypropylene glycol 30/5 alkyl ether, [0671] a
hydroxyl(C.sub.2-C.sub.6 alkyl)methacrylate, and [0672] an ethylene
glycol dimethacrylate.
[0673] The imidazolium compounds according to the invention can be
employed advantageously in detergent cosmetic compositions employed
for cleansing and caring the hair or the skin.
[0674] A first special embodiment of the invention is a cosmetic
composition, comprising in a cosmetically acceptable medium [0675]
at least one imidazolium compound (=component A), [0676] at least
one surfactant and [0677] at least one cosmetically acceptable
active ingredient that is beneficial to keratin materials.
[0678] With regard to suitable and preferred embodiments of
component A), reference is made to the aforementioned general
definition of the imidazolium compounds employed according to the
invention. The at least one imidazolium compound (=component A) may
be used in combination with at least one further cationic polymer
different from the compounds of component (A). With regard to
suitable and preferred additional cationic polymers, reference is
made to the cationic polymers mentioned before as component C).
[0679] With regard to suitable and preferred surfactants, reference
is made to the surfactants mentioned before as component D).
Suitable surfactants and in particular combinations of surfactants
are disclosed in US 2009/0048132 A1 which is incorporated herein by
reference.
[0680] The at least one cosmetically acceptable active ingredient
that is beneficial to keratin materials is preferably selected
from:
(1) hydrolyzed or nonhydrolyzed, modified or unmodified
saccharides, oligosaccharides and polysaccharides, (2) hydrolyzed
or nonhydrolyzed, modified or unmodified amino acids,
oligopeptides, peptides and proteins, (3) branched or unbranched
fatty acids and alcohols, (4) animal, plant and mineral waxes, (5)
ceramides and pseudoceramides, (6) hydroxylated organic acids, (7)
UV-screening agents, (8) antioxidants and free-radical scavengers,
(9) chelating agents, (10) antidandruff agents, (11) seborrhea
regulators, (12) calmatives, (13) cationic surfactants, (14)
organomodified and non-organomodified silicones, (15) mineral,
plant and animal oils, (16) polyisobutenes and
poly([alpha]-olefins), (17) fatty esters, for example those
comprising from 15 to 50 carbon atoms, (18) soluble and dispersed
anionic polymers, and (19) soluble and dispersed nonionic polymers,
and mixtures thereof.
[0681] Suitable compounds (1)-(19) are described in US 2009048132
A1 which is incorporated herein by reference.
[0682] A second special embodiment of the invention is a cosmetic
composition comprising in a cosmetically acceptable medium [0683]
at least one imidazolium compound (=component A), and [0684] at
least one associative polymer.
[0685] Preferably, the composition according to the second special
embodiment further comprises at least one surfactant. With regard
to suitable and preferred surfactants, reference is made to the
surfactants mentioned before as component D).
[0686] Preferably, the composition according to the second special
embodiment further comprises at least one conditioning agent.
Preferably, the at least one conditioning agent is chosen from
silicones, cationic polymers other than the imidazolium compounds
of the present disclosure, mineral, plant, and animal oils,
ceramides, pseudoceramides, poly-.alpha.-olefins, fluoro oils,
fluoro waxes, fluoro gums, carboxylic acid esters, etc. Preferably,
the at least one conditioning agent is present in an amount ranging
from 0.001% to 20% by weight, more preferably 0.01% to 10% by
weight, based the total weight of the composition. In particular,
the conditioner is a rinse-out or leave-in conditioner.
[0687] Preferably, the composition according to the second special
embodiment is in the form of a foaming detergent composition or a
conditioner. In particular, the foaming detergent composition is a
shampoo, shower gel, makeup-removing product, or bubble bath.
[0688] With regard to suitable and preferred embodiments of
component A), reference is made to the aforementioned general
definition of the imidazolium compounds employed according to the
invention. The at least one imidazolium compound (=component A) may
be used in combination with at least one further cationic polymer
different from the compounds of component (A). With regard to
suitable and preferred additional cationic polymers, reference is
made to the cationic polymers mentioned before as component C).
[0689] With regard to suitable and preferred associative polymers,
reference is made to WO 2010/023411 A2 which is incorporated herein
by reference. Suitable cationic associative polymers and anionic
associative polymers are also disclosed in US 2009/0074692 A1 which
is incorporated herein by reference. Preferred associative polymers
can be obtained by polymerization of a monomer mixture comprising
at least one associative vinyl monomer. Non-limiting examples of
the at least one include (meth)acrylates of polyalkoxylated
C.sub.8-C.sub.30 fatty alcohols and mixtures thereof. Preferred
associative vinyl monomers are polyethoxylated cetyl
(meth)acrylates, polyethoxylated cetearyl (meth)acrylates,
polyethoxylated stearyl (meth)acrylates, polyethoxylated arachidyl
(meth)acrylates, polyethoxylated behenyl (meth)acrylates, and
polyethoxylated lauryl (meth)acrylates. The polyalkoxylated portion
of the associative monomer comprises preferably from 10 to 80, such
as from 15 to 40, and such as from 20 to 35 alkylene oxide units,
selected from ethylene oxide, propylene oxide and mixtures thereof.
Preferably, the polyalkoxylated portion of the associative monomer
comprises from 10 to 80, more preferably from 15 to 40, and in
particular from 20 to 35 ethylene oxide units.
[0690] In a preferred embodiment, the at least one associative
polymer is selected from anionic associative polymers. Preferably,
the composition comprises the at least associative polymer in an
amount of from 1 to 50 wt %, more preferably of from 2 to 25 wt %,
based on the total weight of the composition.
[0691] A third special embodiment is an antidandruff composition,
comprising in a cosmetically acceptable medium [0692] at least one
imidazolium compound (=component A), and [0693] optionally at least
one antidandruff agent different from the imidazolium compound.
[0694] With regard to suitable and preferred embodiments of
component A), reference is made to the aforementioned general
definition of the imidazolium compounds employed according to the
invention. The at least one imidazolium compound (=component A) may
be used in combination with at least one further cationic polymer
different from the compounds of component (A). With regard to
suitable and preferred additional cationic polymers, reference is
made to the cationic polymers mentioned before as component C).
[0695] Preferably, the composition according to the third special
embodiment further comprises at least one surfactant. With regard
to suitable and preferred surfactants, reference is made to the
surfactants mentioned before as component D). The surfactant is
generally present in the composition according to the third special
embodiment in an amount ranging from 0.1% to 60% by weight
approximately, preferably from 3% to 40% and even more preferably
from 5% to 30%, relative to the total weight of the
composition.
[0696] The antidandruff agent which is different from the
imidazolium compounds are chosen in particular from: [0697] 1)
Pyridinethione salts, in particular the calcium, magnesium, barium,
strontium, zinc, cadmium, tin and zirconium salts. The zinc salt of
pyridinethione is particularly preferred. The zinc salt of
pyridinethione is sold in particular under the name ZINC OMADINE by
the company OLIN. [0698] 2) 1-Hydroxy-2-pyrrolidone derivatives
represented by formula (IV):
[0698] ##STR00019## [0699] wherein: [0700] R.sub.9 is chosen from
an alkyl group containing from 1 to 17 carbon atoms, an alkenyl
group containing from 2 to 17 carbon atoms, a cycloalkyl group
containing from 5 to 8 carbon atoms, a bicycloalkyl group
containing from 7 to 9 carbon atoms, a cycloalkyl(alkyl) group, an
aryl group wherein the aryl may have as possible substituents a
halogen group, a nitro group, and a cyano group, an aralkyl group
wherein the alkyl contains from 1 to 4 carbon atoms, an arylalkenyl
group wherein the alkenyl contains from 2 to 4 carbon atoms, an
aryloxyalkyl wherein the alkyl contains from 1 to 4 carbon atoms,
arylmercaptoalkyl group wherein the alkyl contains from 1 to 4
carbon atoms, a furylalkenyl group wherein the alkenyl contains
from 2 to 4 carbon atoms or wherein the furyl contains from 2 to 4
carbon atoms, an alkoxy group containing from 1 to 4 carbon atoms,
a nitro group, a cyano group and a halogen atom; [0701] R.sub.10 is
chosen from a hydrogen atom, a (C.sub.1-C.sub.4) alkyl group, a
(C.sub.2-C.sub.4) alkenyl group, a halogen atom, a phenyl group,
and a benzyl group; and [0702] X.sup.+ is chosen from a quaternized
organic base, an alkali metal ion, alkaline-earth metal ion, and an
ammonium ion.
[0703] Compounds of formula (IV) are, for example,
1-hydroxy-4-methyl-2-pyridone, 1-hydroxy-6-methyl-2-pyridone,
1-hydroxy-4,6-dimethyl-2-pyridone,
1-hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2-pyridone,
1-hydroxy-4-methyl-6-cyclohexyl-2-pyridone,
1-hydroxy-4-methyl-6-(methylcyclohexyl)-2-pyridone,
1-hydroxy-4-methyl-6-(2-bicyclo (2,2,1) heptyl)-2-pyridone,
1-hydroxy-4-methyl-6-(4-methylphenyl)-2-pyridone,
1-hydroxy-4-methyl-6-(1-(4-nitrophenoxy)butyl)-2-pyridone,
1-hydroxy-4-methyl-6-(4-cyanophenoxymethyl)-2-pyridone,
1-hydroxy-4-methyl-6-(phenyl-sulphonylmethyl)-2-pyridone or
1-hydroxy-4-methyl-6-(4-bromobenzyl)-2-pyridone.
[0704] The compounds of formula (IV) can be used in the form of
salts with organic or inorganic bases. Examples of organic bases
are, in particular, alkanolamines of low molecular weight, such as
ethanolamine, diethanolamine, N-ethylethanolamine, triethanolamine,
diethylaminoethanol and 2-amino-2-methylpropanediol; non-volatile
bases, such as ethylenediamine, hexamethylenediamine,
cyclohexylamine, benzylamine and N-methylpiperazine; quaternary
ammonium hydroxides, such as trimethylbenzyl hydroxide; guanidine
and its derivatives, and in particular its alkyl derivatives.
Examples of inorganic bases are, in particular, alkali metal salts,
such as sodium and potassium salts; ammonium salts, alkaline-earth
metal, salts such as magnesium and calcium salts; salts of
divalent, trivalent or tetravalent cationic metals, such as zinc,
aluminium or zirconium. The alkanolamines, ethylenediamine and
inorganic bases, such as the alkali metal salts are preferred.
[0705] In a particularly preferred embodiment, in the compound of
formula (IV) R.sub.9 is a radical
##STR00020##
R.sub.10 is a methyl group, and X.sup.+ is
N.sup.+H.sub.3CH.sub.2CH.sub.2OH.
[0706] This compound (IV) is commercially available under the name
OCTOPIROX (1-hydroxy4-methyl-6-(2,4,4-trimethylpentyl)-2-pyridone,
monoethanolamine salt). [0707] 3) 2,2'-Dithiobis(pyridine N-oxide)
of formula (V):
##STR00021##
[0708] The compounds of formula (V) can be introduced into the
composition in the form of inorganic salts. An example of an
inorganic salt is magnesium sulphate. [0709] 4) Trihalocarbamides
of formula (VI) below:
##STR00022##
[0709] wherein: Z is a halogen atom, such as chlorine, or a
(C.sub.1-C.sub.4) trihaloalkyl group, such as CF.sub.3. [0710] 5)
Triclosan, represented by formula (VII):
[0710] ##STR00023## [0711] 6) Azo compounds, such as climbazole,
ketoconazole, clotrinazole, econazole, isoconazole and miconazole;
[0712] 7) Antifungal polymers, such as amphotericin B or nystatin;
[0713] 8) Selenium sulphide; [0714] 9) Other antidandruff agents
are sulphur in its various forms, cadmium sulphide, allantoin, coal
tars or wood tars and derivatives thereof, in particular cade oil,
salicylic acid, undecylenic acid, fumaric acid and allylamines,
such as terbinafine.
[0715] Zinc Omadoine, Octopirox and selenium sulphide are
particularly preferred.
[0716] Preferably, the at least imidazolium compound and the
additional antidandruff agent(s) are present in an amount ranging
from 0.01% to 10% by weight and more particularly from 0.1 to 5% by
weight, based on the total weight of the composition.
[0717] A fourth special embodiment is a composition for the
treatment of acne and cutaneous disorders linked to
hyperseborrhoea, comprising in a cosmetically acceptable medium at
least one imidazolium compound (=component A).
[0718] With regard to suitable and preferred embodiments of
component A), reference is made to the aforementioned general
definition of the imidazolium compounds employed according to the
invention. Suitable formulations are disclosed in WO 03/000221 A1
which is incorporated herein by reference.
[0719] A fifth special embodiment is a hair dye composition,
comprising in a cosmetically acceptable medium [0720] at least one
imidazolium compound (=component A), and [0721] at least one
cationic dye.
[0722] With regard to suitable and preferred embodiments of
component A), reference is made to the aforementioned general
definition of the imidazolium compounds employed according to the
invention. Suitable hair dye formulations are disclosed in FR
2912908 A1 which is incorporated herein by reference. It was
surprisingly found that advantageous properties are obtained, if
the cationic polymers used in the hair dye compositions according
to this document are replaced completely or partly by at least one
imidazolium compound employed according to the invention.
[0723] A sixth special embodiment is a cosmetic composition for
treating a keratinous substrate, comprising in a cosmetically
acceptable medium [0724] at least one imidazolium compound
(=component A), as defined above and in the following, and [0725]
at least one fatty quaternary amine.
[0726] With regard to suitable and preferred embodiments of
component A), reference is made to the aforementioned general
definition of the imidazolium compounds employed according to the
invention.
[0727] The at least one fatty quaternary amine is preferably
selected from compounds containing from about 6 to about 22 carbon
atoms. The anion of the quaternary agent can be a common ion, such
as chloride, ethosulfate, methosulfate, acetate, bromide, lactate,
nitrate, phosphate, or tosylate and mixtures thereof. The long
chain alkyl groups can include additional or replaced carbon or
hydrogen atoms or ether linkages. Other substitutions on the
quaternary nitrogen can be hydrogen, benzyl or short chain alkyl or
hydroxyalkyl groups, such as methyl, ethyl, hydroxymethyl or
hydroxyethyl, hydroxypropyl or combinations thereof.
[0728] Examples of fatty quaternary amines include, but are not
limited to: Behentrimonium chloride, Cocotrimonium chloride,
Cethethyldimonium bromide, Dibehenyldimonium chloride,
Dihydrogenated tallow benzylmonium chloride, disoyadimonium
chloride, Ditallowedimonium chloride, Hydroxycetyl hydroxyethyl
dimonium chloride, Hydroxyethyl Behenamidopropyl dimonium chloride,
Hydroxyethyl Cetyldimonium chloride, Hydroxyethyl tallowedimonium
chloride, myristalkonium chloride, PEG-2 Oleamonium chloride, PEG-5
Stearmonium chloride, PEG-15 cocoyl quaternium 4, PEG-2
stearalkonium 4, lauryltrimonium chloride; Quaternium-16;
Quaternium-18, lauralkonium chloride, olealkonium chloride,
cetylpyridinium chloride, Polyquaternium-5, Polyquaternium-6,
Polyquaternium-7, Polyquaternium-10, Polyquaternium-22,
Polyquaternium-37, Polyquaternium-39, Polyquaternium-47, cetyl
trimonium chloride, dilauryldimonium chloride, cetalkonium
chloride, dicetyldimonium chloride, soyatrimonium chloride, stearyl
octyl dimonium methosulfate, behentrimonium methosulfate (18-MEA),
stearalkonium chloride, and mixtures thereof. Other quaternary
ammonium compounds are listed in the CTFA Cosmetic Ingredient
Handbook, First Edition, on pages 41-42, incorporated herein by
reference.
[0729] A preferred fatty quaternary amine is Incroquat.RTM. Behenyl
18-MEA, which is a mixture of behentrimonium methosulfate,
C.sub.10-40 isoalkylamidopropylethyldimonium ethosulfate
(Quaternium-33) and cetyl alcohol, commercially available from
Croda, Inc.
[0730] The amount of the at least one fatty quaternary amine in the
composition according to the sixth special embodiment is preferably
in a range from 0.001% to 2% by weight, more preferably from 0.01%
to 1.0% by weight, in particular from 0.1% to 0.5% by weight, based
on the total weight of the composition.
[0731] Preferably, the composition according to the sixth special
embodiment further comprises at least one surfactant. With regard
to suitable and preferred surfactants, reference is made to the
surfactants mentioned before as component D). Preferably at least
one nonionic surfactant is employed. The amount of surfactant in
the composition according to the sixth special embodiment is
preferably in a range from 0.5% to 20% by weight, more preferably
from 1.0% to 5.0% by weight, based on the total weight of the
composition.
[0732] Preferably, the composition according to the sixth special
embodiment further comprises at least one ceramide. Ceramides may
be used in the composition for moisturizing the fiber and
maintaining cuticle integrity. Ceramides are available by
extraction from natural sources, or as synthetic ceramides and
pseudoceramides. Preferred ceramides are e.g.
2-oleamido-1,3-octanediol and Ceramide II from Quest. Mixtures of
ceramides are suitable, such as Ceramides LS from Laboratories
Serobiologiques. The amount of ceramide in the composition
according to the sixth special embodiment is preferably in a range
from 0.001% to 0.5% by weight, more preferably from 0.01% to 0.5%
by weight, in particular from 0.01% to 0.1% by weight, based on the
total weight of the composition.
[0733] Preferably, the composition according to the sixth special
embodiment is substantially anhydrous. The term "substantially
anhydrous" means that the composition is either completely free of
water or contains no appreciable amount of water, preferably no
more than 5% by weight, and more preferably no more than 1% by
weight, based on the weight of the composition.
[0734] Suitable formulations are disclosed in US 2008/0131391 which
is incorporated herein by reference. It was surprisingly found that
advantageous properties are obtained, if the quaternary ammonium
polymers a) used in the compositions according to this document are
replaced completely or partly by at least one imidazolium compound
(=component a) according to the invention.
[0735] A seventh special embodiment is a cosmetic composition for
treating a keratinous substrate, comprising in a cosmetically
acceptable medium [0736] at least one imidazolium compound
(=component A), as defined above and in the following, and [0737]
at least one alkoxysilanes with solubilizing functional groups.
[0738] With regard to suitable and preferred embodiments of
component A), reference is made to the aforementioned general
definition of the imidazolium compounds employed according to the
invention. Suitable alkoxysilanes and formulations are disclosed in
FR 2910276 A1 which is incorporated herein by reference.
Home Care Composition
[0739] A further aspect of the invention is a home care composition
comprising [0740] A) at least one imidazolium compound as defined
above, [0741] B) optionally at least one further microbicidal
compound different from the compounds of component (A), [0742] C)
optionally at least one active ingredient and/or auxiliary.
[0743] The home care composition according to the invention can be
a composition that is effective against various microorganisms.
According to this variant, the imidazolium compound itself may act
as active ingredient. Accordingly, in such a composition the use of
a further active ingredients and/or auxiliaries C) is only
optional.
[0744] The home care composition according to the invention can
also be a composition that contains at least one imidazolium
compound (component A) as preservative. Accordingly, in such a
composition the use of a further component B) and/or C) is usually
mandatory.
[0745] A typical home care composition according to the invention
contains at least one imidazolium compound A), optionally at least
one further microbicidal compound B), and at least one further
component C), selected from non-ionic surfactants, anionic
surfactants, amphoteric surfactants, water, alcohols and a
combination thereof. The home care compositions can include
additional components C), such as enzymes, bleaches, whiteners,
color care agents, fabric softeners, suds suppressors, dispersants,
dye transfer inhibitors, chelating agents, aerosol propellants,
gelling agents, thickening agents and a combination thereof.
[0746] The home care composition according to the invention can be
formulated in a variety of ways and may include a hydrophilic
phase, a hydrophobic phase and optionally at least one emulsifying
agent. The home care composition may be in the form of a liquids,
semi-solid, paste, gel, bar, tablet, spray, foam, powder or
granules.
[0747] For the purpose of the invention the term "home care
composition" means a composition for use in the general environment
of human beings and is further described in the following. Home
care compositions are generally nontoxic when applied in the
vicinity of human beings, for example to fabrics and other items
used by humans, when applied to surfaces used by, or in the
vicinity of, humans, or when applied to spaces occupied by
humans.
[0748] A further aspect of the invention is a method of using a
home care composition, as defined above and in the following, by
applying the composition to an article, surface or space. Exemplary
articles, surfaces and spaces include clothes, furniture fabrics,
rugs and carpets, draperies, dishes and cooking utensils, grills,
ovens, and other items used by humans. The term "surface" includes
hard surfaces in the human environment, such as floors, glass
surfaces (such as glass windows, doors and countertops), other
counter surfaces, bath, toilet bowl, sink and other bathroom
surfaces. The term "space" includes the interior portion of
buildings occupied by humans, including the air contained
therein.
[0749] Advantageously, a home care composition comprising at least
one imidazolium compound A) possesses effective antimicrobial
preservative properties. Further, a home care composition
comprising at least one imidazolium compound A) also confers an
antimicrobial effect on articles, surfaces or spaces to which it is
applied. Home care compositions according to the invention include:
[0750] surface cleaning compositions (for example, glass, floor,
counter, bath, toilet bowl, sink, appliance and furniture cleaning
compositions); [0751] deodorants (for example, solid, liquid and
spray deodorants air and/or surface deodorants); [0752]
disinfectants (for example, spray and solid air disinfectants
(including gel); and spray, solid, liquid and paste surface
disinfectants); [0753] waxes and other surface protecting and/or
polishing compositions; [0754] laundry compositions (for example
detergents, fabric softeners and whiteners); and [0755] rug
shampoos.
[0756] Preferably, the home care composition comprises the
components A) and, if present, B) in a fraction of from about 0.001
to 50% by weight, particularly preferably 0.01 to 30% by weight, in
particular 0.1 to 20% by weight, based on the total weight of the
composition.
Pharmaceutical Composition
[0757] A further aspect of the invention is a pharmaceutical
composition comprising [0758] A) at least one imidazolium compound
as defined above, [0759] B) optionally at least one further
microbicidal compound different from the compounds of component
(A), [0760] C) optionally at least one pharmaceutically acceptable
active ingredient, and [0761] D) optionally at least one
pharmaceutically acceptable excipient.
[0762] The pharmaceutical composition according to the invention
can be a composition that is effective against various
microorganisms. According to this variant, the imidazolium compound
itself may act as pharmaceutically active ingredient. Accordingly,
in such a composition the use of a further pharmaceutically
acceptable active ingredient C) is only optional.
[0763] The pharmaceutical composition according to the invention
can also be a composition that contains at least one imidazolium
compound (component A) as preservative. Accordingly, in such a
composition the use of a further pharmaceutically acceptable active
ingredient C) is usually mandatory.
[0764] Preferably, the pharmaceutical composition comprises the
components A) and, if present, B) in a fraction of from about 0.001
to 50% by weight, particularly preferably 0.01 to 30% by weight, in
particular 0.1 to 20% by weight, based on the total weight of the
composition.
[0765] The pharmaceutical composition of the invention is suitable
for administering in principle any type of active pharmaceutical
ingredient C). These include benzodiazepines, antihypertensives,
vitamins, cytostatics, in particular taxol, anesthetics,
neuroleptics, antidepressants, antibiotics, antimycotics,
fungicides, chemotherapeutics, urologics, thrombocyte aggregation
inhibitors, sulfonamides, spasmolytics, hormones, immunoglobulins,
sera, thyroid therapeutic agents, psychopharmacological agents,
antiparkinsonians and other antihyperkinetic agents, ophthalmics,
neuropathy preparations, calcium metabolism regulators, muscle
relaxants, narcotics, antilipemics, hepatic therapeutic agents,
coronary agents, cardiacs, immunotherapeutics, regulatory peptides
and their inhibitors, hypnotics, sedatives, gynecological agents,
antigouts, fibrinolytic agents, enzyme preparations and transport
proteins, enzyme inhibitors, emetics, circulation-promoting agents,
diuretics, diagnostics, corticoids, cholinergics, bile duct
therapeutics, antiasthmatics, broncholytics, beta-receptor
blockers, calcium antagonists, ACE inhibitors,
antiarteriosclerotics, antiinflammatories, anticoagulants,
antihypotensives, antihypoglycemics, antihypertonics,
antifibrinolytics, antiepileptics, antiemetics, antidotes,
antidiabetics, antiarrhythmics, antianemics, antiallergics,
anthelmintics, analgesics, analeptics, aldosterone antagonists and
slimming agents
[0766] Examples of suitable active ingredients C) are: acarbose,
non-steroidal antirheumatics, cardiac glycosides, acetylsalicylic
acid, virustatics, aclarubicin, acyclovir, cisplatin, actinomycin,
alpha- and beta-sympathomimetics, allopurinol, alosetron,
alprostadil, prostaglandins, amantadine, ambroxol, amlodipine,
methotrexate, 5-aminosalicylic acid, amitriptyline, amlodipine,
amoxicillin, anastrozole, atenolol, atorvastatin, azathioprine,
balsalazide, beclomethasone, betahistine, bezafibrate,
bicalutamide, diazepam and diazepam derivatives, budesonide,
bufexamac, buprenorphine, methadone, calcium salts, potassium
salts, magnesium salts, candesartan, carbamazepine, captopril,
cefalosporins, celetoxib, cetirizine, chenodeoxycholic acid,
ursodeoxycholic acid, theophylline and theophylline derivatives,
trypsins, cimetidine, clarithromycin, clavulanic acid, clindamycin,
clobutinol, clonidine, cotrimoxazole, codeine, caffeine, vitamin D
and derivatives of vitamin D, colestyramine, cromoglicic acid,
coumarin and coumarin derivatives, cysteine, cytarabine,
cyclophosphamide, ciclosporin, cyproterone, cytarabine,
dapiprazole, desogestrel, desonide, dihydralazine, diltiazem, ergot
alkaloids, dimenhydrinate, dimethyl sulfoxide, dimethicone,
dipyridamole, domperidone and domperidone derivatives, donepzil,
dopamine, doxazosin, doxorubicin, doxylamine, dapiprazole,
benzodiazepines, diclofenac, glycoside antibiotics, desipramine,
econazole, ACE inhibitors, enalapril, ephedrine, epinephrine,
epoetin and epoetin derivatives, morphinans, calcium antagonists,
irinotecan, modafinil, orlistat, peptide antibiotics, phenytoin,
riluzoles, risedronate, sildenafil, topiramate, macrolide
antibiotics, esomeprazole, estrogen and estrogen derivatives,
progestogen and progestogen derivatives, testosterone and
testosterone derivatives, androgen and androgen derivatives,
ethenzamide, etofenamate, etofibrate, fenofibrate, etofylline,
etoposide, famciclovir, famotidine, felodipine, fenofibrate,
fentanyl, fenticonazole, gyrase inhibitor, fluconazole,
fludarabine, flunarizine, fluorouracil, fluoxetine, flurbiprofen,
ibuprofen, flutamide, fluvastatin, follitropin, formoterol,
fosfomicin, furosemide, fusidic acid, galantamine, gallopamil,
ganciclovir, gemfibrozil, gentamicin, ginkgo, St John's wort,
glibenclamide, urea derivatives as oral antidiabetics, glucagon,
glucosamine and glucosamine derivatives, glutathione, glycerol and
glycerol derivatives, hypothalamus hormones, goserelin,
guanethidine, halofantrine, haloperidol, heparin and heparin
derivatives, hyaluronic acid, hydralazine, hydrochlorothiazide and
hydrochlorothiazide derivatives, salicylates, hydroxyzine,
idarubicin, ifosfamide, imipramine, indometacin, indoramine,
insulin, interferons, iodine and iodine derivatives, isoconazole,
isoprenaline, glucitol and glucitol derivatives, itraconazole,
ketoconazole, ketoprofen, ketotifen, lacidipine, lansoprazole,
levodopa, levomethadone, thyroid hormones, lipoic acid and lipoic
acid derivatives, lisinopril, lisuride, lofepramine, lomustine,
loperamide, loratadine, maprotiline, mebendazole, mebeverine,
meclozine, mefenamic acid, mefloquine, meloxicam, mepindolol,
meprobamate, meropenem, mesalazine, mesuximide, metamizole,
metformin, methotrexate, methylphenidate, methylprednisolone,
metixen, metoclopramide, metoprolol, metronidazole, mianserin,
miconazole, minocycline, minoxidil, misoprostol, mitomycin,
mizolastine, moexipril, morphine and morphine derivatives, evening
primrose, nalbuphine, naloxone, tilidine, naproxen, narcotine,
natamycin, neostigmine, nicergoline, nicethamide, nifedipine,
niflumic acid, nimodipine, nimorazole, nimustine, nisoldipine,
adrenaline, and adrenaline derivatives, norfloxacin,
novaminsulfone, noscapine, nystatin, ofloxacin, olanzapine,
olsalazine, omeprazole, omoconazole, ondansetron, orlistat,
oseltamivir, oxaceprol, oxacillin, oxiconazole, oxymetazoline,
pantoprazole, paracetamol, paroxetine, penciclovir, oral
penicillins, pentazocine, pentifylline, pentoxifylline,
perphenazine, pethidine, plant extracts, phenazone, pheniramine,
barbituric acid derivatives, phenylbutazone, phenytoin, pimozide,
pindolol, piperazine, piracetam, pirenzepine, piribedil, piroxicam,
pramipexol, pravastatin, prazosin, procaine, promazine,
propiverine, propranolol, propyphenazone, prostaglandins,
protionamide, proxyphylline, quetiapine, quinapril, quinaprilate,
ramipril, ranitidine, reproterol, reserpine, ribavirin, rifampicin,
risperidone, ritonavir, ropinirol, rosiglitazone, roxatidine,
roxithromycin, ruscogenin, rutoside and rutoside derivatives,
sabadilla, salbutamol, salmeterol, scopolamine, selegiline,
sertaconazole, sertindole, sertraline, silicates, simvastatin,
sitosterol, sotalol, spaglumic acid, sparfloxacin, spectinomycin,
spiramycin, spirapril, spironolactone, stavudine, streptomycin,
sucralfate, sufentanil, sulbactam, sulfonamides, sulfasalazine,
sulpiride, sultamicillin, sultiam, sumatriptan, suxamethonium
chloride, tacrine, tacrolimus, taliolol, tamoxifen, taurolidine,
tazarotene, tegaserod, temazepam, teniposide, tenoxicam, terazosin,
terbinafine, terbutaline, terfenadine, terlipressin, tertatolol,
tetracyclines, tetryzoline, theobromine, theophylline, butizine,
thiamazole, phenothiazines, thiotepa, tiagabine, tiapride,
propionic acid derivatives, ticlopidine, timolol, tinidazole,
tioconazole, tioguanine, tioxolone, tiropramide, tizanidine,
tolazoline, tolbutamide, tolcapone, tolnaftate, tolperisone,
topotecan, torasemide, antiestrogens, tramadol, tramazoline,
trandolapril, tranylcypromine, trapidil, trazodone, triamcinolone
and triamcinolone derivatives, triamterene, trifluperidol,
trifluridine, trimethoprim, trimipramine, tripelennamine,
triprolidine, trifosfamide, tromantadine, trometamol, tropalpin,
troxerutin, tulobuterol, tyramine, tyrothricin, urapidil,
ursodeoxycholic acid, chenodeoxycholic acid, valaciclovir,
valdecoxib, valproic acid, vancomycin, vecuronium chloride,
venlafaxine, verapamil, vidarabine, vigabatrine, viloxazine,
vinblastine, vincamine, vincristine, vindesine, vinorelbine,
vinpocetine, viquidil, warfarin, xantinol nicotinate, xipamide,
zafirlukast, zalcitabine, zanamivir, zidovudine, zolmitriptan,
zolpidem, zopiclone, zotepine and the like.
[0767] The active ingredients can, if desired, also be used in the
form of their pharmaceutically acceptable salts or derivatives, and
in the case of chiral active ingredients it is possible to employ
both optically active isomers and racemates or mixtures of
diastereoisomers. The compositions of the invention can, if
desired, also comprise two or more active pharmaceutical
ingredients.
[0768] The formulation base of pharmaceutical compositions of the
invention preferably comprises pharmaceutically acceptable
excipients D). Pharmaceutically acceptable excipients are those
known to be usable in the area of pharmacy, food technology and
adjacent sectors, in particular the excipients listed in relevant
pharmacopeias (e.g. DAB, Ph. Eur., BP, USP, JP) and others, whose
properties do not stand in the way of physiological use.
[0769] Suitable excipients D) may be: lubricants, wetting agents,
emulsifying and suspending agents, antioxidants, anti-irritants,
chelating agents, emulsion stabilizers, film formers, gel formers,
odor-masking agents, resins, hydrocolloids, solvents, solubilizers,
neutralizers, permeation promoters, pigments, colorants,
stabilizers, disintegrants, dessicants, opacifiers, thickeners,
waxes, plasticizers, flavors, sweeteners, excipients to reduce
permeation etc. An arrangement concerning this is based on
specialist knowledge as described for example in Fiedler, H. P.
Lexikon der Hilfsstoffe fur Pharmazie, Kosmetik and angrenzende
Gebiete, 4th edition, Aulendorf: ECV-Editio-Cantor-Verlag,
1996.
Plant Protection Composition
[0770] A further aspect of the invention is a plant protection
composition comprising [0771] A) at least one imidazolium compound
as defined above, [0772] B) optionally at least one further
microbicidal compound different from the compounds of component
(A), [0773] C) optionally at least one active substance for plant
protection, and [0774] D) optionally at least one auxiliary.
[0775] The plant protection composition according to the invention
can be a composition that is effective against various
microorganisms. According to this variant, the imidazolium compound
itself may act as active ingredient. Accordingly, in such a
composition the use of a further active substance for plant
protection C) is only optional. Preferably, the plant protection
composition in which the imidazolium compound itself acts as active
ingredient is a fungicidal composition. Such compositions have been
described in detail above.
[0776] The plant protection composition according to the invention
can however also be a composition that contains at least one
imidazolium compound (component A) as preservative. Accordingly, in
such a composition the use of at least one further active substance
for plant protection C) is usually mandatory.
[0777] The pharmaceutical composition of the invention is suitable
in principle any type of active substance for plant protection C).
Examples of at least one active substance for plant protection are
described in the following.
[0778] Examples of fungicidal active substances C) comprise: [0779]
acylalanines, such as benalaxyl, metalaxyl, ofurace or oxadixyl;
[0780] amine derivatives, such as aldimorph, dodine, dodemorph,
fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamine or
tridemorph; [0781] anilinopyrimidines, such as pyrimethanil,
mepanipyrim or cyprodinil; [0782] antibiotics, such as
cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin and
streptomycin; [0783] azoles, such as bitertanol, bromoconazole,
cyproconazole, difenoconazole, diniconazole, epoxiconazole,
fenbuconazole, fluquinconazole, flusilazole, flutriafol,
hexaconazole, imazalil, ipconazole, metconazole, myclobutanil,
penconazole, propiconazole, prochloraz, prothioconazole,
tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole
or triticonazole; [0784] 2-methoxybenzophenones, such as those
disclosed in EP-A 897 904 by the general formula (I), e.g.
metrafenone; [0785] dicarboximides, such as iprodione, myclozolin,
procymidone or vinclozolin; [0786] dithiocarbamates, such as
ferbam, nabam, maneb, mancozeb, metam, metiram, propineb,
polycarbamate, thiram, ziram or zineb; [0787] heterocyclic
compounds, such as anilazine, benomyl, boscalid, carbendazim,
carboxin, oxycarboxin, cyazofamid, dazomet, dithianon, famoxadone,
fenamidone, fenarimol, fuberidazole, flutolanil, furametpyr,
isoprothiolane, mepronil, nuarimol, picobenzamid, probenazole,
proquinazid, pyrifenox, pyroquilon, quinoxyfen, silthiofam,
thiabendazole, thifluzamide, thiophanate-methyl, tiadinil,
tricyclazole or triforine; [0788] nitrophenyl derivatives, such as
binapacryl, dinocap, dinobuton or nitrothal-isopropyl; [0789]
phenylpyrroles, such as fenpiclonil or fludioxonil; [0790]
unclassified fungicides, such as acibenzolar-S-methyl,
benthiavalicarb, carpropamid, chlorothalonil, cyflufenamid,
cymoxanil, diclomezine, diclocymet, diethofencarb, edifenphos,
ethaboxam, fenhexamid, fentin acetate, fenoxanil, ferimzone,
fluazinam, fosetyl, fosetyl-aluminum, iprovalicarb,
hexachlorobenzene, metrafenone, pencycuron, propamocarb, phthalide,
tolclofos-methyl, quintozene or zoxamide; [0791] strobilurins, such
as those disclosed in WO 03/075663 by the general formula (I), for
example azoxystrobin, dimoxystrobin, fluoxastrobin,
kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin,
pyraclostrobin and trifloxystrobin; [0792] sulfenic acid
derivatives, such as captafol, captan, dichlofluanid, folpet or
tolylfluanid; [0793] cinnamamides and analogous compounds, such as
dimethomorph, flumetover or flumorph; [0794]
6-aryl-[1,2,4]triazolo[1,5-a]pyrimidines, such as those disclosed,
e.g., in WO 98/46608, WO 99/41255 or WO 03/004465, in each case by
the general formula (I); [0795] amide fungicides, such as
cyflufenamid and
(Z)--N-[.alpha.-(cyclopropylmethoxyimino)-2,3-difluoro-6-(difluoromethoxy-
)benzyl]-2-phenylacetamide.
[0796] Examples of herbicides C) comprise: [0797]
1,3,4-thiadiazoles, such as buthidazole and cyprazole; [0798]
amides, such as allidochlor, benzoylprop-ethyl, bromobutide,
chlorthiamid, dimepiperate, dimethenamid, diphenamid, etobenzanid,
flamprop-methyl, fosamine, isoxaben, metazachlor, monalide,
naptalam, pronamide or propanil; [0799] aminophosphoric acids, such
as bilanafos, buminafos, glufosinate-ammonium, glyphosate or
sulfosate; [0800] aminotriazoles, such as amitrole, or anilides,
such as anilofos or mefenacet; [0801] aryloxyalkanoic acid, such as
2,4-D, 2,4-DB, clomeprop, dichlorprop, dichlorprop-P, fenoprop,
fluroxypyr, MCPA, MCPB, mecoprop, mecoprop-P, napropamide,
naproanilide or triclopyr; [0802] benzoic acids, such as chloramben
or dicamba; [0803] benzothiadiazinones, such as bentazon; [0804]
bleachers, such as clomazone, diflufenican, fluorochloridone,
flupoxam, fluridone, pyrazolate or sulcotrione; [0805] carbamates,
such as carbetamide, clorbufam, chlorpropham, desmedipham,
phenmedipham or vernolate; [0806] quinolinecarboxylic acids, such
as quinclorac or quinmerac; [0807] dichloropropionic acids, such as
dalapon; [0808] dihydrobenzofurans, such as ethofumesate; [0809]
dhydrofuran-3-ones, such as flurtamone; [0810] dinitroanilines,
such as benefin, butralin, dinitramine, ethalfluralin,
fluchloralin, isopropalin, nitralin, oryzalin, pendimethalin,
prodiamine, profluralin, trifluralin; [0811] dinitrophenols, such
as bromofenoxim, dinoseb, dinoseb acetate, dinoterb, DNOC or
minoterb acetate; [0812] diphenyl ethers, such as
acifluorfen-sodium, aclonifen, bifenox, chlornitrofen, difenoxuron,
ethoxyfen, fluorodifen, fluoroglycofen-ethyl, fomesafen,
furyloxyfen, lactofen, nitrofen, nitrofluorfen or oxyfluorfen;
[0813] dipyridyls, such as cyperquat, difenzoquat metilsulfate,
diquat or paraquat dichloride; [0814] imidazoles, such as
isocarbamid; [0815] imidazolinones, such as imazamethapyr,
imazapyr, imazaquin, imazethabenzmethyl, imazethapyr, imazapic or
imazamox; [0816] oxadiazoles, such as methazole, oxadiargyl or
oxadiazone; [0817] oxiranes, such as tridiphane; [0818] phenols,
such as bromoxynil or ioxynil; [0819] phenoxyphenoxypropionic acid
esters, such as clodinafop, cyhalofop-butyl, diclofop-methyl,
fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenthiaprop-ethyl,
fluazifop-butyl, fluazifop-P-butyl, haloxyfop-ethoxyethyl,
haloxyfop-methyl, haloxyfop-P-methyl, isoxapyrifop, propaquizafop,
quizalofop-ethyl, quizalofop-P-ethyl or quizalofop-P-tefuryl;
[0820] phenylacetic acids, such as chlorfenac; [0821]
phenylpropionic acids, such as chlorphenprop-methyl; [0822]
ppi-active substances (ppi=preplant incorporated), such as
benzofenap, flumiclorac-pentyl, flumioxazin, flumipropyn,
flupropacil, pyrazoxyfen, sulfentrazone or thidiazimin; [0823]
pyrazoles, such as nipyraclofen; [0824] pyridazines, such as
chloridazon, maleic hydrazide, norflurazon or pyridate; [0825]
pyridinecarboxylic acids, such as clopyralid, dithiopyr, picloram
or thiazopyr; [0826] pyrimidyl ethers, such as pyrithiobac acid,
pyrithiobac-sodium, KIH-2023 or KIH-6127; [0827] sulfonamides, such
as flumetsulam or metosulam; [0828] triazolecarboxamides, such as
triazofenamide; [0829] uracils, such as bromacil, lenacil or
terbacil; [0830] furthermore benazolin, benfuresate, bensulide,
benzofluor, bentazon, butamifos, cafenstrole, chlorthal-dimethyl,
cinmethylin, dichlobenil, endothall, fluorbentranil, mefluidide,
perfluidone, piperophos, topramezone and prohexadione-calcium;
[0831] sulfonylureas, such as amidosulfuron, azimsulfuron,
bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron,
cyclosulfamuron, ethametsulfuron-methyl, flazasulfuron,
halosulfuron-methyl, imazosulfuron, metsulfuron-methyl,
nicosulfuron, primisulfuron, prosulfuron, pyrazosulfuron-ethyl,
rimsulfuron, sulfometuron-methyl, thifensulfuron-methyl,
triasulfuron, tribenuron-methyl, triflusulfuron-methyl or
tritosulfuron; [0832] plant protection active substances of the
cyclohexenone type, such as alloxydim, clethodim, cloproxydim,
cycloxydim, sethoxydim and tralkoxydim. Very particularly preferred
herbicidal active substances of the cyclohexenone type are:
tepraloxydim (cf. AGROW, No. 243, 11.3.95, page 21, caloxydim) and
2-(1-[2-{4-chlorphenoxy}propyloxyimino]butyl)-3-hydroxy-5-(2H-tetrahydrot-
hio-pyran-3-yl)-2-cyclohexen-1-one, and of the sulfonylurea type
is:
N-(((4-methoxy-6-[trifluoromethyl]-1,3,5-triazin-2-yl)amino)carbonyl)-2-(-
trifluoromethyl)benzenesulfonamide.
[0833] Examples of insecticides C) comprise: [0834]
organophosphates, such as acephate, azinphos-methyl, chlorpyrifos,
chlorfenvinphos, diazinon, dichlorvos, dimethylvinphos,
dioxabenzofos, dicrotophos, dimethoate, disulfoton, ethion, EPN,
fenitrothion, fenthion, isoxathion, malathion, methamidophos,
methidathion, methyl parathion, mevinphos, monocrotophos,
oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone,
phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl,
profenofos, prothiofos, pirimiphos-ethyl, pyraclofos,
pyridaphenthion, sulprophos, triazophos, trichlorfon,
tetrachlorvinphos or vamidothion; [0835] carbamates, such as
alanycarb, benfuracarb, bendiocarb, carbaryl, carbofuran,
carbosulfan, fenoxycarb, furathiocarb, indoxacarb, methiocarb,
methomyl, oxamyl, pirimicarb, propoxur, thiodicarb or triazamate;
[0836] pyrethroids, such as bifenthrin, cyfluthrin, cycloprothrin,
cypermethrin, deltamethrin, esfenvalerate, etofenprox,
fenpropathrin, fenvalerate, cyhalothrin, lambda-cyhalothrin,
permethrin, silafluofen, tau-fluvalinate, tefluthrin, tralomethrin,
alpha-cypermethrin or zeta-cypermethrin; [0837] arthropodal growth
regulators: a) chitin synthesis inhibitors, e.g. benzoylureas, such
as chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron,
hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron,
buprofezin, diofenolan, hexythiazox, etoxazole or clofentezine; b)
ecdysone antagonists, such as halofenozide, methoxyfenozide or
tebufenozide; c) juvenile hormone mimics, such as pyriproxyfen,
methoprene or fenoxycarb; d) lipid biosynthesis inhibitors such as
spirodiclofen; [0838] neonicotinoids, such as flonicamid,
clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram,
nithiazine, acetamiprid or thiacloprid; [0839] additional
unclassified insecticides, such as abamectin, acequinocyl,
acetamiprid, amitraz, azadirachtin, bensultap, bifenazate, cartap,
chlorfenapyr, chlordimeform, cyromazine, diafenthiuron,
dinotefuran, diofenolan, emamectin, endosulfan, ethiprole,
fenazaquin, fipronil, formetanate, formetanate hydrochloride,
gamma-HCH, hydramethylnon, imidacloprid, indoxacarb, isoprocarb,
metolcarb, pyridaben, pymetrozine, spinosad, tebufenpyrad,
thiamethoxam, thiocyclam, XMC and xylylcarb; [0840]
N-phenylsemicarbazones, such as those disclosed in EP-A 462 456 by
the general formula (I), especially compounds of the general
formula (A)
##STR00024##
[0840] in which R.sup.2 and R.sup.3 represent, independently of one
another, hydrogen, halogen, CN, C.sub.1-C.sub.4 alkyl,
C.sub.1-C.sub.4 alkoxy, C.sub.1-C.sub.4 haloalkyl or
C.sub.1-C.sub.4 haloalkoxy and R.sup.4 represents C.sub.1-C.sub.4
alkoxy, C.sub.1-C.sub.4 haloalkyl or C.sub.1-C.sub.4 haloalkoxy,
e.g. compound IV, in which R.sup.2 represents 3-CF.sub.3, R.sup.3
represents 4-CN and R.sup.4 represents 4-OCF.sub.3.
[0841] Useable growth regulators C) are, e.g., chlormequat
chloride, mepiquat chloride, prohexadione-calcium or the group of
the gibberellins. These include, e.g. the gibberellin GA.sub.1,
GA.sub.3, GA.sub.4, GA.sub.5 and GA.sub.7, and the like, and the
corresponding exo-16,17-dihydrogibberellins, and also the
derivatives thereof, e.g. the esters with C.sub.1-C.sub.4
carboxylic acids, The exo-16,17-dihydro-GA.sub.5 13-acetate is
preferred according to the invention.
Antimicrobial Polymer Composition or Coating Composition
[0842] The imidazolium compounds employed according to the
invention are in particular suitable to provide antimicrobial
polymers and coating compositions, for example compositions for
medical applications. The polymer compositions and coating
compositions show an outstanding antimicrobial activity. Thus, in a
further aspect, the invention provides an antimicrobial polymer
composition or coating composition, wherein the polymer composition
or the coating comprises an effective antimicrobial amount of at
least one polymeric, ionic compound comprising imidazolium groups
(component A), as defined above.
[0843] Preferably, the polymer composition or coating composition
comprises at least one imidazolium compound in an amount of from
about 0.001 to about 15.0 weight percent, more preferably 0.01 to
10.0 weight percent, based on the total weight of the polymer
composition or the coating composition.
[0844] A further aspect of the invention is a polymer composition
or coating composition, comprising [0845] A) at least one
imidazolium compound as defined above, [0846] B) optionally at
least one further microbicidal compound different from the
compounds of component (A), [0847] C) optionally at least one
polymer and/or at least one polymerizable compound, and [0848] D)
optionally at least one additive.
[0849] With regard to suitable and preferred compounds of the
components A) and B), reference is made to the aforementioned
description of suitable and preferred embodiments of those
components.
[0850] The employed polymers may be in any form, for example
fibers, films or molded parts. They may be for example woven or
nonwoven polymer fabrics.
[0851] Suitable polymers C) may be selected from: [0852] 1.
Polymers of monoolefins and diolefins, for example polypropylene,
polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,
polyisoprene or polybutadiene, as well as polymers of cycloolefins,
for instance of cyclopentene or norbornene, polyethylene (which
optionally can be crosslinked), for example high density
polyethylene (HDPE), low density polyethylene (LDPE), linear low
density polyethylene (LLDPE), branched low density polyethylene
(BLDPE) and medium density polyethylene (MDPE). [0853] Polyolefins,
i.e. the polymers of monoolefins exemplified in the preceding
paragraph, preferably polyethylene and polypropylene, can be
prepared by different, and especially by the following, methods:
[0854] a) radical polymerization (normally under high pressure and
at elevated temperature). [0855] b) catalytic polymerization using
a catalyst that normally contains one or more than one metal of
groups IVb, Vb, VIb or VIII of the Periodic Table. These metals
usually have one or more than one ligand, typically oxides,
halides, alcoholates, esters, ethers, amines, alkyls, alkenyls
and/or aryls that may be either p- or s-coordinated. These metal
complexes may be in the free form or fixed on substrates, typically
on activated magnesium chloride, titanium(III) chloride, alumina or
silicon oxide. These catalysts may be soluble or insoluble in the
polymerization medium. The catalysts can be used by themselves in
the polymerization or further activators may be used, typically
metal alkyls, metal hydrides, metal alkyl halides, metal alkyl
oxides or metal alkyloxanes, said metals being elements of groups
Ia, IIa and/or IIIa of the Periodic Table. The activators may be
modified conveniently with further ester, ether, amine or silyl
ether groups. These catalyst systems are usually termed Phillips,
Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene
or single site catalysts (SSC). [0856] 2. Mixtures of the polymers
mentioned under 1), for example mixtures of polypropylene with
polyisobutylene, polypropylene with polyethylene (for example
PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene
(for example LDPE/HDPE). [0857] 3. Copolymers of monoolefins and
diolefins with each other or with other vinyl monomers, for example
ethylene/propylene copolymers, linear low density polyethylene
(LLDPE) and mixtures thereof with low density polyethylene (LDPE),
propylene/but-1-ene copolymers, propylene/isobutylene copolymers,
ethylene/but-1-ene copolymers, ethylene/hexene copolymers,
ethylene/methylpentene copolymers, ethylene/heptene copolymers,
ethylene/octene copolymers, propylene/butadiene copolymers,
isobutylene/isoprene copolymers, ethylene/alkyl acrylate
copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl
acetate copolymers and their copolymers with carbon monoxide or
ethylene/acrylic acid copolymers and their salts (ionomers) as well
as terpolymers of ethylene with propylene and a diene such as
hexadiene, dicyclopentadiene or ethylidenenorbornene; and mixtures
of such copolymers with one another and with polymers mentionedin
1) above, for example polypropylene/ethylene-propylene copolymers,
LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic
acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or
random polyalkylene/carbon monoxide copolymers and mixtures thereof
with other polymers, for example polyamides. [0858] 4. Hydrocarbon
resins (for example C5-C9) including hydrogenated modifications
thereof (e.g. tackifiers) and mixtures of polyalkylenes and starch.
[0859] 5. Polystyrene, poly(p-methylstyrene),
poly(a-methylstyrene). [0860] 6. Copolymers of styrene or
[alpha-methylstyrene with dienes or acrylic derivatives, for
example styrene/butadiene, styrene/unsaturated ester,
styrene/acrylonitrile, styrene/alkyl methacrylate,
styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl
methacrylate, styrene/maleic anhydride,
styrene/acrylonitrile/methyl acrylate; mixtures of high impact
strength of styrene copolymers and another polymer, for example a
polyacrylate, a diene polymer or an ethylene/propylene/diene
terpolymer; and block copolymers of styrene such as
styrene/butadiene/styrene, styrene/isoprene/styrene,
styrene/ethylene/butylene/styrene or
styrene/ethylene/propylene/styrene. [0861] 7. Graft copolymers of
styrene or [alpha-methylstyrene, for example styrene on
polybutadiene, styrene on polybutadiene-styrene or
polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile
(or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and
methyl methacrylate on polybutadiene; styrene and maleic anhydride
on polybutadiene; styrene, acrylonitrile and maleic anhydride or
maleimide on polybutadiene; styrene and maleimide on polybutadiene;
styrene and alkyl acrylates or methacrylates on polybutadiene;
styrene and acrylonitrile on ethylene/propylene/diene terpolymers;
styrene and acrylonitrile on polyalkyl acrylates or polyalkyl
methacrylates, styrene and acrylonitrile on acrylate/butadiene
copolymers, as well as mixtures thereof with the copolymers listed
under 6), for example the copolymer mixtures known as ABS, SAN,
MBS, ASA or AES polymers. [0862] 8. Halogen-containing polymers
such as polychloroprene, chlorinated rubbers, chlorinated or
sulfochlorinated polyethylene, copolymers of ethylene and
chlorinated ethylene, epichlorohydrin homo- and copolymers,
especially polymers of halogen-containing vinyl compounds, for
example polyvinyl chloride, polyvinylidene chloride, polyvinyl
fluoride, polyvinylidene fluoride, as well as copolymers thereof
such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl
acetate or vinylidene chloride/vinyl acetate copolymers. [0863] 9.
Polymers derived from .alpha.,.beta.-unsaturated acids and
derivatives thereof such as polyacrylates and polymethacrylates;
polymethyl methacrylates, polyacrylamides and polyacrylonitriles,
impact-modified with butyl acrylate. [0864] 10. Copolymers of the
monomers mentioned under 9) with each other or with other
unsaturated monomers, for example acrylonitrile/butadiene
copolymers, acrylonitrile/alkyl acrylate copolymers,
acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide
copolymers or acrylonitrile/alkyl methacrylate/butadiene
terpolymers. [0865] 11. Polymers derived from unsaturated alcohols
and amines or the acyl derivatives or acetals thereof, for example
polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl
benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate
or polyallyl melamine; as well as their copolymers with olefins
mentionedin 1) above. [0866] 12. Homopolymers and copolymers of
cyclic ethers such as polyalkylene glycols, polyethylene oxide,
polypropylene oxide or copolymers thereof with bis-glycidyl ethers.
[0867] 13. Polyacetals such as polyoxymethylene and those
polyoxymethylenes which contain ethylene oxide as a comonomer;
polyacetals modified with thermoplastic polyurethanes, acrylates or
MBS. [0868] 14. Polyphenylene oxides and sulfides, and mixtures of
polyphenylene oxides with styrene polymers or polyamides. [0869]
15. Polyurethanes derived from hydroxyl-terminated polyethers,
polyesters or polybutadienes on the one hand and aliphatic or
aromatic polyisocyanates on the other, as well as precursors
thereof. [0870] 16. Polyamides and copolyamides derived from
diamines and dicarboxylic acids and/or from aminocarboxylic acids
or the corresponding lactams, for example polyamide 4, polyamide 6,
polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide
12, aromatic polyamides starting from m-xylene diamine and adipic
acid; polyamides prepared from hexamethylenediamine andisophthalic
or/and terephthalic acid and with or without an elastomer as
modifier, for example poly-2,4,4,-trimethylhexamethylene
terephthalamide or poly-m-phenylene isophthalamide; and also block
copolymers of the aforementioned polyamides with polyolefins,
olefin copolymers, ionomers or chemically bonded or grafted
elastomers; or with polyethers, e.g. with polyethylene glycol,
polypropylene glycol or polytetramethylene glycol; as well as
polyamides or copolyamides modified with EPDM or ABS; and
polyamides condensed during processing (RIM polyamide systems).
[0871] 17. Polyureas, polyimides, polyamide-imides and
polybenzimidazoles. [0872] 18. Polyesters derived from dicarboxylic
acids and diols and/or from hydroxycarboxylic acids or the
corresponding lactones, for example polyethylene terephthalate,
polytrimethylene terephthalate, polybutylene terephthalate,
poly-1,4-dimethylolcyclohexane terephthalate and
polyhydroxybenzoates, as well as block copolyether esters derived
from hydroxyl-terminated polyethers; and also polyesters modified
with polycarbonates or MBS. Polyesters and polyester copolymers as
defined in U.S. Pat. No. 5,807,932 (column 2, line 53),
incorporated herein by reference. [0873] 19. Polycarbonates and
polyester carbonates. [0874] 20. Polysulfones, polyether sulfones
and polyether ketones. [0875] 21. Crosslinked polymers derived from
aldehydes on the one hand and phenols, ureas and melamines on the
other hand, such as phenol/formaldehyde resins, urea/formaldehyde
resins and melamine/formaldehyde resins. [0876] 22. Drying and
non-drying alkyd resins. [0877] 23. Unsaturated polyester resins
derived from copolyesters of saturated and unsaturated dicarboxylic
acids with polyhydric alcohols and vinyl compounds as crosslinking
agents, and also halogen-containing modifications thereof of low
flammability. [0878] 24. Crosslinkable acrylic resins derived from
substituted acrylates, for example epoxy acrylates, urethane
acrylates or polyester acrylates. [0879] 25. Alkyd resins,
polyester resins and acrylate resins crosslinked with melamine
resins, urea resins, polyisocyanates or epoxy resins. [0880] 26.
Crosslinked epoxy resins derived from polyepoxides, for example
from bis glycidyl ethers or from cycloaliphatic diepoxides. [0881]
27. Natural polymers such as cellulose, rubber, gelatin and
chemically modified homologous derivatives thereof, for example
cellulose acetates, cellulose propionates and cellulose butyrates,
or the cellulose ethers, such as methyl cellulose; as well as
rosins and their derivatives. [0882] 28. Blends of the
aforementioned polymers (polyblends), for example PP/EPDM,
Polyamide/-EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,
PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic
PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA
6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO. [0883] 29. Naturally
occurring and synthetic organic materials which are pure monomeric
compounds or mixtures of such compounds, for example mineral oils,
animal and vegetable fats, oil and waxes, or oils, fats and waxes
based on synthetic esters (e.g. phthalates, adipates, phosphates or
trimellitates) and also mixtures of synthetic esters with mineral
oils in any weight ratios, typically those used as spinning
compositions, as well as aqueous emulsions of such materials.
[0884] 30. Aqueous emulsions of natural or synthetic rubber, e.g.
natural latex or latices of carboxylated styrene/butadiene
copolymers. [0885] 31. Polysiloxanes such as the soft, hydrophilic
polysiloxanes described, for example, in U.S. Pat. No. 4,259,467;
and the hard polyorganosiloxanes described, for example, in U.S.
Pat. No. 4,355,147. [0886] 32. Silicone elastomers, for example
liquid silicone rubbers (LSR). Liquid Silicone Rubbers are
available from Dow Chemical and are described for example in U.S.
Pat. Nos. 6,569,536; 6,420,038; 6,297,291; 6,218,466; 6,130,272;
5,994,461; 5,989,719; 5,973,030; 5,908,888; 5,880,199; 5,877,256;
5,859,094; 5,789,084 and 5,661,210. The disclosures of these U.S.
patents are incorporated by reference. [0887] 33. Polyketimines in
combination with unsaturated acrylic polyacetoacetate resins or
with unsaturated acrylic resins. The unsaturated acrylic resins
include the urethane acrylates, polyether acrylates, vinyl or acryl
copolymers with pendant unsaturated groups and the acrylated
melamines. The polyketimines are prepared from polyamines and
ketones in the presence of an acid catalyst. [0888] 34. Radiation
curable compositions containing ethylenically unsaturated monomers
or oligomers and a polyunsaturated aliphatic oligomer. [0889] 35.
Epoxymelamine resins such as light-stable epoxy resins crosslinked
by an epoxy functional coetherified high solids melamine resin such
as LSE-4103 (Monsanto).
[0890] Included also are thermoplastic olefin (TPO), thermoplastic
elastomers, polyetherimide, polymethylpentene, polyphenylene ether,
polyphenylene sulfide, polysulfone or polytetrafluoroethylene
(PTFE).
[0891] Some polymers of specific technical interest include:
Polysulfone (PSF)
Polyethersulfone (PES)
Polyphenylsulfone (PPS)
Polyvinylidene Fluoride (PVDF)
Polypropylene (PP)
Polyethylene (PE)
[0892] Cellulose, Cellulose acetates (CA), Cellulose nitrate
Polyamide (PA)
Polyacrylonitrile (PAN)
Polytetrafluoroethylene (PTFE)
Polycarbonate (PC)
Polymethylmethacrylate (PMMA).
[0893] In particular, the present polymers are those that are
typically employed in medical applications, for example
polyurethanes, polycarbonate, liquid silicone rubbers,
polyethylene, polypropylene, polyethylene/polypropylene copolymers
or polymer composites.
[0894] Polymer composites are for instance natural products
composites, for example a natural product mixed with a
thermoplastic polymer such as a polyolefin. Such composites are
disclosed in published U.S. app. No. 20040235983, the disclosure of
which is hereby incorporated by reference. Natural products are for
instance wood flour, flax, hemp, jute, kenaf or rice husk. The
thermoplastic polymer is for instance polyethylene or
polypropylene.
[0895] A preferred polymer composition or coating composition
according to the invention additionally contains, for example, one
or more components D) selected from antioxidants, light stabilizers
(such as UV absorbers and/or sterically hindered amines,
phosphites, phosphonites), metal deactivators, nucleating agents,
fillers, plasticisers, pigments, flameproofing agents, antistatic
agents, lubricants, emulsifiers, rheology additives, catalysts,
flow-control agents, optical brighteners, blowing agents and
combinations thereof.
[0896] The employed components D), in particular the antioxidants,
light stabilizers, and metal deactivators, preferably have a high
migration fastness and temperature resistance.
[0897] Suitable antioxidants D) are selected from the following
classes: [0898] 1. Alkylated monophenols, for example
2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di-methylphenol,
2,6-di-tert-butyl-4-ethylphenol, etc; [0899] 2.
Alkylthiomethylphenols, for example
2,4-dioctylthiomethyl-6-tert-butylphenol,
2,4-dioctylthiomethyl-6-methylphenol,
2,4-dioctylthiomethyl-6-ethylphenol,
2,6-di-dodecylthiomethyl-4-nonylphenol, etc; [0900] 3.
Hydroquinones and alkylated hydroquinones, for example
2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,
2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,
2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,
3,5-di-tert-butyl-4-hydroxyanisole,
3,5-di-tert-butyl-4-hydroxyphenyl stearate,
bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate, etc; [0901] 4.
Tocopherols; [0902] 5. Hydroxylated thiodiphenyl ethers, for
example 2,2'-thiobis(6-tert-butyl-4-methylphenol),
2,2'-thiobis(4-octylphenol),
4,4'-thiobis(6-tert-butyl-3-methylphenol),
4,4'-thiobis(6-tert-butyl-2-methylphenol),
4,4'-thiobis(3,6-di-sec-amylphenol),
4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)-disulfide, etc; [0903] 6.
Alkylidenebisphenols, for example
2,2'-methylenebis(6-tert-butyl-4-methylphenol),
2,2'methylenebis(6-tert-butyl-4-ethylphenol),
2,2'-methylenebis[4-methyl-6-(.alpha.-methylcyclohexyl)-phenol,
1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,
2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane,
2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane,
1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane, etc;
[0904] 7. O-, N- and S-benzyl compounds, for example
3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether,
octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,
tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,
tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,
bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-dithioterephthalate,
bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide,
isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, etc;
[0905] 8. Hydroxybenzylated malonates, for example
dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate,
di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,
didodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-malonat-
e,
bis[4-(1,1,3,3-tetramethylbutyl)phenyl-2,2-bis(3,5-di-tert-butyl-4-hydr-
oxybenzyl)malonate, etc; [0906] 9. Aromatic hydroxybenzyl
compounds, for example
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenz-
ene,
1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene-
, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-phenol, etc; [0907]
10. Triazine compounds, for example
2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy-anilino)-1,3,5-tria-
zine,
2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-tr-
iazine,
2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5--
triazine,
2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,
1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,
2,4,6-tris-(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,
1,3,5-tris(3,5-di-tert-butyl-4-hyphenylpropionyl)-hexahydro-1,3,5-triazin-
e, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate, etc.
[0908] 11. Benzylphosphonates, for example
dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,
diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the
calcium salt of the monoethyl ester of
3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, etc; [0909] 12.
Acylaminophenols, for example 4-hydroxylauranilide,
4-hydroxystearanilide, octyl
N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate, etc; [0910] 13.
Esters of .beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid
with mono- or polyhydric alcohols; [0911] 14. Esters of
.beta.-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with
mono- or polyhydric alcohols; [0912] 15. Esters of
.beta.-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono-
or polyhydric alcohols; [0913] 16. Esters of
3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or
polyhydric alcohols; [0914] Suitable mono- or polyhydric alcohols
for compounds 13.) to 16.) are methanol, ethanol, octanol,
octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,
1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis-(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2octane. [0915]
17. Amides of .beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic
acid e.g.
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,
N,N'-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)trimethylenediamide,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyphydrazide,
N,N'-bis[2-(3-(3,5-di-tert-butyl-4-hydroxy-phenylpropionyloxy)ethyloxamid-
e (Naugard.RTM.XL-1, supplied by Uniroyal). [0916] 18. Ascorbic
Acid (Vitamin C) [0917] 19. Aminic antioxidants, for example
N,N'-di-isopropyl-p-phenylenediamine,
N,N'-di-sec-butyl-p-phenylenediamine,
N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine,
N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,
N,N'-bis(1-methylheptyl)-p-phenylenediamine,
N,N'-dicyclohexyl-p-phenylenediamine,
N,N'-diphenyl-p-phenylenediamine,
N,N'-bis(2-naphthyl)-p-phenylenediamine,
N-isopropyl-N'-phenyl-p-phenylenediamine,
N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine,
N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine,
N-cyclohexyl-N'-phenyl-p-phenylenediamine,
4-(p-toluenesulfamoyl)diphenylamine,
N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine,
N-allyldiphenylamine, 4-isopropoxydiphenyl-amine,
N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,
N-phenyl-2-naphthylamine, octylated diphenylamine, for example
p,p'-di-tert-octyldiphenylamine, 4-n-butyl-aminophenol,
4-butyrylaminophenol, 4-nonanoylaminophenol,
4-dodecanoylaminophenol, 4-octadecanoylaminophenol,
bis(4-methoxy-phenyl)amine,
2,6-di-tert-butyl-4-dimethylaminomethylphenol,
2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,
N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane,
1,2-bis[(2-methylphenyl)aminoethane, 1,2-bis(phenyl-amino)propane,
(o-tolyl)biguanide, bis[4-(1',3'-dimethylbutyl)phenylamine,
tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and
dialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono-
and dialkylated nonyldiphenylamines, a mixture of mono- and
dialkylated dodecyldiphenylamines, a mixture of mono- and
dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- and
dialkylated tert-butyldiphenylamines,
2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a
mixture of mono- and dialkylated
tert-butyl/tert-octylphenothiazines, a mixture of mono- and
dialkylated tert-octyl-phenothiazines, N-allylphenothiazine,
N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene.
[0918] Suitable light stabilizers (UV absorbers) and metal
deactivators are selected, for example, from groups a) to s):
a) 4,4-diarylbutadienes, b) cinnamic esters, c) benzotriazoles, d)
hydroxybenzophenones, e) diphenylcyanoacrylates, f) oxamides, g)
2-phenyl-1,3,5-triazines; h) antioxidants, i) nickel compounds, j)
sterically hindered amines, k) metal deactivators, I) phosphites
and phosphonites, m) hydroxylamines, n) nitrones, o) amine oxides,
p) benzofuranones and indolinones, q) thiosynergists, r) peroxide
scavengers, and s) basic costabilizers.
[0919] The antimicrobial compounds A), optional B) and optional
additives D) may be added to at least one polymer and/or at least
one polymerizable compound C) individually or mixed with one
another. If desired, the individual components can be mixed with
one another before incorporation into the polymer or polymerizable
composition for example by dry blending.
[0920] The incorporation of the biocides of the invention can be
carried out by known methods, such as dry blending in the form of a
powder or wet mixing in the form of solutions, dispersions or
suspensions for example in an inert solvent, water or oil. The
biocides of the invention may be incorporated, for example, before
or after molding or also by applying the dissolved or dispersed
biocide (or an additive mixture containing the biocide) to the
polymer material or the polymerisable composition, with or without
subsequent evaporation of the solvent or the suspension/dispersion
agent. They may be added directly into the processing apparatus
(e.g. extruders, internal mixers, etc), e.g. as a dry mixture or
powder or as solution or dispersion or suspension.
[0921] The incorporation can be carried out e.g. in any heatable
container equipped with a stirrer, e.g. in a closed apparatus such
as a kneader, mixer or stirred vessel. The incorporation is
preferably carried out in an extruder or in a kneader. The
processing may take place in an inert atmosphere or in the presence
of oxygen.
[0922] The addition of biocide (or an additive mixture containing
the biocide) to the polymer substrate can be carried out in all
customary mixing machines in which the polymer is melted and mixed
with the additives. Suitable machines are known to those skilledin
the art. They are predominantly mixers, kneaders and extruders.
[0923] Processing includes extrusion, co-kneading, pultrusion,
compression molding, sheet extrusion, thermoforming, injection
molding or rotational molding. The process is preferably carried
out in an extruder by introducing the additives during
processing.
[0924] Particularly preferred processing machines are single-screw
extruders, contrarotating and corotating twin-screw extruders,
rotomolding devices, planetary-gear extruders, ring extruders or
cokneaders. It is also possible to use processing machines provided
with at least one gas removal compartment to which a vacuum can be
applied.
[0925] Suitable extruders and kneaders are described, for example,
in Handbuch der Kunststoffextrusion, Vol. 1 Grundlagen, Editors F.
Hensen, W. Knappe, H. Potente, 1989, pp. 3-7, ISBN:3-446-14339-4
(Vol. 2 Extrusionsanlagen 1986, ISBN 3-446-14329-7).
[0926] The biocide (or an additive mixture containing the biocide)
can also be added to the polymer in the form of a masterbatch
("concentrate") which contains the components in a concentration
of, for example, about 1% to about 40% and preferably about 2% to
about 20% by weight incorporated in a polymer. The polymer must not
necessarily be identical to the polymer where the additives are
added finally. In such operations, the polymer can be used in the
form of powder, granules, solutions, suspensions or in the form of
latices. Incorporation can take place prior to or during the
shaping operation, or by applying the dispersed compound to the
polymer, with or without subsequent evaporation of the solvent. A
further possibility for incorporating the biocide of the invention
(or an additive mixture containing the biocide) into polymer
substrates is to add them before, during or directly after the
polymerization of the corresponding monomers or prior to
crosslinking. In this context the additives of the invention can be
added as it is or else in encapsulated form (for example in waxes,
oils or polymers).
[0927] The polymers containing the biocide (or an additive mixture
containing the biocide) described herein can be used for the
production of moldings, rotomolded articles, injection molded
articles, blow molded articles, profiles, films, woven and nonwoven
fabrics, and the like.
[0928] When the polymer composition or coating composition
according to the invention is used in the medical sector, it is for
example a catheter, hose, tube, valve, articles for urology, bone
cement, fabric, toothbrushes, silicone plastics, films, textiles,
diapers and the like.
[0929] The coating composition according to the invention usually
contains a film forming binder.
[0930] The binder can in principle be any binder which is customary
in industry, for example those described in Ullmann's Encyclopedia
of Industrial Chemistry, 5th Edition, Vol. A18, pp. 368-426, VCH,
Weinheim 1991. In general, it is a film forming binder based on a
thermoplastic or thermosetting resin, predominantly on a
thermosetting resin. Examples thereof are alkyd, acrylic, acrylic
alkyd, polyester, phenolic, melamine, epoxy and polyurethane resins
and mixtures thereof. The binder can be a cold-curable or
hot-curable binder; the addition of a curing catalyst may be
advantageous. Suitable catalysts which accelerate curing of the
binder are described, for example, in Ullmann's Encyclopedia of
Industrial Chemistry, Vol. A18, p. 469, VCH Verlagsgesellschaft,
Weinheim 1991.
[0931] The coating compositions according to the invention are for
example employed as a top coat for plastics or metal or as a wood
coating.
[0932] Examples of coatings compositions containing specific
binders are: [0933] 1. paints based on cold- or hot-crosslinkable
alkyd, acrylate, polyester, epoxy or melamine resins or mixtures of
such resins, if desired with addition of a curing catalyst; [0934]
2. two-component polyurethane paints based on hydroxyl-containing
acrylate, polyester or polyether resins and aliphatic or aromatic
isocyanates, isocyanurates or polyisocyanates; [0935] 3.
one-component polyurethane paints based on blocked isocyanates,
isocyanurates or polyisocyanates which are deblocked during baking,
if desired with addition of a melamine resin; [0936] 4.
one-component polyurethane paints based on a
trisalkoxycarbonyltriazine crosslinker and a hydroxyl group
containing resin such as acrylate, polyester or polyether resins;
[0937] 5. one-component polyurethane paints based on aliphatic or
aromatic urethaneacrylates or polyurethaneacrylates having free
amino groups within the urethane structure and melamine resins or
polyether resins, if necessary with curing catalyst; [0938] 6.
two-component paints based on (poly)ketimines and aliphatic or
aromatic isocyanates, isocyanurates or polyisocyanates; [0939] 7.
two-component paints based on (poly)ketimines and an unsaturated
acrylate resin or a polyacetoacetate resin or a
methacrylamidoglycolate methyl ester; [0940] 8. two-component
paints based on carboxyl- or amino-containing polyacrylates and
polyepoxides; [0941] 9. two-component paints based on acrylate
resins containing anhydride groups and on a polyhydroxy or
polyamino component; [0942] 10. two-component paints based on
acrylate-containing anhydrides and polyepoxides; [0943] 11.
two-component paints based on (poly)oxazolines and acrylate resins
containing anhydride groups, or unsaturated acrylate resins, or
aliphatic or aromatic isocyanates, isocyanurates or
polyisocyanates; [0944] 12. two-component paints based on
unsaturated polyacrylates and polymalonates; [0945] 13.
thermoplastic polyacrylate paints based on thermoplastic acrylate
resins or externally crosslinking acrylate resins in combination
with etherified melamine resins; [0946] 14. paint systems based on
siloxane-modified or fluorine-modified acrylate resins.
[0947] The coating compositions may also comprise further
components, examples being solvents, pigments, dyes, plasticizers,
stabilizers, thixotropic agents, drying catalysts and/or levelling
agents. Examples of possible components are those described in
Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol.
A18, pp. 429-471, VCH, Weinheim 1991.
[0948] Possible drying catalysts or curing catalysts are, for
example, organometallic compounds, amines, amino-containing resins
and/or phosphines. Examples of organometallic compounds are metal
carboxylates, especially those of the metals Pb, Mn, Co, Zn, Zr or
Cu, or metal chelates, especially those of the metals Al, Ti or Zr,
or organometallic compounds, such as organotin compounds, for
example.
[0949] Examples of metal carboxylates are the stearates of Pb, Mn
or Zn, the octoates of Co, Zn or Cu, the naphthenates of Mn and Co
or the corresponding linoleates, resinates or tallates.
[0950] Examples of metal chelates are the aluminium, titanium or
zirconium chelates of acetylacetone, ethyl acetylacetate,
salicylaldehyde, salicylaldoxime, o-hydroxyacetophenone or ethyl
trifluoroacetylacetate, and the alkoxides of these metals.
[0951] Examples of organotin compounds are dibutyltin oxide,
dibutyltin dilaurate or dibutyltin dioctoate.
[0952] Examples of amines are, in particular, tertiary amines, for
example tributylamine, triethanolamine, N-methyldiethanolamine,
N-dimethylethanolamine, N-ethylmorpholine, N-methylmorpholine or
diazabicyclooctane (triethylenediamine) and salts thereof. Further
examples are quaternary ammonium salts, for example
trimethylbenzyl-ammonium chloride.
[0953] Amino-containing resins are simultaneously binder and curing
catalyst. Examples thereof are amino-containing acrylate
copolymers.
[0954] The curing catalyst used can also be a phosphine, for
example triphenylphosphine.
[0955] The coating compositions can also be radiation-curable
coating compositions. In this case, the binder essentially
comprises monomeric or oligomeric compounds containing
ethylenically unsaturated bonds, which after application are cured
by actinic radiation, i.e. converted into a crosslinked, high
molecular weight form. Where the system is UV-curing, it generally
contains a photoinitiator as well. Corresponding systems are
described in the above mentioned publication Ullmann's Encyclopedia
of Industrial Chemistry, 5th Edition, Vol. A18, pages 451-453.
[0956] The coating compositions according to the invention can be
applied to any desired substrates, for example to metal, wood,
plastic, ceramic materials or plastic wood composites.
[0957] The coating compositions according to the invention are also
suitable for protecting a wood surface. In this case, the coating
compositions can be applied in form of a varnish, paint, etc or by
impregnation. A further aspect of the invention is a method for
providing antimicrobial activity to a wood surface which method
comprises applying a present coatings composition, especially a
varnish, paint, stain or impregnation on wood. The coating
composition may be applied by impregnation or as base coat (primer)
or top coat.
[0958] If the coating composition is employed for protecting a wood
surface, preferably a solvent is used, selected e.g. from the group
consisting of aliphatic hydrocarbons, cycloaliphatic hydrocarbons,
aromatic hydrocarbons, alcohols, ethers, esters, ketones, glycols,
glycol ethers, glycol esters, polyglycols or mixtures thereof.
Preferably, in this case the binder is selected from the group
consisting of alkyd resins, modified alkyd resins, autocrosslinking
or non-autocrosslinking acrylic resins, polyester resins, drying
oils, phenolic resins, nitrocellulose or mixtures thereof.
[0959] Other additives like fungicides or insecticides are
possible. Suitable components are known to the skilled artisan.
[0960] Any coating composition suitable for coating wood may be
used as a top coat. It will normally contain a binder, dissolved or
dispersed in an organic solvent or in water or a mixture of water
and solvent. The binder may typically be a surface coating resin
which dries in the air or hardens at room temperature. Exemplary of
such binders are nitrocellulose, polyvinyl acetate, polyvinyl
chloride, unsaturated polyester resins, polyacrylates,
polyurethanes, epoxy resins, phenolic resins, and especially alkyd
resins. The binder may also be a mixture of different surface
coating resins. Provided the binders are curable binders, they are
normally used together with a hardener and/or accelerator.
[0961] The top coat may also be a radiation-curable, solvent-free
formulation of photopolymerizable compounds. Illustrative examples
are mixtures of acrylates or methacrylates, unsaturated
polyester/styrene mixtures or mixtures of other ethylenically
unsaturated monomers or oligomers.
[0962] The top coat may contain a soluble dye and/or a pigment
and/or a filler. The pigment may be an organic, inorganic or
metallic pigment. The pigments may be opaque or transparent, such
as for example transparent iron oxides. The filler may be typically
kaolin, calcium carbonate or aluminium silicate. Preferably, the
top coat is a clear varnish, i.e. it contains no undissolved
components.
[0963] The present invention is particularly useful for the
following applications: in home applications, such as furniture,
wood floors, chipboards or timber work; outdoor applications, such
as fences, construction parts, wooden fronts, window frames and the
like.
[0964] The present coatings compositions may be applied to the
substrates by the customary methods, for example by brushing,
spraying, pouring, dipping or electrophoresis; see also Ullmann's
Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pp.
491-500.
[0965] Depending on the binder system, the coatings may be cured at
room temperature or by heating. The coatings may for example be
cured at 50 to 150.degree. C., and, e.g. in the case of powder
coatings or coil coatings, even at higher temperatures.
[0966] The coating compositions can comprise an organic solvent or
solvent mixture in which the binder is soluble. The coating
compositions can otherwise be an aqueous solution or dispersion.
The vehicle can also be a mixture of organic solvent and water. The
coating composition may be a high-solids paint or can be
solvent-free (e.g. a powder coating material). Powder coatings are,
for example, those described in Ullmann's Encyclopedia of
Industrial Chemistry, 5th Ed., A18, pages 438-444. The powder
coating material may also have the form of a powder-slurry
(dispersion of the powder preferably in water).
[0967] The pigments can be inorganic, organic or metallic pigments.
The present coatings compositions may contain no pigments and may
be used as a clearcoat.
[0968] The following examples illustrate the invention without
restricting it.
EXAMPLES
A) Biocide Compositions
[0969] Determination of the Minimum Inhibitory Concentration
(MIC):
[0970] The effects of the biocidal compositions comprising an
imidazolium polymer were tested in Minimum Inhibitory Concentration
tests against Staphylococcus aureus and Pseudomonas aeruginosa as
exemplary members of the harmful microorganisms mentioned above.
The MIC measurements were performed following a procedure described
by J. M. Andrews, J. Antimicrobial Chemotherapy, (2001) 48, Suppl.
S1, 5-16 based on the commendations of the British Society for
Antimicrobial Chemotherapy.
[0971] For pre-cultivation of the bacteria, Staphylococcus aureus
ATCC 29213 and Pseudomonas aeruginosa ATCC 27853 were streaked onto
IsoSensitest agar plates, respectively, and incubated at 37.degree.
C. overnight. Single colonies were used to inoculate 50 mL of
IsoSensitest broth in 250 mL of baffled Erlenmeyer flasks at 190
rpm and 37.degree. C. for 15 hours, respectively. Then, 50 mL of
IsoSensitest broth were inoculated with the precultures to a final
optical density of OD=0.1, respectively.
[0972] Stock solutions of the biocidal composition comprising an
imidazolium polymer were prepared at 10 mg/mL and 1 mg/mL in
deionized water. Dilution series (log 2, from 4096 .mu.g/mL to 0.25
.mu.g/mL) with deionized water were made. Concentrations from 4096
.mu.g/mL to 8 .mu.g/mL were made using the 10 mg/mL stock solution;
Concentrations from 4 .mu.g/mL to 0.25 .mu.g/mL were made using the
1 mg/mL stock solution. 75 .mu.l quantities of each dilution were
added to 8 wells of a 96 well microtiter-plate, respectively. Then,
75 .mu.l of the bacterial suspension with an optical density of
OD=0.1 were added to the wells. Wells charged with 75 .mu.l of
water and 75 .mu.l of non-inoculated IsoSensitest broth served as
sterile control. Wells charged with 75 .mu.l of water and 75 .mu.l
of bacterial suspension served as positive control for unrestricted
growth. The microtiter-plates were incubated for 24 hours at
37.degree. C. and 750 rpm and the growth of microorganisms was
determined by measuring the optical density. The optical density
was measured in a time frame from 1.5 h to 24 h. As Minimum
Inhibitory Concentration, these concentrations were determined,
where no growth could be observed after 24 h (OD smaller than 0.1).
As a control, three known antibiotics were chosen (J. M. Andrews,
J. Antimicrobial Chemotherapy, (2001), 48, Suppl. S1, 5-16) to
offer a comparison of the biocidal composition comprising an
imidazolium polymer with known antibiotics.
TABLE-US-00001 TABLE 1 Imidazolium polymers and their biological
activity: MIC MIC Staphylococcus Pseudomonas aureus aeruginosa ATCC
29213 = ATCC 27853 = Repeating unit of the imidazolium DSM 2569 DSM
1117 No. Diamine Acid polymer [.mu.g/mL] [.mu.g/mL] 1 1,4- Butane-
diamine Acetic acid ##STR00025## 4 4 2 1,4- Butane- diamine
Phosphoric acid ##STR00026## 4 2 3 1,4- Butane- diamine Methane
sulfonic acid ##STR00027## 16 8 4 1,4- Butane- diamine Sulfuric
acid ##STR00028## 2 2 5 1,4- Butane- diamine Hexanoic acid
##STR00029## 8 4 6 1,4- Butane- diamine Octanoic acid ##STR00030##
8 8 7 1,4- Butane- diamine Adipic acid ##STR00031## 32 16 8 1,4-
Butane- diamine Terephthalic acid ##STR00032## 4 4 9 1,5- Pentane-
diamin Acetic acid ##STR00033## 4 8 10 1,6- Hexane- diamin Acetic
acid ##STR00034## 8 64 11 1,6- Hexane- diamin Methane sulfonic acid
##STR00035## 8 16 12 1,6- Hexane- diamin [2-(2-methoxy- ethoxy)-
ethoxy]-acetic acid ##STR00036## 4 8 13 1,12- Dodecane- diamine
Acetic acid ##STR00037## 8 32 14 Poly(vinyl- formamid- co- vinyl-
amine) ca. 50% hydrolysis grade Acetic acid -- 128 15 1,8- Diamino-
3,6- dioxa- octane Acetic acid ##STR00038## 16 16 17 1,8- Diamino-
3,6- dioxa- octane Sulfuric acid ##STR00039## 32 16 18 Tris(2-
Acetic acid 32 -- amino- ethylamine) 0.5 parts + 1,6-hexane-
diamine 0.5 parts 19 Tris(2- Acetic acid 64 amino- ethylamine) 0.5
parts + 1,6-hexane- diamine 1 part 20 Tris(2- Acetic acid 16 --
amino- ethylamine) 0.3 parts + 1,6-hexane- diamine 1 part 21
Tris(2- Acetic acid 32 -- amino- ethylamine) 0.5 parts +
1,4-butane- diamine 0.5 parts 22 Tris(2- Acetic acid 64 -- amino-
ethylamine) 0.3 parts + 1,4-butane- diamine 1 parts 23 Tris(2-
Acetic acid 64 -- amino- ethylamine) 0.7 parts 24 Tris(2- Acetic
acid 64 -- amino- ethylamine) 0.5 parts + ethylene diamine 0.5
parts
TABLE-US-00002 TABLE 2 Known biocidal polymers and their biological
activity MIC MIC Pseudomonas Staphylococcus aeruginosa aureus ATCC
ATCC 27853 = Comparative structure of the prior art 29213 = DSM DSM
1117 No. polymers polymer 2569 [.mu.g/mL] [.mu.g/mL] C1
Poly(vinylformamid- 256 256 co-vinylamine) >90% hydrolysis grade
C2 1,3- Dibutyl- imidazolium acetate ##STR00040## 2048 4096
TABLE-US-00003 TABLE 3 Known antibiotics and their biological
activity as control MIC MIC Staphylococcus Pseudomonas aureus
aeruginosa ATCC 29213 = ATCC 27853 = Control DSM 2569 DSM 1117 No.
antibiotics [.mu.g/mL] [.mu.g/mL] Control 1 Cephalexine 4 >4096
Control 2 Tetracycline 1 32 Control 3 Nalidixic acid 64 1024
B) Cosmetic Compositions
[0973] The active materials (AM) are given in percentages.
Examples 1 to 4 (Shampoo Compositions)
TABLE-US-00004 [0974] In g AM example no. 1 2 3 4 Cocoglucoside [1]
5 5 5 5 Cocoamidopropyl 5.4 5.4 5.4 5.4 betaine [2] Sodium lauryl
ether (5 OE) carboxylate [3] 3 3 3 3 Sodium lauryl ether sulfate
[4] 4 4 4 4 Imidazolium compound according to 0.4 0.4 0.4 0.4
example 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17,
18, 19, 20, 21, 22, 23, 24 Polydimethylsiloxane 2.6 1 0.5 0.1
(Dimethicone) [5] Preserving agent qs qs qs qs Fragrance qs qs qs
qs Citric acid qs qs qs qs pH 6.5 6.5 6.5 6.5 Water qs 100 g 100 g
100 g 100 g [1] PLANTACARE .RTM. 818 UP sold by Cognis [2] DEHYTO
.RTM. AB 30 sold by Cognis [3] AKYPO .RTM. RLM 45 CA sold by KAO
[4] TEXAPON .RTM. N 702 sold by Cognis [5] DC 200 Fluid 60000 CS
sold by Dow Corning
Example 5 (Hair Conditioner with Anionic Associative Polymer)
TABLE-US-00005 [0975] Imidazolium compound according to example 1,
1 g 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19,
20, 21, 22, 23, 24 Methacrylic acid/ethyl acrylate/oxyethylenated
0.1 g AM (25 EO) behenyl methacrylate terpolymer as an aqueous
emulsion (20 wt %) [1] Chlorhexidine digluconate solution 0.2 g
Methyl p-hydroxybenzoate 0.3 g Lactic acid qs pH 4.0 +- 0.2
Cetylstearyl alcohol [2]g 5 g Water qs 100 g [1] sold under the
trade name Aculyn 28 by Rohm & Haas [2] sold under the trade
name Lanette O OR by the company Cognis
[0976] The obtained hair conditioner composition was stable and
viscous. When applied to wet hair after shampooing, it could be
easily applied, had a good spreadability and good wash-out
properties. The treated hair was smooth and shiny.
Example 6 (Antidandruff Shampoo Composition)
TABLE-US-00006 [0977] Sodium lauryl ether sulphate (2.2 EO) 17 g AM
Cocoylbetaine as an aqueous 30% solution 2.5 g AM (DEHYTON AB 30
from Henkel) Terpolymer of methacrylamidopropyl- 1 g AM
trimethylammonium chloride, acrylic acid and stearyl methacrylate
(49 mol %/49 mol %/2 mol %) Sodium cetostearyl sulphate 0.75 g
Coconut acid monoisopropanolamide 0.6 g Imidazolium compound
according to example 1, 2, 0.5 g 3, 4, 5, 6, 7, 8, 9, 10, 11, 12,
13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 Preserving agents,
fragrance qs Water qs 100 g
Example 7 (Cream for Treatment of Acne and Hyperseborrhoea)
TABLE-US-00007 [0978] Imidazolium compound according to example 1,
2, 1.00% 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18,
19, 20, 21, 22, 23, 24 Sorbitane tristearate 1.00% perfume 0.30%
crosslinked acrylic acid homopolymer 0.40% xanthane gum 0.50%
copolymer of ethylene glycol dimethacrylate/lauryl 1.00%
methacrylate cyclopenta dimethylsiloxane 6.00% glycerine 3.00%
mixture of cetyl/stearyl alcohol, ethoxylated stearyl 4.00% alcohol
(6 EO and 32 EO) demineralized water qs 100
Example 8 (Mineral Oil)
TABLE-US-00008 [0979] oleth-5 5.00 cetyl alcohol (and)
behentrimonium 1.00 methosulfate (and) Quaternium-33
2-oleamido-1,3-octadecandiol 0.10 oleth-20 5.00 Imidazolium
compound according to example 1, 0.50 2, 3, 4, 5, 6, 7, 8, 9, 10,
11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24
Example 9 (Foam Conditioner)
TABLE-US-00009 [0980] [%] Imidazolium compound according to example
1, 2, 3, 4, 5, 6, 7, 8, 20.00 9, 10, 11, 12, 13, 14, 15, 16, 17,
18, 19, 20, 21, 22, 23, 24 Cremophor A 25 (Ceteareth 25/BASF) 0.2
Comperlan KD (Coamide DEA/Henkel) 0.1 Water 69.7 Propane/butane
10.0 Further additive: perfume, preservative . . .
[0981] Preparation: Weigh in and dissolve with stirring. Bottle and
add propellant gas.
Example 10 (Hair Gel)
TABLE-US-00010 [0982] [%] Phase 1: Imidazolium compound according
to example 1, 2, 3, 4, 5, 6, 7, 8, 12.00 9, 10, 11, 12, 13, 14, 15,
16, 17, 18, 19, 20, 21, 22, 23, 24 Water, dist. 37.00
Aminomethylpropanol (38% strength solution) 1.0 Further additive:
preservative, soluble ethoxylated silicone, perfume . . . Phase 2:
Aculyn 28 (1% strength aqueous suspension) 50.00
[0983] Preparation:
[0984] Phases 1 and 2 are weighed in and homogenized separately.
Phase 2 is then slowly stirred into phase 1. An essentially clear,
stable gel forms.
Example 11 (Hair Gel)
TABLE-US-00011 [0985] [%] Phase 1: Imidazolium compound according
to example 1, 2, 3, 4, 5, 6, 7, 8, 12.00 9, 10, 11, 12, 13, 14, 15,
16, 17, 18, 19, 20, 21, 22, 23, 24 Water, dist. 30.00 Further
additive: preservative, soluble ethoxylated silicone, perfume . . .
Phase 2: Natrosol HR 250 (5% strength solution) 50.00
Hydroxyethylcellulose (Hercules)
[0986] Preparation:
[0987] Phases 1 and 2 are weighed in and homogenized separately.
Phase 2 is then slowly stirred into phase 1. An essentially clear,
stable gel forms.
C) Fungicidal Activity
[0988] The following polymers F1 to F27 were prepared according to
the procedures described in WO 2010/0725721. C1 is a comparative
example.
[0989] The .alpha.-dicarbonyl compound a) used was glyoxal, the
aldehyde b) used was a formaldehyde source and the diamine c) used
is indicated in the table.
[0990] Polymers F28 and F29 were prepared as follows:
[0991] F28: 1,4-Diaminobutane (1.1 mol) and glyoxal (1.1 mol) were
added at room temperature simultaneously dropwise to benzaldehyde
(1.1 moles) in of acetic acid (4.3 mol). The mixture was heated for
three hours to reflux. Water was distilled off to give the polymer
as a dark oil.
[0992] .sup.1H-NMR (D.sub.2O) .delta.=7.86-7.15 (m, 1H); 4.31-4.18
(m, 0.3H); 3.31-2.99 (m, 0.5H); 2.05 (s, 1.6H); 2.01-1.83 (m,
0.8H).
[0993] F29: The polymer was prepared in analogy to polymer F28,
using however dodecanal as aldehyde.
[0994] .sup.1H-NMR (D.sub.2O) .delta.=7.61-7.48 (m, 1H); 4.32-4.15
(m, 2.2H); 3.10-2.96 (m, 2.5H); 2.04 (s, 21H); 2.01-1.86 (m, 3.3H);
1.81-1.65 (m, 3.2H); 1.47-1.14 (m, 12H).
[0995] M.sub.w is the weight-average molecular weight as obtained
by GPC (gel permeation chromatography/size exclusion
chromatography) using 0.02 mol/l formic acid+0.2 mol/l KCl in water
as elution agent and pullulan standard (linear polymaltotriose and
maltohexose; from PSS, Germany), or using
hexafluoroisopropanol+0.05% potassium trifluoroacetate in water as
elution agent and PMMA standard. PDI is the polydispersity
M.sub.w/M.sub.n (M.sub.n=number-average molecular weight).
TABLE-US-00012 No. amine repeating units M.sub.w PDI F1
1,4-diamino-butane ##STR00041## 30000 8 F2 1,4-diamino-butane
##STR00042## F3 1,4-diamino-butane ##STR00043## F4
1,6-diamino-hexane ##STR00044## F5 1,4-diamino-butane ##STR00045##
F6 1,6-diamino-hexane ##STR00046## 10700 5.4 F7
2,6-diamino-hexanoic acid ##STR00047## 10200 4.3 F8
1,6-diamino-hexane ##STR00048## 19600 12.3 F9
NH.sub.2--(CH.sub.2).sub.3--(OCH.sub.2CH.sub.2)O--(CH.sub.2).sub.3--NH.-
sub.2 ##STR00049## F10
NH.sub.2--[(CH.sub.2).sub.2O].sub.2--(CH.sub.2).sub.2--NH.sub.2
##STR00050## F11
NH.sub.2--[(CH.sub.2).sub.2O].sub.2--(CH.sub.2).sub.2--NH.sub.2
##STR00051## F12 1,4-diamino-butane ##STR00052## 10000 7.2 F13
1,4-diamino-butane ##STR00053## 13200 6.4 F14 1,6-diamino-hexane
##STR00054## F15 1,4-diamino-butane ##STR00055## 38500 2.5 F16
1,12-diamino-dodecane ##STR00056## 70000 2.5 F17 1,4-diamino-butane
##STR00057## 2310 F18 1,4-diamino-butane ##STR00058## 112000 F19
1,4-diamino-butane ##STR00059## 40000 F20 1,4-diamino-butane
##STR00060## 8770 F21 80% 1,4-diamino-butane + 20% anion: acetate
3000
CH.sub.3CH.sub.2C--(OCH.sub.2CH.sub.2--CH(CH.sub.3)NH.sub.2).sub.3
F22 see F21 anion: acetate 14000 F23
Bis(4-amino-cyclohexyl)-methane ##STR00061## 12000 F24
1,8-diamino-octane ##STR00062## 43000 F25 1,6-diamino-hexane
##STR00063## 70000 F26 3-amino-methylbenzyl-amine ##STR00064##
20000 F27 isophoron-diamine ##STR00065## 49800 F28
1,4-diamino-butane ##STR00066## 1200 1.9 F29 1,4-diamino-butane
##STR00067## C1 1,4-diamino-2-hydroxy-propane ##STR00068##
C.1) Green House Tests
[0996] The spray solutions were prepared in several steps:
[0997] The stock solutions were prepared: a mixture of acetone
and/or dimethylsulfoxide and the wetting agent/emulsifier Wettol,
which is based on ethoxylated alkylphenoles, in a relation (volume)
solvent-emulsifier of 99 to 1 was added to 25 mg of the active
compound to give a total of 5 ml. Water was then added to total
volume of 100 ml. This stock solution was diluted with the
described solvent-emulsifier-water mixture to the given
concentration.
C.1.1) Preventative Fungicidal Control of Botrytis cinerea on
Leaves of Green Pepper
[0998] Young seedlings of green pepper were grown in pots to the 4
to 5 leaf stage. These plants were sprayed to run-off with an
aqueous suspension, containing the concentration of active
ingredient or their mixture mentioned in the table below. The next
day the plants were inoculated with an aqueous biomalt solution
containing the spore suspension of Botrytis cinerea. Then the
plants were immediately transferred to a humid chamber. After 5
days at 22 to 24.degree. C. and a relative humidity close to 100%
the extent of fungal attack on the leaves was visually assessed as
% diseased leaf area.
[0999] The untreated control showed 90% disease.
[1000] Plants treated with 250 ppm of compounds F1 and F13,
respectively, had at most 40% diseased leaf area. Plants treated
with 250 ppm of compound C1 showed 90% diseased leaf area.
[1001] Plants treated with 500 ppm of compounds F1, F5, F8, F11,
F18, F20 and F26, respectively, had at most 7% diseased leaf
area.
C.1.2) Protective Control of Soy Bean Rust on Soy Beans Caused by
Phakopsora pachyrhizi
[1002] Leaves of pot-grown soy bean seedlings were sprayed to
run-off with an aqueous suspension, containing the concentration of
active ingredient or their mixture as described below. The plants
were allowed to air-dry. The trial plants were cultivated for 1 day
in a greenhouse chamber at 23-27.degree. C. and a relative humidity
between 60 and 80%. Then the plants were inoculated with spores of
Phakopsora pachyrhizi. To ensure the success the artificial
inoculation, the plants were transferred to a humid chamber with a
relative humidity of about 95% and 20 to 24.degree. C. for 24 h.
The trial plants were cultivated for fourteen days in a greenhouse
chamber at 23-27.degree. C. and a relative humidity between 60 and
80%. The extent of fungal attack on the leaves was visually
assessed as % diseased leaf area.
[1003] The untreated control showed 70% diseased leaf area.
[1004] Plants treated with 250 ppm of compounds F1 and F15,
respectively, had at most 30% diseased leaf area. Plants treated
with 250 ppm of compound C1 showed 70% diseased leaf area.
[1005] Plants treated with 500 ppm of compounds F2, F3, F4, F5,
F10, F13, F14, F21, F22, F23, F24 and F25, respectively, had at
most 20% diseased leaf area.
C.1.3) Control of Late Blight on Tomatoes Caused by Phytophthora
infestans
[1006] Young seedlings of tomato plants were grown in pots. These
plants were sprayed to run-off with an aqueous suspension,
containing the concentration of active ingredient or their mixture
mentioned in the table below. The next day, the treated plants were
inoculated with an aqueous suspension of sporangia of Phytophthora
infestans. After inoculation, the trial plants were immediately
transferred to a humid chamber. After 6 days at 18 to 20.degree. C.
and a relative humidity close to 100% the extent of fungal attack
on the leaves was visually assessed as % diseased leaf area.
[1007] The untreated control showed 90% diseased leaf area.
[1008] Plants treated with 500 ppm of compounds F1, F8, F11, F15,
F16, F18, F22, F23, F24, F25 and F26, respectively, had at most 20%
diseased leaf area.
C.2) Microtests
[1009] The active compounds were formulated separately as a stock
solution having a concentration of 10000 ppm in dimethyl
sulfoxide.
C.2.1) Activity Against the Grey Mold Botrytis cinerea in the
Microtiterplate Test (Botrci)
[1010] The stock solutions were mixed according to the ratio,
pipetted onto a micro titer plate (MTP) and diluted with water to
the stated concentrations. A spore suspension of Botrci cinerea in
an aqueous biomalt or yeast-bactopeptone-sodiumacetate solution was
then added. The plates were placed in a water vapor-saturated
chamber at a temperature of 18.degree. C. Using an absorption
photometer, the MTPs were measured at 405 nm 7 days after the
inoculation.
[1011] The measured parameters were compared to the growth of the
active compound-free control variant (100%) and the fungus-free and
active compound-free blank value to determine the relative growth
in % of the pathogens in the respective active compounds.
C.2.2) Activity Against the Late Blight Pathogen Phytophthora
infestans in the Microtiter Test (Phytin)
[1012] The stock solutions were mixed according to the ratio,
pipetted onto a micro titer plate (MTP) and diluted with water to
the stated concentrations. A spore suspension of Phytophtora
infestans containing a pea juice-based aqueous nutrient medium or
DDC medium was then added. The plates were placed in a water
vapor-saturated chamber at a temperature of 18.degree. C. Using an
absorption photometer, the MTPs were measured at 405 nm 7 days
after the inoculation.
[1013] The measured parameters were compared to the growth of the
active compound-free control variant (100%) and the fungus-free and
active compound-free blank value to determine the relative growth
in % of the pathogens in the respective active compounds.
C.2.3) Activity Against Leaf Blotch on Wheat Caused by Septoria
tritici (Septtr)
[1014] The stock solutions were mixed according to the ratio,
pipetted onto a micro titer plate (MTP) and diluted with water to
the stated concentrations. A spore suspension of Septoria tritici
in an aqueous biomalt or yeast-bactopeptone-glycerine solution was
then added. The plates were placed in a water vapor-saturated
chamber at a temperature of 18.degree. C. Using an absorption
photometer, the MTPs were measured at 405 nm 7 days after the
inoculation.
[1015] The measured parameters were compared to the growth of the
active compound-free control variant (100%) and the fungus-free and
active compound-free blank value to determine the relative growth
in % of the pathogens in the respective active compounds.
TABLE-US-00013 Growth (%) Growth (%) Growth (%) Compound at 32 pm
at 32 pm at 32 pm no. Botrci Phytin Septtr F1 0 F3 0 F4 0 F5 0 F6 0
1 0 F8 0 F11 0 F12 0 0 0 F13 0 F15 0 F16 2
C.3) Microtests with Mixtures of Active Compounds
[1016] The active compounds were formulated separately as a stock
solution having a concentration of 10000 ppm in dimethyl
sulfoxide.
C.3.1) Activity Against the Late Blight Pathogen Phytophthora
infestans in the Microtiter Test (Phytin)
[1017] The stock solutions were mixed according to the ratio,
pipetted onto a micro titer plate (MTP) and diluted with water to
the stated concentrations. A spore suspension of Phytophtora
infestans containing a pea juice-based aqueous nutrient medium or
DDC medium was then added. The plates were placed in a water
vapor-saturated chamber at a temperature of 18.degree. C. Using an
absorption photometer, the MTPs were measured at 405 nm 7 days
after the inoculation.
[1018] The measured parameters were compared to the growth of the
active compound-free control variant (100%) and the fungus-free and
active compound-free blank value to determine the relative growth
in % of the pathogens in the respective active compounds. These
percentages were converted into efficacies.
[1019] The expected efficacies of active compound mixtures were
determined using Colby's formula [R. S. Colby, "Calculating
synergistic and antagonistic responses of herbicide combinations",
Weeds 15, 20-22 (1967)] and compared with the observed
efficacies.
TABLE-US-00014 Calculated efficacy Active Con- according compound/
centration Observed to Colby Synergism active mixture (ppm) Mixture
efficacy (%) (%) F15 1 -- 46 Pyraclostrobin 0.063 -- 24
Epoxiconazole 0.25 -- 11 Azole* 4 -- 20 Fluxapyroxad 0.063 -- 12
F15 1 16:1 87 59 28 Pyraclostrobin 0.063 F15 1 4:1 86 52 34
Epoxiconazole 0.25 F15 1 1:4 91 57 34 Azole* 4 F15 1 16:1 84 53 31
Fluxapyroxad 0.063
C.3.2) Activity Against the Grey Mold Botrytis cinerea in the
Microtiterplate Test (Botrci)
[1020] The stock solutions were mixed according to the ratio,
pipetted onto a micro titer plate (MTP) and diluted with water to
the stated concentrations. A spore suspension of Botrci cinerea in
an aqueous biomalt or yeast-bactopeptone-sodiumacetate solution was
then added. The plates were placed in a water vapor-saturated
chamber at a temperature of 18.degree. C. Using an absorption
photometer, the MTPs were measured at 405 nm 7 days after the
inoculation.
TABLE-US-00015 Calculated efficacy Active Con- according compound/
centration Observed to Colby Synergism active mixture (ppm) Mixture
efficacy (%) (%) F15 1 -- 18 Pyraclostrobin 0.016 -- 0
Epoxiconazole 0.063 -- 34 Azole* 1 -- 15 Fluxapyroxad 0.016 -- 13
F15 1 63:1 69 18 51 Pyraclostrobin 0.016 F15 1 16:1 99 45 54
Epoxiconazole 0.063 F15 1 1:1 100 30 70 Azole* 1 F15 1 63:1 98 28
70 Fluxapyroxad 0.016
C.3.3) Activity Against Rice Blast Pyricularia oryzae in the
Microtiterplate Test (Pyrior)
[1021] The stock solutions were mixed according to the ratio,
pipetted onto a micro titer plate (MTP) and diluted with water to
the stated concentrations. A spore suspension of Pyricularia oryzae
in an aqueous biomalt or yeast-bactopeptone-glycerine solution was
then added. The plates were placed in a water vapor-saturated
chamber at a temperature of 18.degree. C. Using an absorption
photometer, the MTPs were measured at 405 nm 7 days after the
inoculation.
TABLE-US-00016 Calculated efficacy Active Con- according compound/
centration Observed to Colby Synergism active mixture (ppm) Mixture
efficacy (%) (%) F15 4 -- 8 1 -- 0 F19 4 -- 14 1 -- 5 Azole* 16 --
65 Epoxiconazole 0.25 -- 5 F15 1 1:16 96 65 31 Azole* 16 F15 4 16:1
66 12 54 Epoxiconazole 0.25 F19 1 1:16 86 67 19 Azole* 16 F19 4
16:1 36 18 18 Epoxiconazole 0.25
C.3.4) Activity Against Leaf Blotch on Wheat Caused by Septoria
tritici (Septtr)
[1022] The stock solutions were mixed according to the ratio,
pipetted onto a micro titer plate (MTP) and diluted with water to
the stated concentrations. A spore suspension of Septoria tritici
in an aqueous biomalt or yeast-bactopeptone-glycerine solution was
then added. The plates were placed in a water vapor-saturated
chamber at a temperature of 18.degree. C. Using an absorption
photometer, the MTPs were measured at 405 nm 7 days after the
inoculation.
TABLE-US-00017 Calculated efficacy Active Con- according compound/
centration Observed to Colby Synergism active mixture (ppm) Mixture
efficacy (%) (%) F19 0.016 -- 0 F24 0.063 -- 1 Pyraclostrobin 0.001
-- 38 Azole* 4 -- 40 0.25 -- 4 F19 0.016 16:1 63 38 25
Pyraclostrobin 0.001 F24 0.063 1:4 33 4 29 Azole* 0.25 Azole* =
2-[rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranyl-
methyl]-2H-[1,2,4]triazole-3-thiol
* * * * *
References