U.S. patent application number 11/805738 was filed with the patent office on 2007-10-04 for amine reaction compounds comprising one or more active ingredient.
This patent application is currently assigned to The Procter & Gamble Company Attention: Chief Patent Counsel. Invention is credited to Jean-Luc Philippe Bettiol, Alfred Busch, Hugo Denutte, Christophe Laudamiel, Peter Marie Kamiel Perneel, Marie Montserrat Sanchez-Pena, Johan Smets.
Application Number | 20070232507 11/805738 |
Document ID | / |
Family ID | 32930974 |
Filed Date | 2007-10-04 |
United States Patent
Application |
20070232507 |
Kind Code |
A1 |
Bettiol; Jean-Luc Philippe ;
et al. |
October 4, 2007 |
Amine reaction compounds comprising one or more active
ingredient
Abstract
The present invention relates to a product of reaction between a
primary and/or secondary amine and one or more active ingredients.
By the present invention, there is provided a release of the active
component over a longer period of time than by the use of the
active itself.
Inventors: |
Bettiol; Jean-Luc Philippe;
(Brussels, BE) ; Busch; Alfred; (Londerzeel,
BE) ; Denutte; Hugo; (Hofstade, BE) ;
Laudamiel; Christophe; (New York, NY) ; Perneel;
Peter Marie Kamiel; (Brugge, BE) ; Sanchez-Pena;
Marie Montserrat; (Brussels, BE) ; Smets; Johan;
(Lubbeek, BE) |
Correspondence
Address: |
THE PROCTER & GAMBLE COMPANY;INTELLECTUAL PROPERTY DIVISION - WEST BLDG.
WINTON HILL BUSINESS CENTER - BOX 412
6250 CENTER HILL AVENUE
CINCINNATI
OH
45224
US
|
Assignee: |
The Procter & Gamble Company
Attention: Chief Patent Counsel
6090 Center Hill Road
Cincinnati
OH
45224
|
Family ID: |
32930974 |
Appl. No.: |
11/805738 |
Filed: |
May 24, 2007 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11636052 |
Dec 8, 2006 |
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11805738 |
May 24, 2007 |
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11395716 |
Mar 31, 2006 |
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11636052 |
Dec 8, 2006 |
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11165644 |
Jun 24, 2005 |
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11395716 |
Mar 31, 2006 |
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10911283 |
Aug 4, 2004 |
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11165644 |
Jun 24, 2005 |
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10403867 |
Mar 31, 2003 |
6790815 |
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10911283 |
Aug 4, 2004 |
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10157790 |
May 29, 2002 |
6566312 |
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10403867 |
Mar 31, 2003 |
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09720395 |
Dec 20, 2000 |
6413920 |
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10157790 |
May 29, 2002 |
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Current U.S.
Class: |
510/103 |
Current CPC
Class: |
C11D 3/37 20130101; C11D
3/3742 20130101; C11D 3/2072 20130101; C11D 17/06 20130101; C11D
3/3769 20130101; C11D 3/3723 20130101; C11D 3/0015 20130101; C11D
3/502 20130101; C11D 3/2093 20130101; C11D 3/001 20130101; C11D
17/0039 20130101; C11D 3/50 20130101; C11D 3/22 20130101; C11D
3/507 20130101 |
Class at
Publication: |
510/103 |
International
Class: |
C11D 3/50 20060101
C11D003/50 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 12, 1999 |
US |
PCT/US99/15665 |
Jul 10, 1998 |
EP |
98870156.1 |
Oct 28, 1998 |
EP |
98870227.0 |
Claims
1. A product of reaction between: a.) an amine containing component
comprising a primary or secondary amine, said component having an
Odor Intensity Index of less than that of a 1% solution of
methylanthranilate in dipropylene glycol, with the proviso that
said amine containing component is not an aminostyrene; b.) an
active component selected from a ketone, an aldehyde, and mixtures
thereof; said product of reaction having a Dry Surface Odor Index
of more than 5.
2. A product of reaction according to claim 1, wherein said amine
containing component is selected from the group consisting of amino
substituted polysaccharides, dendrimers, amino acids, amino acid
derivatives, polyalkyleneimines, polyethyleneimines, partially
alkoxylated polyethylenimines, partially alkoxylated
polyalkyleneimines, polyaminoalkylpolysiloxanes, amino
functionalized polydialkylsiloxanes, amino functionalized organo
silanes, amino functionalized organic-organosilicon copolymers,
alkyleneamines, 2,2',2''-triaminotriethylamine; polyetheramines,
polyoxyalkyleneamines, 2,2'-diamino-diethylamine;
3,3'-diamino-dipropylamine, 1,3 bis aminoethyl-cyclohexane;
piperazines with more then one amine groups; and mixtures
thereof.
3. A product of reaction according to claim 1, wherein said amine
containing component comprises dendrimers of polyethyleneimines,
polypropyleneimines or polyamidoamines, polyalkyleneimines,
polyethyleneimines, and mixtures thereof.
4. A product of reaction according to claim 1, wherein said amine
containing component comprises polyaminoalkylpolysiloxanes,
polyetheramines, alkyleneamines, piperazines with more then one
amine group and mixtures thereof.
5. A product of reaction according to claim 1, wherein said amine
containing component comprises a material having at least 2 amine
groups, said material being selected from the group consisting of
polyethyleneimines, polyaminoalkylpolysiloxanes, polyetheramines,
alkanolamines, ethyleneamines, polysaccharides, alkyleneamines and
mixtures thereof.
6. A softening composition comprising the product of reaction of
claim 1.
7. A softening composition according to claim 6, wherein said
product of reaction is preformed before being incorporated into the
fully-formulated composition.
8. A softening composition according to claim 6, wherein said
product of reaction is present in an amount of from 0.001% to 10%
by weight of the composition.
9. A softening composition according to claim 8, wherein said
product of reaction is present in an amount of from 0.005% to 5% by
weight of the composition.
10. A softening composition according to claim 9, wherein said
product of reaction is present in an amount of from 0.01% to 2% by
weight of the composition.
11. A product of reaction according to claim 1, wherein said active
compound is selected from the group consisting of flavour ketone or
aldehyde ingredients, pharmaceutical ketone or aldehyde actives,
biocontrol ketone or aldehyde agents, perfume ketone or aldehyde
components, refreshing cooling ketone or aldehyde agents and
mixtures thereof.
12. A product of reaction according to claim 11, wherein said
active component comprises an insect and/or moth repellant.
13. A product of reaction according to claim 12 comprising an
insect and/or moth repellant selected from the group consisting of
citronellal, citral, N, N diethyl meta toluamide, Rotundial,
8-acetoxycarvotanacenone and mixtures thereof.
14. A product of reaction according to claim 11, wherein said
active component comprises an anti-microbial.
15. A product of reaction according to claim 14, wherein said
active component comprises an anti-microbial selected from the
group consisting of Glutaraldehyde, Cinnamaldehyde and mixtures
thereof.
16. A product of reaction according to claim 11, wherein said
active component comprises a perfume aldehyde.
17. A product of reaction according to claim 16, wherein said
active component comprises a perfume aldehyde, selected from the
group consisting of 1-decanal, benzaldehyde, florhydral,
2,4-dimethyl-3-cyclohexen-1-carboxaldehyde;
cis/trans-3,7-dimethyl-2,6-octadien-1-al; heliotropin;
2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde; 2,6-nonadienal;
alpha-n-amyl cinnamic aldehyde, alpha-n-hexyl cinnamic aldehyde,
P.T. Bucinal, lyral, cymal, methyl nonyl acetaldehyde, hexanal,
trans-2-hexenal, and mixtures thereof.
18. A product of reaction according to claim 11, wherein said
active component comprises a perfume ketone.
19. A product of reaction according to claim 18, wherein said
active component comprises a perfume ketone selected from the group
consisting of Alpha Damascone, Delta Damascone, Iso Damascone,
Carvone, Gamma-Methyl-Ionone, Iso-E-Super,
2,4,4,7-Tetramethyl-oct-6-en-3-one, Benzyl Acetone, Beta Damascone,
Damascenone, methyl dihydrojasmonate, methyl cedrylone, and
mixtures thereof.
20. A product of reaction according to claim 11 wherein said
perfume has an Odor Detection Threshold lower than or equal to 1
ppm.
21. A product of reaction according to claim 11 wherein said
perfume has an Odor Detection Threshold lower than or equal to 10
ppb.
22. A product of reaction according to claim 20 wherein said
perfume is selected from the group consisting of undecylenic
aldehyde, undecalactone gamma, heliotropin, dodecalactone gamma,
p-anisic aldehyde, para hydroxy-phenyl-butanone, cymal, benzyl
acetone, ionone alpha, p.t. bucinal, damascenone, ionone beta and
methyl-nonyl ketone, and mixtures thereof.
23. A softening composition comprising a product of reaction
according to claim 1 wherein: a.) said amine containing component
is selected from the group consisting of amino substituted
polysaccharides, dendrimers, amino acids, amino acid derivatives,
polyalkyleneimines, polyethyleneimines, partially alkoxylated
polyethylenimines, partially alkoxylated polyalkyleneimines,
polyaminoalkylpolysiloxanes, amino functionalized
polydialkylsiloxanes, amino functionalized organo silanes, amino
functionalized organic-organosilicon copolymers, alkyleneamines,
2,2',2''-triaminotriethylamine, polyetheramines,
polyoxyalkyleneamines, 2,2'-diamino-diethylamine,
3,3'-diamino-dipropylamine, 1,3 bis aminoethyl-cyclohexane,
piperazines with more then one amine groups, and mixtures thereof;
and b.) said active component comprises a perfume selected from the
group consisting of undecylenic aldehyde, undecalactone gamma,
heliotropin, dodecalactone gamma, p-anisic aldehyde, para
hydroxy-phenyl-butanone, cymal, benzyl acetone, ionone alpha, p.t.
bucinal, damascenone, ionone beta and methyl-nonyl ketone, and
mixtures thereof.
24. A method of delivering residual fragrance to a surface, said
method comprising the steps of contacting said surface with a
product of reaction according to claim 1 and thereafter contacting
the treated surface with a material so that the active from the
product of reaction is released.
25. A method according to claim 24, wherein said material is
water.
26. A method according to claim 24, wherein said surface is a
fabric.
Description
CROSS-REFERENCE
[0001] This application is a continuation of and claims priority
under 35 U.S.C. .sctn. 120 to U.S. application Ser. No. 11/636,052
filed Dec. 8, 2006, which in turn is a continuation of and claims
priority under 35 U.S.C. .sctn. 120 to U.S. application Ser. No.
11/395,716 filed Mar. 31, 2006, which in turn is a continuation of
and claims priority under 35 U.S.C. .sctn. 120 to U.S. application
Ser. No. 11/165,644, filed Jun. 24, 2005, (now abandoned) which in
turn claims priority under 35 U.S.C. .sctn. 120 to U.S. application
Ser. No. 10,911,283, filed Aug. 4, 2004, (now abandoned) which in
turn claims priority under 35 U.S.C. .sctn.120 to U.S. application
Ser. No. 10/403,867, (now U.S. Pat. No. 6,790,815) filed Mar. 31,
2003, which in turn claims priority under 35 U.S.C. .sctn.120 to
U.S. application Ser. No. 10/157,790, filed May 29, 2002, (now U.S.
Pat. No. 6,566,312 B2) which in turn claims priority under 35
U.S.C. .sctn.120 to U.S. application Ser. No. 09/720,395, filed
Dec. 20, 2000, (now U.S. Pat. No. 6,413,920 B1) which is an entry
into the U.S. National Stage under 35 U.S.C. .sctn. 371 of PCT
International Application Serial No. PCT/US99/15665, filed Jul. 12,
1999, which claims priority under 35 U.S.C. .sctn. 119 to European
Application Serial Number 98870156.1, filed Jul. 10, 1998 and
European Application Serial Number 98870227.0, filed Oct. 28,
1998.
FIELD OF THE INVENTION
[0002] The present invention relates to product of reaction between
an amine and an active component, in particular an active aldehyde
or ketone, more preferably an aldehyde or ketone perfume. More
particularly, it relates to such product of reaction for use in
softening compositions.
BACKGROUND OF THE INVENTION
[0003] Perfumed products are well-known in the art. However,
consumer acceptance of such perfumed products like softening
products is determined not only by the performance achieved with
these products but also by the aesthetics associated therewith. The
perfume components are therefore an important aspect of the
successful formulation of such commercial products.
[0004] It is also desired by consumers for treated fabrics to
maintain the pleasing fragrance over time. Indeed, perfume
additives make such compositions more aesthetically pleasing to the
consumer, and in some cases the perfume imparts a pleasant
fragrance to fabrics treated therewith. However, the amount of
perfume carried-over from an aqueous laundry bath onto fabrics is
often marginal and does not last long on the fabric. Furthermore,
fragrance materials are often very costly and their inefficient use
in laundry and cleaning compositions and ineffective delivery to
fabrics results in a very high cost to both consumers and laundry
and cleaning manufacturers. Industry, therefore, continues to seek
with urgency for more efficient and effective fragrance delivery in
laundry and cleaning products, especially for improvement in the
provision of long-lasting fragrance to the fabrics.
[0005] One solution is to use carrier mechanisms for perfume
delivery, such as by encapsulation. This is taught in the prior art
and described in U.S. Pat. No. 5,188,753.
[0006] Still another solution is to formulate compounds which
provide a delayed release of the perfume over a longer period of
time than by the use of the perfume itself. Disclosure of such
compounds may be found in WO 95/04809, WO 95/08976 and co-pending
application EP 95303762.9.
[0007] However, notwithstanding the advances in the art, there is
still a need for a compound which provides a delayed release of the
active component, in particular a perfume ingredient.
[0008] That need is even more acute for perfume ingredients which
are characteristic of the fresh notes, namely the aldehydes and
ketones perfume ingredients. Indeed, whilst these provide a fresh
fragrance, these perfumes are also very volatile and have a low
substantivity on the surface to be treated like fabrics.
[0009] Accordingly, it is a further object of the invention to
provide a softening composition comprising a perfume component
which provides a fresh fragrance and is substantive to the treated
surface.
[0010] The Applicant has now found that specific reaction products
of amine compounds with an active aldehyde or ketone, such as
imines compounds, also provide a delayed release of the active such
as a perfume.
[0011] Imine compounds are known in the art under the name of
Schiff bases which is the condensation of an aldehyde perfume
ingredient with an anthranilate. A typical description can be found
in U.S. Pat. No. 4,853,369. By means of this compound, the aldehyde
perfume is made substantive to the fabrics. However, a problem
encountered with these Schiff bases is that the methylanthranilate
compound also exhibits a strong scent, which as a result produces a
mixture of fragrances, thereby reducing or even inhibiting the
aldehyde and/or ketone fragrance perception.
[0012] To achieve such perfume composition with comparable aldehyde
or ketones fresh notes whilst still having satisfactory fabric
substantivity, perfumers have formulated around the composition.
For example, by having a carrier or encapsulating material for such
notes such as with cyclodextrin, zeolites or starch.
[0013] Still another solution is the use of a glucosamine as
described in JP 09040687. However, this compound has been found to
give a very low stability in the wash process. As a result,
insufficient perfume residuality on the treated fabric has been
found with these glucosamine compounds. Its use in softening
composition is not disclosed.
[0014] A further solution is described in Chemical release control,
Kamogawa et Al., J. Poly. Sci. Polym. Chem. Ed. Vol 20, 3121 (1982)
which describe the use of amino styrene compounds condensed with
aldehydes perfumes, whereby the release of the perfume is triggered
by means of copolymerisation or acidification of the compound. Its
application is however not mentioned.
[0015] The Applicant has now found that a reaction product between
a specific primary and/or secondary amine and an active component
also fulfill such a need.
[0016] Another advantage of the compounds of the invention is their
ease of manufacture rendering their use most desirable.
SUMMARY OF THE INVENTION
[0017] The present invention relates to product of reaction between
a primary and/or secondary amine compound and an active component
selected from ketone, aldehyde, and mixtures thereof, characterised
in that said amine compound has an Odor Intensity Index of less
than that of a 1% solution of methylanthranilate in dipropylene
glycol, Dry Surface Odor Index of more than 5; and with the proviso
that said amine compound is not an aminostyrene.
[0018] In another aspect of the invention, there is provided a
softening composition comprising a primary and/or secondary amine
compound and an active component selected from ketone, aldehyde,
and mixtures thereof, characterised in that said amine compound has
an Odor Intensity Index of less than that of a 1% solution of
methylanthranilate in dipropylene glycol.
[0019] In a further aspect of the invention, there is provided a
method of delivering residual fragrance to a surface which
comprises the steps of contacting said surface with a compound or
composition of the invention and thereafter contacting the treated
fabric with a material so that the active is released from the
reaction product between the amine and the active.
DETAILED DESCRIPTION OF THE INVENTION
[0020] The essential component of the invention is the product of
reaction between a primary and/or secondary amine compound and an
active component selected from ketone, aldehyde, and mixtures
thereof, characterised in that said amine compound has an Odor
Intensity Index of less than that of a 1% solution of
methylanthranilate in dipropylene glycol, Dry Surface Odor Index of
more than 5; and with the proviso that said amine compound is not
an aminostyrene.
[0021] When incorporated in softening compositions, the amine
reaction product is a product of reaction between a primary and/or
secondary amine compound and an active component selected from
ketone, aldehyde, and mixtures thereof, characterised in that said
amine compound has an Odor Intensity Index of less than that of a
1% solution of methylanthranilate in dipropylene glycol.
[0022] Preferably, this compound has a Dry Surface Odor Index of
more than 5.
I-Product of Reaction Between a Compound Containing a Primary
and/or Secondary Amine Functional Group and a Perfume Component
[0023] An essential component of the invention is a product of
reaction between a compound containing a primary and/or secondary
amine functional group and a perfume component, so called
hereinafter "amine reaction product".
[0024] A-Primary and/or Secondary Amine
[0025] By "primary and/or secondary amine", it is meant a compound
which carries at least one primary and/or secondary amine and/or
amide function.
[0026] The primary and/or secondary amine compound is also
characterized by an Odor Intensity Index of less than that of a 1%
solution of methylanthranilate in dipropylene glycol.
Odor Intensity Index Method
[0027] By Odor Intensity Index, it meant that the pure chemicals
were diluted at 1% in Dipropylene Glycol, odor-free solvent used in
perfumery. This percentage is more representative of usage levels.
Smelling strips, or so called "blotters", were dipped and presented
to the expert panellist for evaluation. Expert panellists are
assessors trained for at least six months in odor grading and whose
gradings are checked for accuracy and reproducibility versus a
reference on an on-going basis. For each amine compound, the
panellist was presented two blotters: one reference (Me
Anthranilate, unknown from the panellist) and the sample. The
panellist was asked to rank both smelling strips on the 0-5 odor
intensity scale, 0 being no odor detected, 5 being very strong odor
present.
Results:
[0028] The following represents the Odor Intensity Index of an
amine compound suitable for use in the present invention and
according to the above procedure. In each case, numbers are
arithmetic averages among 5 expert panellists and the results are
statistically significantly different at 95% confidence level:
TABLE-US-00001 Methylanthranilate 1% (reference) 3.4
Ethyl-4-aminobenzoate (EAB) 1% 0.9
[0029] A general structure for the primary amine compound of the
invention is as follows: [0030] B--(NH2).sub.n; [0031] wherein B is
a carrier material, and n is an index of value of at least 1.
[0032] Compounds containing a secondary amine group have a
structure similar to the above excepted that the compound comprises
one or more --NH-- groups instead of --NH2. Further, the compound
structure may also have one or more of both --NH2 and --NH--
groups.
[0033] Preferred B carriers are inorganic or organic carriers.
[0034] By "inorganic carrier", it is meant a carrier which is
non-or substantially non carbon based backbones.
[0035] Among the inorganic carriers, preferred inorganic carriers
are mono or polymers or organic-organosilicon copolymers of amino
derivatised organo silane, siloxane, silazane, alumane, aluminum
siloxane, or aluminum silicate compounds. Typical examples of such
carriers are: organosiloxanes with at least one primary amine
moiety like the diaminoalkylsiloxane [H2NCH2(CH3) 2Si]O, or the
organoaminosilane (C6H5) 3SiNH2 described in: Chemistry and
Technology of Silicone, W. Noll, Academic Press Inc. 1998, London,
pp 209, 106).
[0036] Mono or polymer or organic-organosilicon copolymers
containing one or more organosilylhydrasine moiety are also
preferred. A typical example of such a class of carrier material is
the N,N'-bis(trimethylsilyl)hydrazine (Me3Si) 2NNH2 described in:
The OrganoSilicon Chemistry Second international Symposium, Pure
and Applied Chemistry, Vol, 19 Nos 3-4, (1969).
[0037] The following are also preferred mono or poly silazanes and
which are exemplified by the
1,1,1,3,3,3,-hexamethyl-2-phenyldiaminosilyldisilasane [(CH3) 3Si]
2NSi(C6H5)NH2) 2 described in: OrganoSilicon Compounds, 1965, V.
Bazant and al. Academic Press). Still other preferred examples of
polymer silicone derivatives are the cyclic 1,1,5,5,7,7,711,11
-Octamethyl-3-9-bis-[2-(2-aminoethylamino)-ethyl]-1,5,7,11-tetrasila-3,9--
diaza-6,12-dioxacyclododecane and the Hexaethoxydiamino
cyclotetrasiloxane (C6H5) (NH2) 2Si4O4, id, Vol 2 part 2, p 474,
p454).
[0038] Preferred amino functionalized inorganic polymeric carriers
for use herein are polyaminoalkyl polysiloxanes. Typical disclosure
can be found in JP 79,131,096, and EP 058 493. Still other
inorganic polymeric carriers suitable for use herein are the amino
functionalized polydialkylsiloxanes, as described in EP 150 867 and
having the general formula: ##STR1##
[0039] Wherein R.dbd.C.sub.1-16 preferentially C.sub.1-4 alkyl; n
is an integer from 0 to 16 preferentially from 1 to 6, R'=nil, O,
C.dbd.O, COO, NC.dbd.O, C.dbd.O--NR, NR, SO.sub.m, m=2,3.
[0040] By organic carriers, it meant carriers having essentially
carbon bond backbones. Typical amines having organic carrier
include aminoaryl derivatives, polyamines, aminoacids and
derivatives, substituted amines and amides, glucamines, dendrimers
and amino-substitued mono-, di-, oligo-, poly-saccharides.
[0041] Of course, the amine compound can be interrupted or
substituted by linkers or cellulose substantive group. A general
formula for this amine compound may be represented as follows:
NH2.sub.n-L.sub.m-B-L.sub.m-R*.sub.m; wherein each m is an index of
value 0 or at least 1, and n is an index of value of at least 1 as
defined herein before. As can be seen above, the amine group is
linked to a carrier molecule as defined by classes hereinafter
described. The primary and/or secondary amine group is either
directly linked to the carrier group or via a linker group L. The
carrier can also be substituted by a R* substituent, and R* can be
linked to the carrier either directly or via a linker group L. Of
course, R* can also contain branching groups like e.g. tertiary
amine and amide groups.
[0042] It is important for the purpose of the invention that the
amine compound comprises at least one primary and/or secondary
amine group to react with the perfume aldehyde and/or ketone to
form the reaction products. Of course, the amine compound is not
limited to having only one amine function. Indeed, more preferably,
the amine compound comprises more than one amine function, thereby
enabling the amine compound to react with several aldehydes and/or
ketones. Accordingly, reaction products carrying mixed aldehyde(s)
and/or ketone(s) can be achieved, thereby resulting in a mixed
release of such fragrances.
[0043] Typical linker group include: ##STR2##
[0044] L can also contain --O-- if this group is not directly
linked to N e.g. H.sub.2N--CH.sub.2--CH.sub.2O--
[0045] Most of the compounds described in the classes of amine
compounds hereinafter will contain at least one substituent group
classified as R*.
[0046] R* contains 1 to 22 carbon atoms in the main chain and
optionally can be an alkyl, alkenyl, or alkylbenzene chain. It can
also contain alicyclic, aromatic, heteroaromatic or heterocyclic
systems, either inserted into the main chain or by substitution of
an H atom of the main chain. Further, R* can either be linked to
the carrier B material or via a linker L, as defined herein before.
In this instance, L can also be --O--.
[0047] The main chain can contain from 1 to up to 15 R* groups.
[0048] Typical R* insertion groups include: ##STR3##
[0049] R* can also contain several insertion groups linked
together: e.g. e.g.: ##STR4##
[0050] Furthermore, R* can carry a functional end group E that
provides additional surface substantivity. Typical organic groups
of this end group E include ##STR5##
[0051] E can also be an aromatic, alicyclic, heteroaromatic, or
heterocyclic group including mono-, di-, oligo-, polysaccharides
##STR6##
[0052] In addition, the R* group can also be modified via
substitution of one or more H atoms in the main chain. The
substitution group can either be E or the insertion groups as
defined above where the insertion group is terminated by any of H,
E, or R*.
[0053] R* can also be a group made of ethoxy or epoxy groups with n
ranging from 1 to 15, including groups like:
--(CH.sub.2CH.sub.2O).sub.n--H --(O--CH.sub.2CH.sub.2).sub.n--OH
--(C.sub.3H.sub.6O).sub.n.H --(O--C.sub.3H.sub.6).sub.n--OH
[0054] As defined herein before, preferred amine having organic
carrier material B may be selected from aminoaryl derivatives,
polyamines, aminoacids and derivatives, substituted amines and
amides, glucamines, amino-substituted mono-, di-, oligo-,
poly-saccharides, dendrimers and/or mixtures thereof.
1-Amino Aryl Derivatives
[0055] In this class of compounds, the amino group is preferably
attached to a benzene ring. The benzene ring is further substituted
in the para- and/or meta-position with R* as defined herein before.
R* can be attached to the benzene ring via a linker L. The benzene
ring can be substituted by other aromatic ring systems including
naphtalene, indole, benzimidazole, pyrimidine, purine, and mixtures
thereof.
[0056] Preferably, the R* is attached to the benzene ring in its
para position.
[0057] Typical amino-benzene derivatives have the following
formula: ##STR7##
[0058] Preferred amino-benzene derivatives have the following
formula: ##STR8##
[0059] Preferred amino-benzene derivatives are alkyl esters of
4-amino benzoate compounds, preferably selected from ethyl-4-amino
benzoate, phenylethyl-4-aminobenzoate, phenyl-4-aminobenzoate,
4-amino-N'-(3-aminopropyl)-benzamide, and mixtures thereof.
2-Polyamines
[0060] The polyamines of the invention need to have at least one,
preferably more than one free and unmodified primary and/or
secondary amine group, to react with the active aldehyde or ketone.
In the polyamines, H can be substituted by R*, optionally via a
linker group L. Additionally, the primary and/or secondary amine
group can be linked to the polymer end via a linker group L.
[0061] The polyamines compounds suitable for use in the present
invention are water-soluble or dispersible, polyamines. Typically,
the polyamines for use herein have a molecular weight between 150
and 2*10.sup.6, preferably between 400 and 10.sup.6, most
preferably between 5000 and 10.sup.6. These polyamines comprise
backbones that can be either linear or cyclic. The polyamine
backbones can also comprise polyamine branching chains to a greater
or lesser degree. Preferably, the polyamine backbones described
herein are modified in such a manner that at least one, preferably
each nitrogen of the polyamine chain is thereafter described in
terms of a unit that is substituted, quaternized, oxidized, or
combinations thereof.
[0062] For the purposes of the present invention the term
"modification" as it relates to the chemical structure of the
polyamines is defined as replacing a backbone --NH hydrogen atom by
an R' unit (substitution), quaternizing a backbone nitrogen
(quaternized) or oxidizing a backbone nitrogen to the N-oxide
(oxidized). The terms "modification" and "substitution" are used
interchangeably when referring to the process of replacing a
hydrogen atom attached to a backbone nitrogen with an R' unit.
Quaternization or oxidation may take place in some circumstances
without substitution, but substitution is preferably accompanied by
oxidation or quaternization of at least one backbone nitrogen.
[0063] The linear or non-cyclic polyamine backbones that comprise
the polyamine have the general formula: ##STR9##
[0064] The cyclic polyamine backbones that comprise the polyamine
have the general formula: ##STR10##
[0065] The above backbones prior to optional but preferred
subsequent modification, comprise primary, secondary and tertiary
amine nitrogens connected by R "linking" units
[0066] For the purpose of the present invention, primary amine
nitrogens comprising the backbone or branching chain once modified
are defined as V or Z "terminal" units. For example, when a primary
amine moiety, located at the end of the main polyamine backbone or
branching chain having the structure H2N--[R]-- is modified
according to the present invention, it is thereafter defined as a V
"terminal" unit, or simply a V unit. However, for the purposes of
the present invention, some or all of the primary amine moieties
can remain unmodified subject to the restrictions further described
herein below. These unmodified primary amine moieties by virtue of
their position in the backbone chain remain "terminal" units.
Likewise, when a primary amine moiety, located at the end of the
main polyamine backbone having the structure --NH2 is modified
according to the present invention, it is thereafter defined as a Z
"terminal" unit, or simply a Z unit. This unit can remain
unmodified subject to the restrictions further described herein
below.
[0067] In a similar manner, secondary amine nitrogens comprising
the backbone or branching chain once modified are defined as W
"backbone" units. For example, when a secondary amine moiety, the
major constituent of the backbones and branching chains of the
present invention, having the structure ##STR11## is modified
according to the present invention, it is thereafter defined as a W
"backbone" unit, or simply a W unit. However, for the purposes of
the present invention, some or all of the secondary amine moieties
can remain unmodified. These unmodified secondary amine moieties by
virtue of their position in the backbone chain remain "backbone"
units.
[0068] In a further similar manner, tertiary amine nitrogens
comprising the backbone or branching chain once modified are
further referred to as Y "branching" units. For example, when a
tertiary amine moiety, which is a chain branch point of either the
polyamine backbone or other branching chains or rings, having the
structure ##STR12## is modified according to the present invention,
it is thereafter defined as a Y "branching" unit, or simply a Y
unit. However, for the purposes of the present invention, some or
all or the tertiary amine moieties can remain unmodified. These
unmodified tertiary amine moieties by virtue of their position in
the backbone chain remain "branching" units. The R units associated
with the V, W and Y unit nitrogens which serve to connect the
polyamine nitrogens, are described herein below.
[0069] The final modified structure of the polyamines of the
present invention can be therefore represented by the general
formula V(n+1)WmYnZ for linear polyamine and by the general formula
V(n-k+1)WmYnY'kZ for cyclic polyamine. For the case of polyamines
comprising rings, a Y' unit of the formula ##STR13## serves as a
branch point for a backbone or branch ring. For every Y' unit there
is a Y unit having the formula ##STR14## that will form the
connection point of the ring to the main polymer chain or branch.
In the unique case where the backbone is a complete ring, the
polyamine backbone has the formula ##STR15## therefore comprising
no Z terminal unit and having the formula Vn-kWmYnY'k wherein k is
the number of ring forming branching units. Preferably the
polyamine backbones of the present invention comprise no rings.
[0070] In the case of non-cyclic polyamines, the ratio of the index
n to the index m relates to the relative degree of branching. A
fully non-branched linear modified polyamine according to the
present invention has the formula VWmZ that is, n is equal to 0.
The greater the value of n (the lower the ratio of m to n), the
greater the degree of branching in the molecule. Typically the
value for m ranges from a minimum value of 2 to 700, preferably 4
to 400, however larger values of m, especially when the value of
the index n is very low or nearly 0, are also preferred.
[0071] Each polyamine nitrogen whether primary, secondary or
tertiary, once modified according to the present invention, is
further defined as being a member of one of three general classes;
simple substituted, quaternized or oxidized. Those polyamine
nitrogen units not modified are classed into V, W, Y, Y' or Z units
depending on whether they are primary, secondary or tertiary
nitrogens. That is unmodified primary amine nitrogens are V or Z
units, unmodified secondary amine nitrogens are W units or Y' units
and unmodified tertiary amine nitrogens are Y units for the
purposes of the present invention.
[0072] Modified primary amine moieties are defined as V "terminal"
units having one of three forms: [0073] a) simple substituted units
having the structure: ##STR16## [0074] b) quaternized units having
the structure: ##STR17## [0075] wherein X is a suitable counter ion
providing charge balance; and [0076] c) oxidized units having the
structure: ##STR18##
[0077] Modified secondary amine moieties are defined as W
"backbone" units having one of three forms: [0078] a) simple
substituted units having the structure: ##STR19## [0079] b)
quaternized units having the structure: ##STR20## [0080] wherein X
is a suitable counter ion providing charge balance; and [0081] c)
oxidized units having the structure: ##STR21##
[0082] Other modified secondary amine moieties are defined as Y'
units having one of three forms: [0083] a) simple substituted units
having the structure: ##STR22## [0084] b) quaternized units having
the structure: ##STR23## [0085] wherein X is a suitable counter ion
providing charge balance; and [0086] c) oxidized units having the
structure: ##STR24##
[0087] Modified tertiary amine moieties are defined as Y
"branching" units having one of three forms: [0088] a) unmodified
units having the structure: ##STR25## [0089] b) quaternized units
having the structure: ##STR26## [0090] wherein X is a suitable
counter ion providing charge balance; and [0091] c) oxidized units
having the structure: ##STR27##
[0092] Certain modified primary amine moieties are defined as Z
"terminal" units having one of three forms: [0093] a) simple
substituted units having the structure: ##STR28## [0094] b)
quaternized units having the structure: ##STR29## [0095] wherein X
is a suitable counter ion providing charge balance; and [0096] c)
oxidized units having the structure: ##STR30##
[0097] When any position on a nitrogen is unsubstituted of
unmodified, it is understood that hydrogen will substitute for R'.
For example, a primary amine unit comprising one R' unit in the
form of a hydroxyethyl moiety is a V terminal unit having the
formula (HOCH2CH2)HN--.
[0098] For the purposes of the present invention there are two
types of chain terminating units, the V and Z units. The Z
"terminal" unit derives from a terminal primary amino moiety of the
structure --NH2. Non-cyclic polyamine backbones according to the
present invention comprise only one Z unit whereas cyclic
polyamines can comprise no Z units. The Z "terminal" unit can be
substituted with any of the R' units described further herein
below, except when the Z unit is modified to form an N-oxide. In
the case where the Z unit nitrogen is oxidized to an N-oxide, the
nitrogen must be modified and therefore R' cannot be a
hydrogen.
[0099] The polyamines of the present invention comprise backbone R
"linking" units that serve to connect the nitrogen atoms of the
backbone. R units comprise units that for the purposes of the
present invention are referred to as "hydrocarbyl R" units and "oxy
R" units. The "hydrocarbyl" R units are C2-C12 alkylene, C4-C12
alkenylene, C3-C12 hydroxyalkylene wherein the hydroxyl moiety may
take any position on the R unit chain except the carbon atoms
directly connected to the polyamine backbone nitrogens; C4-C12
dihydroxyalkylene wherein the hydroxyl moieties may occupy any two
of the carbon atoms of the R unit chain except those carbon atoms
directly connected to the polyamine backbone nitrogens; C8-C12
dialkylarylene which for the purpose of the present invention are
arylene moieties having two alkyl substituent groups as part of the
linking chain. For example, a dialkylarylene unit has the formula
##STR31## although the unit need not be 1,4-substituted, but can
also be 1,2 or 1,3 substituted C2-C12 alkylene, preferably
ethylene, 1,2-propylene, and mixtures thereof, more preferably
ethylene. The "oxy" R units comprise --(R1O)xR5(OR1)x--,
CH2CH(OR2)CH2O)z(R1O)yR1(OCH2CH(OR2)CH2)w--, --CH2CH(OR2)CH2--,
--(R1O)xR1--, and mixtures thereof. Preferred R units are selected
from the group consisting of C2-C12 alkylene, C3-C12
hydroxy-alkylene, C4-C12 dihydroxyalkylene, C8-C12 dialkylarylene,
--(R1O)xR1--, --CH2CH(OR2)CH2--,
--(CH2CH(OH)CH2O)z(R1O)yR1(OCH2CH--(OH)CH2)w--, --(R1O)xR5(OR1)x--,
more preferred R units are C2-C12 alkylene, C3-C12
hydroxy-alkylene, C4-C12 dihydroxyalkylene, --(R1O)xR1--,
--(R1O)xR5(OR1)x--, (CH2CH(OH)CH2O)z(R1O)yR1(OCH2CH--(OH)CH2)w--,
and mixtures thereof, even more preferred R units are C2-C12
alkylene, C3 hydroxyalkylene, and mixtures thereof, most preferred
are C2-C6 alkylene. The most preferred backbones of the present
invention comprise at least 50% R units that are ethylene.
[0100] R1 units are C2-C6 alkylene, and mixtures thereof,
preferably ethylene.
[0101] R2 is hydrogen, and --(R1O)xB, preferably hydrogen.
[0102] R3 is C1-C18 alkyl, C7-C12 arylalkylene, C7-C12 alkyl
substituted aryl, C6-C12 aryl, and mixtures thereof, preferably
C1-C12 alkyl, C7-C12 arylalkylene, more preferably C1-C12 alkyl,
most preferably methyl. R3 units serve as part of R' units
described herein below.
[0103] R4 is C1-C12 alkylene, C4-C12 alkenylene, C8-C12
arylalkylene, C6-C10 arylene, preferably C1-C10 alkylene, C8-C12
arylalkylene, more preferably C2-C8 alkylene, most preferably
ethylene or butylene.
[0104] R5 is C1-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12
dihydroxyalkylene, C8-C12 dialkylarylene, --C(O)--,
--C(O)NHR6NHC(O)--, --C(O)(R4)rC(O)--, --R1(OR1)--,
--CH2CH(OH)CH20(R1O)yR1OCH2CH(OH)CH2--, --C(O)(R4)rC(O)--,
--CH2CH(OH)CH2--, R5 is preferably ethylene, --C(O)--,
--C(O)NHR6NHC(O)--, --R1(OR1)--, --CH2CH(OH)CH2--,
--CH2CH(OH)CH2O(R1O)yR1OCH2CH--(OH)CH2--, more preferably
--CH2CH(OH)CH2--.
[0105] R6 is C2-C12 alkylene or C6-C12 arylene.
[0106] The preferred "oxy" R units are further defined in terms of
the R1, R2, and R5 units. Preferred "oxy" R units comprise the
preferred R1, R2, and R5 units. The preferred polyamines of the
present invention comprise at least 50% R1 units that are ethylene.
Preferred R1, R2, and R5 units are combined with the "oxy" R units
to yield the preferred "oxy" R units in the following manner.
[0107] i) Substituting more preferred R5 into
--(CH2CH2O)xR5(OCH2CH2)x-- yields
--(CH2CH2O)xCH2CHOHCH2(OCH2CH2)x--. [0108] ii) Substituting
preferred R1 and R2 into
--(CH2CH(OR2)CH2O)z--(R1O)yR1O(CH2CH(OR2)CH2)w-- yields
--(CH2CH(OH)CH2O)z--(CH2CH2O)yCH2CH2O(CH2CH(OH)CH2)w--. [0109] iii)
Substituting preferred R2 into --CH2CH(OR2)CH2-- yields
--CH2CH(OH)CH2--.
[0110] R' units are selected from the group consisting of hydrogen,
C1-C22 alkyl, C3-C22 alkenyl, C7-C22 arylalkyl, C2-C22
hydroxyalkyl, --(CH2)pCO2M, --(CH2)qSO3M, --CH(CH2CO2M)CO2M,
--(CH2)pPO3M, --(R1O)mB, --C(O)R3, preferably hydrogen, C2-C22
hydroxyalkylene, benzyl, C1-C22 alkylene, --(R1O)mB, --C(O)R3,
--(CH2)pCO2M, --(CH2)qSO3M, --CH(CH2CO2M)CO2M, more preferably
C1-C22 alkylene, --(R1O)xB, --C(O)R3, --(CH2)pCO2M, --(CH2)qSO3M,
--CH(CH2CO2M)CO2M, most preferably C1-C22 alkylene, --(R1O)xB,
and--C(O)R3. When no modification or substitution is made on a
nitrogen then hydrogen atom will remain as the moiety representing
R'. A most preferred R' unit is (R1O)xB.
[0111] R' units do not comprise hydrogen atom when the V, W or Z
units are oxidized, that is the nitrogens are N-oxides. For
example, the backbone chain or branching chains do not comprise
units of the following structure: ##STR32##
[0112] Additionally, R' units do not comprise carbonyl moieties
directly bonded to a nitrogen atom when the V, W or Z units are
oxidized, that is, the nitrogens are N-oxides. According to the
present invention, the R' unit--C(O)R3 moiety is not bonded to an
N-oxide modified nitrogen, that is, there are no N-oxide amides
having the structure ##STR33## or combinations thereof.
[0113] B is hydrogen, C1-C6 alkyl, --(CH2)qSO3M, --(CH2)pCO2M,
--(CH2)q--(CHSO3M)CH2SO3M, --(CH2)q(CHSO2M)CH2SO3M, --(CH2)pPO3M,
--PO3M, preferably hydrogen, --(CH2)qSO3M, --(CH2)q(CHSO3M)CH2SO3M,
--(CH2)q--(CHSO2M)CH2SO3M, more preferably hydrogen or
--(CH2)qSO3M.
[0114] M is hydrogen or a water soluble cation in sufficient amount
to satisfy charge balance. For example, a sodium cation equally
satisfies --(CH2)pCO2M, and --(CH2)qSO3M, thereby resulting in
--(CH2)pCO2Na, and --(CH2)qSO3Na moieties. More than one monovalent
cation, (sodium, potassium, etc.) can be combined to satisfy the
required chemical charge balance. However, more than one anionic
group may be charge balanced by a divalent cation, or more than one
mono-valent cation may be necessary to satisfy the charge
requirements of a poly-anionic radical. For example, a --(CH2)pPO3M
moiety substituted with sodium atoms has the formula
--(CH2)pPO3Na3. Divalent cations such as calcium (Ca2+) or
magnesium (Mg2+) may be substituted for or combined with other
suitable mono-valent water soluble cations. Preferred cations are
sodium and potassium, more preferred is sodium.
[0115] X is a water soluble anion such as chlorine (Cl--), bromine
(Br--) and iodine (I--) or X can be any negatively charged radical
such as sulfate (SO42--) and methosulfate (CH3SO3--).
[0116] The formula indices have the following values: p has the
value from 1 to 6, q has the value from 0 to 6; r has the value 0
or 1; w has the value 0 or 1, x has the value from 1 to 100; y has
the value from 0 to 100; z has the value 0 or 1; m has the value
from 2 to 700, preferably from 4 to 400, n has the value from 0 to
350, preferably from 0 to 200; m+n has the value of at least 5.
Preferably x has a value lying in the range of from 1 to 20,
preferably from 1 to 10.
[0117] The preferred polyamines of the present invention comprise
polyamine backbones wherein less than 50% of the R groups comprise
"oxy" R units, preferably less than 20% , more preferably less than
5%, most preferably the R units comprise no "oxy" R units.
[0118] The most preferred polyamines which comprise no "oxy" R
units comprise polyamine backbones wherein less than 50% of the R
groups comprise more than 3 carbon atoms. For example, ethylene,
1,2-propylene, and 1,3-propylene comprise 3 or less carbon atoms
and are the preferred "hydrocarbyl" R units. That is when backbone
R units are C2-C12 alkylene, preferred is C2-C3 alkylene, most
preferred is ethylene.
[0119] The polyamines of the present invention comprise modified
homogeneous and non-homogeneous polyamine backbones, wherein 100%
or less of the --NH units are modified. For the purpose of the
present invention the term "homogeneous polyamine backbone" is
defined as a polyamine backbone having R units that are the same
(i.e., all ethylene). However, this sameness definition does not
exclude polyamines that comprise other extraneous units comprising
the polymer backbone which are present due to an artifact of the
chosen method of chemical synthesis. For example, it is known to
those skilled in the art that ethanolamine may be used as an
"initiator" in the synthesis of polyethyleneimines, therefore a
sample of polyethyleneimine that comprises one hydroxyethyl moiety
resulting from the polymerization "initiator" would be considered
to comprise a homogeneous polyamine backbone for the purposes of
the present invention. A polyamine backbone comprising all ethylene
R units wherein no branching Y units are present is a homogeneous
backbone. A polyamine backbone comprising all ethylene R units is a
homogeneous backbone regardless of the degree of branching or the
number of cyclic branches present.
[0120] For the purposes of the present invention the term
"non-homogeneous polymer backbone" refers to polyamine backbones
that are a composite of various R unit lengths and R unit types.
For example, a non-homogeneous backbone comprises R units that are
a mixture of ethylene and 1,2-propylene units. For the purposes of
the present invention a mixture of "hydrocarbyl" and "oxy" R units
is not necessary to provide a non-homogeneous backbone.
[0121] Preferred polyamines of the present invention comprise
homogeneous polyamine backbones that are totally or partially
substituted by polyethyleneoxy moieties, totally or partially
quaternized amines, nitrogens totally or partially oxidized to
N-oxides, and mixtures thereof. However, not all backbone amine
nitrogens must be modified in the same manner, the choice of
modification being left to the specific needs of the formulator.
The degree of ethoxylation is also determined by the specific
requirements of the formulator.
[0122] The preferred polyamines that comprise the backbone of the
compounds of the present invention are generally polyalkyleneimines
(PAI's), preferably polyethyleneimines (PEI's), or PEI's connected
by moieties having longer R units than the parent PAI's or
PEI's.
[0123] Preferred amine polymer backbones comprise R units that are
C2 alkylene (ethylene) units, also known as polyethylenimines
(PEI's). Preferred PEI's have at least moderate branching, that is
the ratio of m to n is less than 4:1, however PEI's having a ratio
of m to n of 2:1 are most preferred. Preferred backbones, prior to
modification have the general formula: ##STR34## wherein R', m and
n are the same as defined herein above. Preferred PEI's will have a
molecular weight greater than 200 daltons.
[0124] The relative proportions of primary, secondary and tertiary
amine units in the polyamine backbone, especially in the case of
PEI's, will vary, depending on the manner of preparation. Each
hydrogen atom attached to each nitrogen atom of the polyamine
backbone chain represents a potential site for subsequent
substitution, quaternization or oxidation.
[0125] These polyamines can be prepared, for example, by
polymerizing ethyleneimine in the presence of a catalyst such as
carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide,
hydrochloric acid, acetic acid, etc. Specific methods for preparing
these polyamine backbones are disclosed in U.S. Pat. No. 2,182,306,
Ulrich et al., issued Dec. 5, 1939; U.S. Pat. No. 3,033,746, Mayle
et al., issued May 8, 1962; U.S. Pat. No. 2,208,095, Esselmann et
al., issued Jul. 16, 1940; U.S. Pat. No. 2,806,839, Crowther,
issued Sep. 17, 1957; and U.S. Pat. No. 2,553,696, Wilson, issued
May 21, 1951; all herein incorporated by reference.
[0126] Preferred polyamines are polyethyleneimines commercially
available under the tradename Lupasol like Lupasol FG (MW 800),
G20wfv (MW 1300), PR8515 (MW 2000), WF (MW 25000), FC (MW 800), G20
(MW 1300), G35 (MW 1200), G100 (MW 2000), HF (MW 25000), P (MW
750000), PS (MW 750000), SK (MW 2000000), SNA (MW 1000000).
[0127] Still other polyamines suitable for use in the present
invention are poly[oxy(methyl-1,2-ethanediyl)],
.alpha.-(2-aminomethylethyl)-.omega.-(2-aminomethyl-ethoxy)-(=C.A.S.
No. 9046-10-0); poly[oxy(methyl-1,2-ethanediyl)],
.alpha.-hydro-)-.omega.-(2-aminomethylethoxy)--, ether with
2-ethyl-2-(hydroxymethyl)-1,3-propanediol (=C.A.S. No. 39423-51-3);
commercially available under the tradename Jeffamines T-403, D-230,
D-400, D-2000; 2,2',2''-triaminotriethylamine;
2,2'-diamino-diethylamine; 3,3'-diamino-dipropyl-amine, 1,3 bis
aminoethylcyclohexane commercially available from Mitsibushi and
the C12 Sternamines commercially available from Clariant like the
C12 Sternamin(propylenamine).sub.n with n=3/4, and mixtures
thereof.
3-Amino Acids and Derivatives
[0128] Still other suitable compounds for use in the present
invention are aminoacids and their derivatives, especially ester
and amide derivatives. More preferred compounds are those providing
enhanced surface substantivity due to its structural feature. For
clarification, the term amino acids and derivatives does not
encompass polymeric compounds.
[0129] Suitable amino acids have the following functionality of
formula: ##STR35##
[0130] Wherein R.sub.1.dbd.H, R* or (L)-R* and R is the amino acid
side group, generally referred to as the "R group" such as in
"Principles of Biochemistry" by Lehninger et al., 1997, Second
Edition, Worth, pp 114-116.
[0131] Preferred amino acids for use herein are selected tyrosine,
tryptophane, lysine, glutamic acid, glutamine, aspartic acid,
arginine, asparagine, phenylalanine, proline, glycine, serine,
histidine, threonine, methionine, and mixture thereof, most
preferably selected from tyrosine, tryptophane, and mixture
thereof.
[0132] Still other preferred compound are the amino acid
derivatives selected from tyrosine ethylate, glycine methylate,
tryptophane ethylate and mixture thereof,
4-Substituted Amines and Amides
[0133] For clarification, the term substituted amines and amides
does not encompass polymeric compounds. Substituted amine and amide
compounds suitable for use herein have the following general
formula: [0134] NH2-L-R**, in which L is --CO-- in case of an
amide.
[0135] Other optional linker group may be as defined under R*.
[0136] R** is as defined herein before under R* with the proviso
that it contains at least 6 carbon atoms and/or N atoms and/or
cyclohexyl-, piperidine, piperazine, and other heterocyclic groups
like: ##STR36##
[0137] Optionally, H in NH can be substituted by R*.
[0138] Preferred substituted amines and amides for use herein are
selected from nipecotamide, N-coco-1,3-propenediamine;
N-oleyl-1,3-propenediamine; N--(tallow alkyl)-1,3-propenediamine;
1,4-diamino cyclohexane; 1,2-diamino-cyclohexane; 1,1
2-diaminododecane, and mixtures thereof.
5-Glucamines
[0139] Still a further preferred class of amine compound is the
class of glucamines of general structure:
NH2--CH2--(CH(OH)).sub.x--CH2OH, wherein one or several OH-function
can be substituted, preferably by --OR*, and wherein x is an
integer of value 3 or 4. R* can be linked to the OH groups either
directly or via linker unit as mentioned herein before under L.
[0140] For clarification, the term glucamine does not encompass
polymeric compounds.
[0141] Preferred compound of this class are selected from
2,3,4,5,6-pentamethoxy-glucamine; 6-acetylglucamine, glucamine, and
mixture thereof.
6-Dendrimers
[0142] Another further class of amine compounds is the class of
dendrimers. Suitable dendrimers carry free primary and/or secondary
amine groups at the periphery of the spherical molecules, that can
be reacted with (perfume) aldehydes or ketones to form the desired
amine reaction product (perfume component) of the invention.
[0143] By dendrimers it is understood that the molecule is built up
from a core molecule as described e.g. in WO 96/02588 and in
Synthesis, February 1978, p. 155-158 or in Encyclopedia of Polymer
Science & Engineering, 2nd ed., Hedstrand et al., in particular
pages 46-91. The core is typically connected to multifunctional
components to build up the "generations". For the purpose of the
present invention, the nature of the inner generations is not
critical. They can be based on e.g. polyamidoamines,
polyamidoalcohols, polyethers, polyamides, polyethylenimines, etc.
Important for the purpose of the present invention is that the
outer generation(s) contain accessible primary and/or secondary
amino functions.
[0144] Also suitable are the glyco dendrimers as described in e.g.
Nachrichten aus Chemie 11 (1996), p. 1073-1079 and in WO 97/48711
provided that free primary and/or secondary amine groups are
present at the surface of these molecules.
[0145] Preferred compounds are the polyethylenimine and
polypropylenimine dendrimers, the commercially available
Starburst.RTM. polyamidoamines (PAMAM) dendrimers, generation
G0-G10 from Dendritech and the dendrimers Astromols.RTM.,
generation 1-5 from DSM being DiAminoButane PolyAmine DAB (PA)x
with x=2.sup.n.times.4 and n being generally comprised between 0
and 4.
7-Amino-Substituted Mono-, Di-, Oligo-, Poly-Saccharides
[0146] Also suitable for the purpose of the present invention are
specific amino-substituted mono-, di-, oligo-,
poly-saccharides.
[0147] For the amino-substituted mono-saccharides of the present
invention, it is necessary that the hemi-acetal and/or hemi-ketal
functionality is blocked via a suitable substituent to provide
sufficient stability for the intended application. As indicated
here above, glucoseamine is not a suitable amine. However, if the
hemi-acetal OH function is substituted by R*, said monosaccharide
becomes suitable for the purpose of the present invention. The
amino group can be in position 2 to 5 or 6 depending on the type of
monosaccharide and is preferably in C2, C5 or C6 position. Suitable
amino-substituted mono-saccharides are: [0148] C5 aldosen/ketosen:
ribose, arabinose, xylose, lyxose, ribulose, xylulose; [0149] C6
aldosen/ketosen allose, altrose, glucose, mannose, gulose, idose,
galactose, talose, fructose, sorbose, tagatose, psicose.
[0150] For amino-substituted di-saccharides with non-substituted
aldose or ketose groups, the free OH-- group needs to be
substituted by R*, e.g. in lactose and maltose, whereas in sucrose
there is no free acetal/ketal OH group. Optionally, more than one
OH group can be substituted by R*. Suitable amino-substituted
di-saccharides are amino substituted lactose, maltose, sucrose,
cellobiose and trehalose.
[0151] Suitable amino-substituted oligo-, poly-saccharides are
amino-substituted starch, cyclodextrin, dextran, glycogen,
cellulose, mannan, gueran, levan, alternan glucose, mannose,
galactose, fructose, lactose, maltose, sucrose, cellobiose,
cyclodextrin, chitosan, and/or mixtures thereof. The molecules need
to carry at least 1, preferably several, amino groups. Chitosan
does not require additional amino substitution.
[0152] Also suitable for coupling carboxyl- or aldehyde-containing
compounds are the following functionalised oligo-, poly-saccharides
& glycans commercially available from the company Carbomer.
Please find in brackets the reference number from Carbomer: Amino
alginate (5,00002), Diamino alginate (5,00003), Hexanediamine
alginate (5,00004-5,00006-5,00008), dodecanediamine alginate
(5,00005-5,00007-5,00009), 6-amino-6-deoxy cellulose (5,00020),
O-ethylamine cellulose (5,00022), O-methylamine cellulose
(5,00023), 3-amino-3-deoxy cellulose (5,00024), 2-amino-2 deoxy
cellulose (5,00025), 2,3-diamino-2,3-dideoxy cellulose (5,00026),
6-[N-(1,6-hexanediamine)]-6-deoxy cellulose (5,00027),
6-[N-(1,12-docedanediamine)]-6-deoxy cellulose (5,00028),
O-[methyl-(N-1,6-hexanediamine)] cellulose (5,00029),
O-[methyl-(N1,12-dodecanediamine)] cellulose (5,00030),
2,3-di-[N-(1,12-dodecanediamine)] cellulose (5,00031),
2,3-diamino-2,3-deoxy alpha-cyclodextrin (5,00050),
2,3-diamino-2,3-deoxy beta-cyclodextrin (5,00051),
2,3-diamino-2,3-deoxy gamma-cyclodextrin (5,00052), 6-amino-6-deoxy
alpha-cyclodextrin (5,00053), 6-amino-6-deoxy beta-cyclodextrin
(5,00054), O-ethyleamino beta-cyclodextrin (5,00055),
6[N-(1,6-hexanediamino)-6-deoxy alpha cyclodextrin (5,00056),
6[N-(1,6-hexanediamino)-6-deoxy beta cyclodextrin (5,00057), Amino
dextran (5,00060), N-[di-(1,6-hexanediamine)] dextran (5,00061),
N-[di-(1,12-dodecanediamine)] dextran (5,00062),
6-amino-6-deoxy-alpha-D-galactosyl-guaran (5,00070), O-ethylamino
guaran (5,00071), Diamino guaran (5,00072), 6-amino-6-deoxy-starch
(5,00080), O-ethylamino starch (5,00081), 2,3-diamine-2,3-dideoxy
starch (5,00082), N-[6-(1,6-hexanediamine)]-6-deoxy starch
(5,00083), N-[6-(1,12-dodecanediamine)]-6-deoxy starch (5,00084)
and 2,3-di-[N(1,6-hexanediamine)]-2,3-dideoxy starch (5,00085)
[0153] Furthermore, with the use of some of the above compound
comprising at least one primary and/or secondary amine group like
the polyamine, the resulting amine reaction product will
beneficially provide fabric appearance benefits, in particular
color care and protection against fabric wear. Indeed, the
appearance of fabrics, e.g., clothing, bedding, household fabrics
like table linens is one of the area of concern to consumers.
Indeed, upon typical consumer's uses of the fabrics such as
wearing, washing, rinsing and/or tumble-drying of fabrics, a loss
in the fabric appearance; which can be at least partly due to loss
of color fidelity and color definition, is observed. Such a problem
of color loss is even more acute after multiwash cycles. It has
been found that the compositions of the present invention provide
improved fabric appearance and protection against fabric wear and
improved color care to laundered fabrics, especially after
multiwash cycles.
[0154] Therefore, the compositions of the present invention can
provide simultaneously fabric care and long lasting perfume
benefits.
B-Active Ketone and/or Aldehyde
[0155] Preferably, for the above mentioned compounds, by active
ketone or active aldehyde, it is meant any chain containing at
least I carbon atom, preferably at least 5 carbon atoms.
[0156] Preferably, the active ketone or active aldehyde is
respectively selected from a flavour ketone or aldehyde ingredient,
a pharmaceutical ketone or aldehyde active, a biocontrol ketone or
aldehyde agent, a perfume ketone or aldehyde component, a
refreshing cooling ketone or aldehyde agent and mixtures
thereof.
[0157] Flavour ingredients include spices, flavor enhancers that
contribute to the overall flavour perception.
[0158] Pharmaceutical actives include drugs.
[0159] Biocontrol agents include biocides, antimicrobials,
bactericides, fungicides, algaecides, mildewcides, disinfectants,
antiseptics, insecticides, vermicides, plant growth hormones.
[0160] Biocontrol agents include biocides, antimicrobials,
bactericides, fungicides, algaecides, mildewcides, disinfectants,
sanitiser like bleach, antiseptics, insecticides, insect and/or
moth
[0161] repellant, vermicides, plant growth hormones.
[0162] Typical antimicrobials include Glutaraldehyde,
Cinnamaldehyde, and mixtures thereof. Typical insect and/or moth
repellants are perfume ingredients, such as citronellal, citral, N,
N diethyl meta toluamide, Rotundial, 8-acetoxycarvotanacenone, and
mixtures thereof. Other examples of insect and/or moth repellant
for use herein are disclosed in U.S. Pat. Nos. 4,449,987,
4,693,890, 4,696,676, 4,933,371, 5,030,660, 5,196,200, and "Semio
Activity of Flavor and Fragrance molecules on various Insect
Species", B. D. Mookherjee et al., published in Bioactive Volatile
Compounds from Plants, ASC Symposium Series 525, R. Teranishi, R.
G. Buttery, and H. Sugisawa, 1993, pp. 35-48.
[0163] A typical disclosure of suitable ketone and/or aldehydes,
traditionally used in perfumery, can be found in "perfume and
Flavor Chemicals", Vol. I and II, S. Arctander, Allured Publishing,
1994, ISBN 0-931710-35-5.
[0164] Perfume ketones components include components having
odoriferous properties.
[0165] Preferably, for the above mentioned compounds, the perfume
ketone is selected for its odor character from buccoxime; iso
jasmone; methyl beta naphthyl ketone; musk indanone; tonalid/musk
plus; Alpha-Damascone, Beta-Damascone, Delta-Damascone,
Iso-Damascone, Damascenone, Damarose, Methyl-Dihydrojasmonate,
Menthone, Carvone, Camphor, Fenchone, Alpha-Ionone, Beta-Ionone,
Gamma-Methyl so-called Ionone, Fleuramone, Dihydrojasmone,
Cis-Jasmone, Iso-E-Super, Methyl-Cedrenyl-ketone or
Methyl-Cedrylone, Acetophenone, Methyl-Acetophenone,
Para-Methoxy-Acetophenone, Methyl-Beta-Naphtyl-Ketone,
Benzyl-Acetone, Benzophenone, Para-Hydroxy-Phenyl-Butanone, Celery
Ketone or Livescone, 6-Isopropyldecahydro-2-naphtone,
Dimethyl-Octenone, Freskomenthe,
4-(1-Ethoxyvinyl)-3,3,5,5,-tetramethyl-Cyclohexanone,
Methyl-Heptenone,
2-(2-(4-Methyl-3-cyclohexen-1-yl)propyl)-cyclopentanone,
1-(p-Menthen-6(2)-yl)-1-propanone,
4-(4-Hydroxy-3-methoxyphenyl)-2-butanone,
2-Acetyl-3,3-Dimethyl-Norbornane,
6,7-Dihydro-1,1,2,3,3-Pentamethyl-4(5H)-Indanone, 4-Damascol,
Dulcinyl or Cassione, Gelsone, Hexalon, Isocyclemone E, Methyl
Cyclocitrone, Methyl-Lavender-Ketone, Orivon,
Para-tertiary-Butyl-Cyclohexanone, Verdone, Delphone, Muscone,
Neobutenone, Plicatone, Veloutone,
2,4,4,7-Tetramethyl-oct-6-en-3-one, Tetrameran.
[0166] Preferably, for the above mentioned compounds, the preferred
ketones are selected from Alpha Damascone, Delta Damascone, Iso
Damascone, Carvone, Gamma-Methyl-Ionone, Iso-E-Super,
2,4,4,7-Tetramethyl-oct-6-en-3-one, Benzyl Acetone, Beta Damascone,
Damascenone, methyl dihydrojasmonate, methyl cedrylone, and
mixtures thereof.
[0167] Perfume aldehyde components include components having
odoriferous properties.
[0168] Preferably, for the above mentioned compounds, the perfume
aldehyde is selected for its odor character from adoxal; anisic
aldehyde; cymal; ethyl vanillin; florhydral; helional; heliotropin;
hydroxycitronellal; koavone; lauric aldehyde; lyral; methyl nonyl
acetaldehyde; P. T. bucinal; phenyl acetaldehyde; undecylenic
aldehyde; vanillin; 2,6,10-trimethyl-9-undecenal, 3-dodecen-1-al,
alpha-n-amyl cinnamic aldehyde, 4-methoxybenzaldehyde,
benzaldehyde, 3-(4-tert butylphenyl)-propanal,
2-methyl-3-(para-methoxyphenyl propanal,
2-methyl-4-(2,6,6-trimethyl-2(1)-cyclohexen-1-yl) butanal,
3-phenyl-2-propenal, cis-/trans-3,7-dimethyl-2,6-octadien-1-al,
3,7-dimethyl-6-octen-1-al, [(3,7-dimethyl-6-octenyl) oxy]
acetaldehyde, 4-isopropylbenzyaldehyde,
1,2,3,4,5,6,7,8-octahydro-8,8-dimethyl-2-naphthaldehyde,
2,4-dimethyl-3-cyclohexen-1-carboxaldehyde,
2-methyl-3-(isopropylphenyl)propanal, 1-decanal; decyl aldehyde,
2,6-dimethyl-5-heptenal,
4-(tricyclo[5.2.1.0(2,6)]-decylidene-8)-butanal,
octahydro-4,7-methano-1H-indenecarboxaldehyde, 3-ethoxy-4-hydroxy
benzaldehyde, para-ethyl-alpha, alpha-dimethyl hydrocinnamaldehyde,
alpha-methyl-3,4-(methylenedioxy)-hydrocinnamaldehyde,
3,4-methylenedioxybenzaldehyde, alpha-n-hexyl cinnamic aldehyde,
m-cymene-7-carboxaldehyde, alpha-methyl phenyl acetaldehyde,
7-hydroxy-3,7-dimethyl octanal, Undecenal,
2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde,
4-(3)(4-methyl-3-pentenyl)-3-cyclohexen-carboxaldehyde,
1-dodecanal, 2,4-dimethyl cyclohexene-3-carbox-aldehyde,
4-(4-hydroxy-4-methyl pentyl)-3-cylohexene-1-carboxaldehyde,
7-methoxy-3,7-dimethyloctan-1-al, 2-methyl undecanal, 2-methyl
decanal, 1-nonanal, 1-octanal, 2,6,10-trimethyl-5,9-undecadienal,
2-methyl-3-(4-tertbutyl) propanal, dihydrocinnamic aldehyde,
1-methyl-4-(4-methyl-3-pentenyl)-3-cyclo-hexene-1-carboxaldehyde, 5
or 6 methoxy0hexahydro-4,7-methanoindan-1 or 2-carboxaldehyde,
3,7-dimethyloctan-1-al, 1-undecanal, 10-undecen-1-al,
4-hydroxy-3-methoxy benzaldehyde,
1-methyl-3-(4-methylpentyl)-3-cyclhexene-carboxaldehyde,
7-hydroxy-3,7-dimethyl-octanal, trans-4-decenal, 2,6-nonadienal,
para-tolylacetaldehyde; 4-methylphenylacetaldehyde,
2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal,
ortho-methoxycinnamic aldehyde, 3,5,6-trimethyl-3-cyclohexene
carboxaldehyde, 3,7-dimethyl-2-methylene-6-octenal,
phenoxyacetaldehyde, 5,9-dimethyl-4,8-decadienal, peony aldehyde
(6,10-dimethyl-3-oxa-5,9-undecadien-1-al),
hexahydro-4,7-methanoindan-1-carboxaldehyde, 2-methyl octanal,
alpha-methyl-4-(1-methyl ethyl) benzene acetaldehyde,
6,6-dimethyl-2-norpinene-2-propionaldehyde, para methyl phenoxy
acetaldehyde, 2-methyl-3-phenyl-2-propen-1-al, 3,5,5-trimethyl
hexanal, Hexahydro-8,8-dimethyl-2-naphthaldehyde,
3-propyl-bicyclo[2.2.1 ]-hept-5-ene-2-carbaldehyde, 9-decenal,
3-methyl-5-phenyl-1-pentanal, methylnonyl acetaldehyde, hexanal,
trans-2-hexenal, 1-p-menthene-q-carboxaldehyde and mixtures
thereof.
[0169] Most preferred aldehydes are selected from 1-decanal,
benzaldehyde, florhydral,
2,4-dimethyl-3-cyclohexen-1-carboxaldehyde;
cis/trans-3,7-dimethyl-2,6-octadien-1-al; heliotropin;
2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde; 2,6-nonadienal;
alpha-n-amyl cinnamic aldehyde, alpha-n-hexyl cinnamic aldehyde,
P.T. Bucinal, lyral, cymal, methyl nonyl acetaldehyde, hexanal,
trans-2-hexenal, and mixture thereof.
[0170] In the above list of perfume ingredients, some are
commercial names conventionally known to one skilled in the art,
and also includes isomers. Such isomers are also suitable for use
in the present invention.
[0171] In another embodiment, especially suitable for the purpose
of the present invention are the perfume compounds, preferably the
perfume ketones or active aldehydes, characterised by having a low
Odor Detection Threshold. Such Odor Detection Threshold (ODT)
should be lower than or equal to 1 ppm, preferably lower than or
equal to 10 ppb--measured at controlled Gas Chromatography (GC)
conditions such as described here below. This parameter refers to
the value commonly used in the perfumery arts and which is the
lowest concentration at which significant detection takes place
that some odorous material is present. Please refer for example in
"Compilation of Odor and Taste Threshold Value Data (ASTM DS 48
A)", edited by F. A. Fazzalari, International Business Machines,
Hopwell Junction, N.Y. and in Calkin et al., Perfumery, Practice
and Principles, John Willey & Sons, Inc., page 243 et seq
(1994). For the purpose of the present invention, the Odor
Detection Threshold is measured according to the following
method:
[0172] The gas chromatograph is characterized to determine the
exact volume of material injected by the syringe, the precise split
ratio, and the hydrocarbon response using a hydrocarbon standard of
known concentration and chain-length distribution. The air flow
rate is accurately measured and, assuming the duration of a human
inhalation to last 0.02 minutes, the sampled volume is calculated.
Since the precise concentration at the detector at any point in
time is known, the mass per volume inhaled is known and hence the
concentration of material. To determine the ODT of a perfume
material, solutions are delivered to the sniff port at the
back-calculated concentration. A panelist sniffs the GC effluent
and identifies the retention time when odor is noticed. The average
over all panelists determines the threshold of noticeability. The
necessary amount of analyte is injected onto the column to achieve
a certain concentration, such as 10 ppb, at the detector. Typical
gas chromatograph parameters for determining odor detection
thresholds are listed below. [0173] GC: 5890 Series II with FID
detector [0174] 7673 Autosampler [0175] Column: J&W Scientific
DB-1 [0176] Length 30 meters ID 0.25 mm film thickness 1 micron
[0177] Method: [0178] Split Injection: 17/1 split ratio [0179]
Autosampler: 1.13 microliters per injection [0180] Column Flow:
1.10 mL/minute [0181] Air Flow: 345 mL/minute [0182] Inlet Temp.
245.quadrature.C [0183] Detector Temp. 285.quadrature.C [0184]
Temperature Information [0185] Initial Temperature: 50.quadrature.C
[0186] Rate: 5C/minute [0187] Final Temperature: 280.quadrature.C
[0188] Final Time: 6 minutes [0189] Leading assumptions: 0.02
minutes per sniff [0190] GC air adds to sample dilution
[0191] Examples of such preferred perfume components are those
selected from : 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde,
1-(2,6,6-trimethyl-2-cyclohexan-1-yl)-2-buten-1-one and/or
para-methoxy-acetophenone. Even more preferred are the following
compounds having an ODT .ltoreq.10 ppb measured with the method
described above: undecylenic aldehyde, undecalactone gamma,
heliotropin, dodecalactone gamma, p-anisic aldehyde, para
hydroxy-phenyl-butanone, cymal, benzyl acetone, ionone alpha, p.t.
bucinal, damascenone, ionone beta and methyl-nonyl ketone.
[0192] Typically the level of active is of from 10 to 90%,
preferably from 30 to 85%, more preferably from 45 to 80% by weight
of the amine reaction product.
[0193] Preferred amine reaction products are those resulting from
the reaction of polethyleneimine polymer like Lupasol polymers,
with one or more of the following Alpha Damascone, Delta Damascone,
Carvone, Hedione, Florhydral, Lilial, Heliotropine,
Gamma-Methyl-Ionone and 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde.
Still other preferred amine reaction products are those resulting
from the reaction of Astramol Dendrimers with Carvone as well as
those resulting from the reaction of ethyl-4-amino benzoate with
2,4-dimethyl-3-cyclohexen-1-carboxaldehyde.
[0194] Most preferred amine reaction products are those from the
reaction of Lupasol HF with Delta Damascone; LupasolG35 with Alpha
Damascone; LupasolG100 with
2,4-dimethyl-3-cyclohexen-1-carboxaldehyde, ethyl-4-amino benzoate
with 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde.
Process
[0195] Preparation of the component is made as follows in the
Synthesis Examples. In general, the nitrogen analogs of ketones and
aldehydes are called azomethines, Schiff bases or the more
preferred name imines. These imines can easily be prepared by
condensation of primary amines and carbonyl compounds by
elimination of water.
[0196] A typical reaction profile is as follows: ##STR37##
.alpha.,.beta.-Unsaturated ketones do not only condense with amines
to form imines, but can also undergo a competitive 1,4-addition to
form .beta.-aminoketones. ##STR38##
[0197] By means of this simple method, compound and composition
containing said compounds are made which achieve a delayed release
of the active ingredient.
[0198] As can be observed, the perfume ingredient is typically
present in equimolar amount to the amine function so as to enable
the reaction to take place and provide the resulting amine reaction
product. Of course, higher amount are not excluded and even
preferred when the amine compound comprises more than one amine
function. When the amine compound has more than one free primary
and/or secondary amine function, several different perfume raw
materials can be linked to the amine compound.
Mechanism of Release
[0199] By the present invention, a delayed release of a perfume
ingredient, i.e. ketone or aldehyde is obtained. Not to be bound by
theory, the release is believed to occur by the following
mechanisms:
[0200] For imine compounds, the perfume components are released
upon breaking down of the imine bond, leading to the release of the
perfume component and of the primary amine compound. This can be
achieved by either hydrolysis, photochemical cleavage, oxidative
cleavage, or enzymatic cleavage.
[0201] For .beta.-aminoketone compounds, treatment with air
moisture and/or water successfully releases the perfume component
and the amine compound. However, other means of release are not
excluded like hydrolysis, photochemical cleavage, oxidative
cleavage, or enzymatic cleavage.
[0202] Still other means of release for imine as well as
.beta.-aminoketone compounds can be considered such as by the
steaming step of ironing the treated fabric, tumble-drying, and/or
wearing.
Applications Compositions
[0203] The present invention application compositions include
compositions where there is a need of a delayed release of an
active ketone or aldehyde. This includes compositions for use in
the rinse such as softening compositions, personal cleansing such
as shower gels, deodorants, bars, shampoos; stand alone
compositions such deodorising compositions, insecticides, etc . . .
. Preferred are those compositions which result in contacting the
compound of the invention with fabric. The composition of the
invention are suitable for use in any step of the domestic
treatment, that is a pre- and/or post-treatment composition, as a
wash additive, as a composition suitable for use in the rinse
process. Obviously, multiple applications can be made such as
treating the fabric with a pre-treatment composition of the
invention and thereafter with the composition suitable for use in
the rinse process and/or drying process.
[0204] By compositions suitable for use in the rinse process, these
are to be understood to include compositions such as rinse added
fabric softener compositions and dryer added compositions (e.g.
sheets) which provide softening and/or antistatic benefits, as well
as rinse additives.
[0205] Preferred are those compositions which result in contacting
the compound of the invention with fabric. These are to be
understood to include compositions such as rinse added fabric
softener compositions and dryer added compositions (e.g. sheets)
which provide softening and/or antistatic benefits.
[0206] Preferably, the amine reaction product(s) which is
incorporated into such compositions provides a dry surface Odor
Index of more than 5 preferably at least 10.
[0207] By Dry Surface Odor Index, it is meant that the amine
reaction product(s) provides a Delta of more than 5, wherein Delta
is the difference between the Odor Index of the dry surface treated
with amine reaction product(s) and of the Odor Index of the dry
surface treated with only the perfume raw material.
Measurement Method of Dry Surface Odor Index for Fabric Surface
Product Preparation:
[0208] The amine reaction product is added to the unperfumed
product base.
[0209] The unperfumed product base, wherein the abreviations are as
defined herein after for the examples, is as follows:
TABLE-US-00002 Component % by weight DEQA 19.0 HCl 0.02 PEG 0.6
Silicone antifoam 0.01 Electrolyte (ppm) 1200 Dye (ppm) 50 Water
and minors to balance to 100%
[0210] Levels of amine reaction product are selected so as to
obtain an odor grade on the dry fabric of at least 20. After
careful mixing, by shaking the container in case of a liquid, with
a spatula in case of a powder, the product is allowed to sit for 24
hrs.
Washing Process:
[0211] The resulting product is added into the washing machine in
the dosage and in the dispenser appropriate for its category. The
quantity corresponds to recommended dosages made for the
corresponding market products: typically between 70 and 150 g for a
detergent powder or liquid via current dosing device like
granulette, or ariellette, and 25 and 40 ml for a liquid fabric
softener. The load is composed of four bath towels (170 g) using a
Miele W830 washing machine at 40.degree. C. short cycle, water
input: 15.degree. Hardness at a temperature of 10-18.degree. C.,
and full spin of 1200 rpm .
[0212] The same process is applied for the corresponding free
perfume ingredient in consideration and is used as the reference.
Dosages, fabric loads and washing cycles for the reference and the
sample are identical.
Drying Process:
[0213] Within two hours after the end of the washing cycle, the
spinned but still wet fabrics are assessed for their odors using
the scale mentioned below. Afterwards, half of the fabric pieces
are hung on a line for 24 hr drying, away from any possible
contaminations. Unless specified, this drying takes place indoor.
Ambient conditions are at temperature between 18-25.degree. C. and
air moisture between 50-80%. The other half is placed in a tumble
drier and undergoes a full "very dry" cycle, i.e. in a Miele,
Novotronic T430 set on program white-extra dry (full cycle). Tumble
dry fabrics are also assessed on the next day. Fabrics are then
stored in opened aluminum bags in an odor free room, and assessed
again after 7 days.
Odor Evaluations:
[0214] Odor is assessed by expert panellists smelling carefully the
fabrics. A 0-100 scale is used for all fabric odor gradings. The
grading scale is as follows: [0215] 100=extremely strong perfume
odor [0216] 75=very strong perfume odor [0217] 50=strong odor
[0218] 40=moderate perfume odor [0219] 30=slight perfume odor
[0220] 20=weak perfume odor [0221] 10=very weak perfume odor [0222]
0=no odor
[0223] A difference of more than 5 grades after I day and/or 7 days
between the amine reaction product and the perfume raw material is
statistically significant. A difference of 10 grades or more after
one day and/or 7 days represents a step-change. In other words,
when a difference of grade of more than 5, preferably at least 10
is observed between the amine reaction product and the perfume raw
material, after either 1 day or 7 day or both 1 day and 7 days, it
can be concluded that the amine reaction product is suitable for
use in the present invention, provided that the amine compound
fulfill the Odor Intensity Index.
[0224] The amine reaction product as defined herein before
typically is comprised at from 0.0001% to 10%, preferably from
0.001% to 5%, and more preferably from 0.01% to 2%, by weight of
the composition. Mixtures of the compounds may also be used
herein.
[0225] Incorporation of the amine reaction product in the invention
compositions can conveniently, if necessary, be carried out by
conventional incorporation means, such as by spray-on,
encapsulation like starch encapsulation, e.g. such as described in
GB 1464616, dry addition, or by encapsulation in cyclodextrin.
Preferably, the amine reaction product is preformed before
incorporation into the invention compositions. In other words, the
perfume component and the amine compound are first reacted together
to obtain the resulting amine reaction product as defined in the
present invention and only once formed incorporated into the
invention compositions. By being preformed before the incorporation
in fully formulated composition, a better control of the compound
being made is obtained. Hence, the interaction with perfume
composition which may be present in fully formulated composition is
avoided as well as side reaction that could occur. Further, by such
means of incorporation, efficient control of the yield and purity
of the compound is obtained.
[0226] Most preferably, when the invention composition comprises a
perfume, the amine reaction product is incorporated in the
composition separately from the perfume. By this means, the amine
reaction product and its subsequent perfume release is more
controlled.
[0227] Typically the invention composition comprises surfactancy
ingredients such as a fabric softening agent, or a surfactant as
described hereinafter as optional ingredients.
[0228] When the compositions comprises a softening agent, the
resulting composition is a softening composition.
Fabric Softening Agents:
[0229] A fabric softener component provides softness and
antistastic properties to the treated fabrics. When used, the
fabric softener component will typically be present at a level
sufficient to provide softening and antistatic properties.
[0230] Said fabric softening component may be selected from
cationic, nonionic, amphoteric or anionic fabric softening
component.
[0231] Typical of the cationic softening components are the
quaternary ammonium compounds or amine precursors thereof as
defined hereinafter.
A)-Quaternary Ammonium Fabric Softening Active Compound
[0232] (1) Preferred quaternary ammonium fabric softening active
compound have the formula ##STR39## or the formula: ##STR40##
wherein Q is a carbonyl unit having the formula: ##STR41## each R
unit is independently hydrogen, C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 hydroxyalkyl, and mixtures thereof, preferably
methyl or hydroxy alkyl; each R.sup.1 unit is independently linear
or branched C.sub.11-C.sub.22 alkyl, linear or branched
C.sub.11-C.sub.22 alkenyl, and mixtures thereof, R.sup.2 is
hydrogen, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 hydroxyalkyl, and
mixtures thereof; X is an anion which is compatible with fabric
softener actives and adjunct ingredients; the index m is from 1 to
4, preferably 2; the index n is from 1 to 4, preferably 2.
[0233] An example of a preferred fabric softener active is a
mixture of quaternized amines having the formula: ##STR42## wherein
R is preferably methyl; R.sup.1 is a linear or branched alkyl or
alkenyl chain comprising at least 11 atoms, preferably at least 15
atoms. In the above fabric softener example, the unit
--O.sub.2CR.sup.1 represents a fatty acyl unit which is typically
derived from a triglyceride source. The triglyceride source is
preferably derived from tallow, partially hydrogenated tallow,
lard, partially hydrogenated lard, vegetable oils and/or partially
hydrogenated vegetable oils, such as, canola oil, safflower oil,
peanut oil, sunflower oil, corn oil, soybean oil, tall oil, rice
bran oil, etc. and mixtures of these oils.
[0234] The preferred fabric softening actives of the present
invention are the Diester and/or Diamide Quaternary Ammonium (DEQA)
compounds, the diesters and diamides having the formula: ##STR43##
wherein R, R.sup.1, X, and n are the same as defined herein above
for formulae (1) and (2), and Q has the formula: ##STR44##
[0235] These preferred fabric softening actives are formed from the
reaction of an amine with a fatty acyl unit to form an amine
intermediate having the formula: ##STR45## wherein R is preferably
methyl, Q and R.sup.1 are as defined herein before; followed by
quaternization to the final softener active.
[0236] Non-limiting examples of preferred amines which are used to
form the DEQA fabric softening actives according to the present
invention include methyl bis(2-hydroxyethyl)amine having the
formula: ##STR46## methyl bis(2-hydroxypropyl)amine having the
formula: ##STR47## methyl (3-aminopropyl) (2-hydroxyethyl)amine
having the formula: ##STR48## methyl bis(2-aminoethyl)amine having
the formula: ##STR49## triethanol amine having the formula:
##STR50## di(2-aminoethyl) ethanolamine having the formula:
##STR51##
[0237] The counterion, X.sup.(-) above, can be any
softener-compatible anion, preferably the anion of a strong acid,
for example, chloride, bromide, methylsulfate, ethylsulfate,
sulfate, nitrate and the like, more preferably chloride or methyl
sulfate. The anion can also, but less preferably, carry a double
charge in which case X.sup.(-) represents half a group.
[0238] Tallow and canola oil are convenient and inexpensive sources
of fatty acyl units which are suitable for use in the present
invention as R.sup.1 units. The following are non-limiting examples
of quaternary ammonium compounds suitable for use in the
compositions of the present invention. The term "tallowyl" as used
herein below indicates the R.sup.1 unit is derived from a tallow
triglyceride source and is a mixture of fatty acyl units. Likewise,
the use of the term canolyl refers to a mixture of fatty acyl units
derived from canola oil. TABLE-US-00003 TABLE II Fabric Softener
Actives N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(canolyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium
chloride; N,N-di(canolyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl)
ammonium chloride; N,N-di(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethyl
ammonium chloride; N,N-di(2-canolyloxy-2-oxo-ethyl)-N,N-dimethyl
ammonium chloride
N,N-di(2-tallowyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammonium
chloride; N,N-di(2-canolyloxyethylcarbonyloxyethyl)-N,N-dimethyl
ammonium chloride;
N-(2-tallowoyloxy-2-ethyl)-N-(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethyl
ammonium chloride;
N-(2-canolyloxy-2-ethyl)-N-(2-canolyloxy-2-oxo-ethyl)-N,N-dimethyl
ammonium chloride; N,N,N-tri(tallowyl-oxy-ethyl)-N-methyl ammonium
chloride; N,N,N-tricanolyl-oxy-ethyl)-N-methyl ammonium chloride;
N-(2-tallowyloxy-2-oxoethyl)-N-(tallowyl)-N,N-dimethyl ammonium
chloride; N-(2-canolyloxy-2-oxoethyl)-N-(canolyl)-N,N-dimethyl
ammonium chloride;
1,2-ditallowyloxy-3-N,N,N-trimethylammoniopropane chloride; and
1,2-dicanolyloxy-3-N,N,N-trimethylammoniopropane chloride; and
mixtures of the above actives.
[0239] Other examples of quaternay ammoniun softening compounds are
methylbis(tallowamidoethyl)(2-hydroxyethyl)ammonium methylsulfate
and methylbis(hydrogenated
tallowamidoethyl)(2-hydroxyethyl)ammonium methyl-sulfate; these
materials are available from Witco Chemical Company under the trade
names Varisoft.RTM. 222 and Varisoft.RTM. 110, respectively.
[0240] Particularly preferred is
N,N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium chloride, where
the tallow chains are at least partially unsaturated.
[0241] The level of unsaturation contained within the tallow,
canola, or other fatty acyl unit chain can be measured by the
Iodine Value (IV) of the corresponding fatty acid, which in the
present case should preferably be in the range of from 5 to 100
with two categories of compounds being distinguished, having a IV
below or above 25.
[0242] Indeed, for compounds having the formula: ##STR52## derived
from tallow fatty acids, when the Iodine Value is from 5 to 25,
preferably 15 to 20, it has been found that a cis/trans isomer
weight ratio greater than 30/70, preferably greater than 50/50 and
more preferably greater than 70/30 provides optimal
concentrability.
[0243] For compounds of this type made from tallow fatty acids
having a Iodine Value of above 25, the ratio of cis to trans
isomers has been found to be less critical unless very high
concentrations are needed.
[0244] Other suitable examples of fabric softener actives are
derived from fatty acyl groups wherein the terms "tallowyl" and
canolyl" in the above examples are replaced by the terms "cocoyl,
palmyl, lauryl, oleyl, ricinoleyl, stearyl, palmityl," which
correspond to the triglyceride source from which the fatty acyl
units are derived. These alternative fatty acyl sources can
comprise either fully saturated, or preferably at least partly
unsaturated chains.
[0245] As described herein before, R units are preferably methyl,
however, suitable fabric softener actives are described by
replacing the term "methyl" in the above examples in Table II with
the units "ethyl, ethoxy, propyl, propoxy, isopropyl, butyl,
isobutyl and t-butyl.
[0246] The counter ion, X, in the examples of Table II can be
suitably replaced by bromide, methylsulfate, formate, sulfate,
nitrate, and mixtures thereof. In fact, the anion, X, is merely
present as a counterion of the positively charged quaternary
ammonium compounds. The scope of this invention is not considered
limited to any particular anion.
[0247] For the preceding ester fabric softening agents, the pH of
the compositions herein is an important parameter of the present
invention. Indeed, it influences the stability of the quaternary
ammonium or amine precursors compounds, especially in prolonged
storage conditions. The pH, as defined in the present context, is
measured in the neat compositions at 20.degree. C. While these
compositions are operable at pH of less than 6.0, for optimum
hydrolytic stability of these compositions, the neat pH, measured
in the above-mentioned conditions, must preferably be in the range
of from 2.0 to 5, preferably in the range of 2.5 to 4.5, preferably
2.5 to 3.5. The pH of these compositions herein can be regulated by
the addition of a Bronsted acid.
[0248] Examples of suitable acids include the inorganic mineral
acids, carboxylic acids, in particular the low molecular weight
(C.sub.1-C.sub.5) carboxylic acids, and alkylsulfonic acids.
Suitable inorganic acids include HCl, H.sub.2SO.sub.4, HNO.sub.3
and H.sub.3PO.sub.4. Suitable organic acids include formic, acetic,
citric, methylsulfonic and ethylsulfonic acid. Preferred acids are
citric, hydrochloric, phosphoric, formic, methylsulfonic acid, and
benzoic acids.
[0249] As used herein, when the diester is specified, it will
include the monoester that is normally present in manufacture. For
softening, under no/low detergent carry-over laundry conditions the
percentage of monoester should be as low as possible, preferably no
more than 2.5%. However, under high detergent carry-over
conditions, some monoester is preferred. The overall ratios of
diester to monoester are from 100:1 to 2:1, preferably from 50:1 to
5:1, more preferably from 13:1 to 8:1. Under high detergent
carry-over conditions, the di/monoester ratio is preferably 11:1.
The level of monoester present can be controlled in the
manufacturing of the softener compound.
[0250] Mixtures of actives of formula (1) and (2) may also be
prepared.
[0251] 2)-Still other suitable quaternary ammonium fabric softening
compounds for use herein are cationic nitrogenous salts having two
or more long chain acyclic aliphatic C.sub.8-C.sub.22 hydrocarbon
groups or one said group and an arylalkyl group which can be used
either alone or as part of a mixture are selected from the group
consisting of: [0252] (i) acyclic quaternary ammonium salts having
the formula: ##STR53## [0253] wherein R.sup.4 is an acyclic
aliphatic C.sub.8-C.sub.22 hydrocarbon group, R.sup.5 is a
C.sub.1-C.sub.4 saturated alkyl or hydroxyalkyl group, R.sup.8 is
selected from the group consisting of R.sup.4 and R.sup.5 groups,
and A- is an anion defined as above; [0254] (ii) diamino
alkoxylated quaternary ammonium salts having the formula: ##STR54##
[0255] wherein n is equal to 1 to 5, and R.sup.1, R.sup.2, R.sup.5
and A.sup.- are as defined above; [0256] (iii) mixtures
thereof.
[0257] Examples of the above class cationic nitrogenous salts are
the well-known dialkyldi methylammonium salts such as
ditallowdimethylammonium chloride, ditallowdimethylammonium
methylsulfate, di(hydrogenatedtallow)dimethyl-ammonium chloride,
distearyldimethylammonium chloride, dibehenyldimethyl-ammonium
chloride. Di(hydrogenatedtallow)di methylammonium chloride and
ditallowdimethylammonium chloride are preferred. Examples of
commercially available dialkyldimethyl ammonium salts usable in the
present invention are di(hydrogenatedtallow)dimethylammonium
chloride (trade name Adogen.RTM. 442), ditallowdimethylammonium
chloride (trade name Adogen.RTM. 470, Praepagen.RTM. 3445),
distearyl dimethylammonium chloride (trade name Arosurf.RTM.
TA-100), all available from Witco Chemical Company.
Dibehenyldimethylammonium chloride is sold under the trade name
Kemamine Q-2802C by Humko Chemical Division of Witco Chemical
Corporation. Dimethylstearylbenzyl ammonium chloride is sold under
the trade names Varisoft.RTM. SDC by Witco Chemical Company and
Ammonyx.RTM. 490 by Onyx Chemical Company.
[0258] B)-Amine Fabric Softening Active Compound
[0259] Suitable amine fabric softening compounds for use herein,
which may be in amine form or cationic form are selected from:
[0260] (i)-Reaction products of higher fatty acids with a polyamine
selected from the group consisting of hydroxyalkylalkylenediamines
and dialkylenetriamines and mixtures thereof. These reaction
products are mixtures of several compounds in view of the
multi-functional structure of the polyamines.
[0261] The preferred Component (i) is a nitrogenous compound
selected from the group consisting of the reaction product mixtures
or some selected components of the mixtures. One preferred
component (i) is a compound selected from the group consisting of
substituted imidazoline compounds having the formula: ##STR55##
wherein R.sup.7 is an acyclic aliphatic C.sub.15-C.sub.21
hydrocarbon group and R.sup.8 is a divalent C.sub.1-C.sub.3
alkylene group.
[0262] Component (i) materials are commercially available as:
Mazamide.RTM. 6, sold by Mazer Chemicals, or Ceranine.RTM. HC, sold
by Sandoz Colors & Chemicals; stearic hydroxyethyl imidazoline
sold under the trade names of Alkazine.RTM. ST by Alkaril
Chemicals, Inc., or Schercozoline.RTM. S by Scher Chemicals, Inc.;
N,N''-ditallowalkoyldiethylenetriamine;
1-tallowamidoethyl-2-tallowimidazoline (wherein in the preceding
structure R.sup.1 is an aliphatic C.sub.15-C.sub.17 hydrocarbon
group and R.sup.8 is a divalent ethylene group).
[0263] Certain of the Components (i) can also be first dispersed in
a Bronsted acid dispersing aid having a pKa value of not greater
than 4; provided that the pH of the final composition is not
greater than 6. Some preferred dispersing aids are hydrochloric
acid, phosphoric acid, or methylsulfonic acid.
[0264] Both N,N''-ditallowalkoyldiethylenetriamine and
1-tallow(amidoethyl)-2-tallowimidazoline are reaction products of
tallow fatty acids and diethylenetriamine, and are precursors of
the cationic fabric softening agent
methyl-1-tallowamidoethyl-2-tallowimidazolinium methylsulfate (see
"Cationic Surface Active Agents as Fabric Softeners," R. R. Egan,
Journal of the American Oil Chemicals' Society, January 1978, pages
118-121). N,N''-ditallow alkoyldiethylenetriamine and
1-tallowamidoethyl-2-tallowimidazoline can be obtained from Witco
Chemical Company as experimental chemicals.
Methyl-1-tallowamidoethyl-2-tallowimidazolinium methylsulfate is
sold by Witco Chemical Company under the tradename Varisoft.RTM.
475.
[0265] (ii)-softener having the formula: ##STR56## wherein each
R.sup.2 is a C.sub.1-6 alkylene group, preferably an ethylene
group; and G is an oxygen atom or an --NR-- group; and each R,
R.sup.1, R.sup.2 and R.sup.5 have the definitions given above and
A.sup.- has the definitions given above for X.sup.-.
[0266] An example of Compound (ii) is
1-oleylamidoethyl-2-oleylimidazolinium chloride wherein R.sup.1 is
an acyclic aliphatic C.sub.15-C.sub.17 hydrocarbon group, R.sup.2
is an ethylene group, G is a NH group, R.sup.5 is a methyl group
and A.sup.- is a chloride anion.
[0267] (iii)-softener having the formula: ##STR57## wherein R,
R.sup.1, R.sup.2, and A.sup.- are defined as above.
[0268] An example of Compound (iii) is the compound having the
formula: ##STR58## wherein R.sup.1 is derived from oleic acid.
[0269] Additional fabric softening materials may be used in
addition or alternatively to the cationic fabric softener. These
may be selected from nonionic, amphoteric or anionic fabric
softening material. Disclosure of such materials may be found in
U.S. Pat. No. 4,327,133; U.S. Pat. No. 4,421,792; U.S. Pat. No.
4,426,299; U.S. Pat. No. 4,460,485; U.S. Pat. No. 3,644,203; U.S.
Pat. No. 4,661,269; U.S. Pat. No. 4,439,335; U.S. Pat. No.
3,861,870; U.S. Pat. No. 4,308,151; U.S. Pat. No. 3,886,075; U.S.
Pat. No. 4,233,164; U.S. Pat. No. 4,401,578; U.S. Pat. No.
3,974,076; U.S. Pat. No. 4,237,016 and EP 472,178.
[0270] Typically, such nonionic fabric softener materials have an
HLB of from 2 to 9, more typically from 3 to 7. Such nonionic
fabric softener materials tend to be readily dispersed either by
themselves, or when combined with other materials such as
single-long-chain alkyl cationic surfactant described in detail
hereinafter. Dispersibility can be improved by using more
single-long-chain alkyl cationic surfactant, mixture with other
materials as set forth hereinafter, use of hotter water, and/or
more agitation. In general, the materials selected should be
relatively crystalline, higher melting, (e.g. >40.degree. C.)
and relatively water-insoluble.
[0271] Preferred nonionic softeners are fatty acid partial esters
of polyhydric alcohols, or anhydrides thereof, wherein the alcohol,
or anhydride, contains from 2 to 18, preferably from 2 to 8, carbon
atoms, and each fatty acid moiety contains from 12 to 30,
preferably from 16 to 20, carbon atoms. Typically, such softeners
contain from one to 3, preferably 2 fatty acid groups per
molecule.
[0272] The polyhydric alcohol portion of the ester can be ethylene
glycol, glycerol, poly (e.g., di-, tri-, tetra, penta-, and/or
hexa-) glycerol, xylitol, sucrose, erythritol, pentaerythritol,
sorbitol or sorbitan. Sorbitan esters and polyglycerol monostearate
are particularly preferred.
[0273] The fatty acid portion of the ester is normally derived from
fatty acids having from 12 to 30, preferably from 16 to 20, carbon
atoms, typical examples of said fatty acids being lauric acid,
myristic acid, palmitic acid, stearic acid and behenic acid. Highly
preferred optional nonionic softening agents for use in the present
invention are the sorbitan esters, which are esterified dehydration
products of sorbitol, and the glycerol esters.
[0274] Commercial sorbitan monostearate is a suitable material.
Mixtures of sorbitan stearate and sorbitan palmitate having
stearate/palmitate weight ratios varying between 10:1 and 1:10, and
1,5-sorbitan esters are also useful.
[0275] Glycerol and polyglycerol esters, especially glycerol,
diglycerol, triglycerol, and polyglycerol mono- and/or di-esters,
preferably mono-, are preferred herein (e.g. polyglycerol
monostearate with a trade name of Radiasurf 7248).
[0276] Useful glycerol and polyglycerol esters include mono-esters
with stearic, oleic, palmitic, lauric, isostearic, myristic, and/or
behenic acids and the diesters of stearic, oleic, palmitic, lauric,
isostearic, behenic, and/or myristic acids. It is understood that
the typical mono-ester contains some di- and tri-ester, etc.
[0277] The "glycerol esters" also include the polyglycerol, e.g.,
diglycerol through octaglycerol esters. The polyglycerol polyols
are formed by condensing glycerin or epichlorohydrin together to
link the glycerol moieties via ether linkages. The mono- and/or
diesters of the polyglycerol polyols are preferred, the fatty acyl
groups typically being those described herein before for the
sorbitan and glycerol esters.
[0278] Further fabric softening components suitable for use herein
are the softening clays, such as the low ion-exchange-capacity ones
described in EP-A-0,150,531.
[0279] Of course, the term "softening active" can also encompass
mixed softening active agents.
[0280] Preferred among the classes of softener compounds disclosed
herein before are the diester or diamido quaternary ammonium fabric
softening active compound (DEQA).
[0281] The fabric softener compounds herein are present at levels
of from 1% to 80% of compositions herein, depending on the
composition execution which can be dilute with a preferred level of
active from 5% to 15%, or concentrated, with a preferred level of
active from 15% to 50%, most preferably 15% to 35% by weight of the
composition.
[0282] Fully formulated softening compositions preferably contain,
in addition to the herein before described components, one or more
of the following ingredients.
[0283] (A) Brighteners
[0284] The compositions herein can also optionally contain from
0.005% to 5% by weight of certain types of hydrophilic optical
brighteners which also provide a dye transfer inhibition action. If
used, the compositions herein will preferably comprise from 0.001%
to 1% by weight of such optical brighteners.
[0285] The hydrophilic optical brighteners useful in the present
invention are those having the structural formula: ##STR59##
wherein R.sub.1 is selected from anilino, N-2-bis-hydroxyethyl and
NH-2-hydroxyethyl; R.sub.2 is selected from N-2-bis-hydroxyethyl,
N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M
is a salt-forming cation such as sodium or potassium.
[0286] When in the above formula, R.sub.1 is anilino, R.sub.2 is
N-2-bis-hydroxyethyl and M is a cation such as sodium, the
brightener is
4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-
-stilbenedisulfonic acid and disodium salt. This particular
brightener species is commercially marketed under the tradename
Tinopal-UNPA-GX.RTM. by Ciba-Geigy Corporation. Tinopal-UNPA-GX is
the preferred hydrophilic optical brightener useful in the rinse
added compositions herein.
[0287] When in the above formula, R.sub.1 is anilino, R.sub.2 is
N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium,
the brightener is
4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)am-
ino]2,2'-stilbenedisulfonic acid disodium salt. This particular
brightener species is commercially marketed under the tradename
Tinopal 5BM-GX.RTM. by Ciba-Geigy Corporation.
[0288] When in the above formula, R.sup.1 is anilino, R.sub.2 is
morphilino and M is a cation such as sodium, the brightener is
4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisul-
fonic acid, sodium salt. This particular brightener species is
commercially marketed under the tradename Tinopal AMS-GX.RTM. by
Ciba Geigy Corporation.
[0289] (B) Dispersibility Aids
[0290] Relatively concentrated compositions containing both
saturated and unsaturated diester quaternary ammonium compounds can
be prepared that are stable without the addition of concentration
aids. However, the compositions of the present invention may
require organic and/or inorganic concentration aids to go to even
higher concentrations and/or to meet higher stability standards
depending on the other ingredients. These concentration aids which
typically can be viscosity modifiers may be needed, or preferred,
for ensuring stability under extreme conditions when particular
softener active levels are used. The surfactant concentration aids
are typically selected from the group consisting of (1) single long
chain alkyl cationic surfactants; (2) nonionic surfactants; (3)
amine oxides; (4) fatty acids; and (5) mixtures thereof. These aids
are described in WO 94/20597, specifically on page 14, line 12 to
page 20, line 12, which is herein incorporated by reference.
[0291] When said dispersibility aids are present, the total level
is from 2% to 25%, preferably from 3% to 17%, more preferably from
4% to 15%, and even more preferably from 5% to 13% by weight of the
composition. These materials can either be added as part of the
active softener raw material, (I), e.g., the mono-long chain alkyl
cationic surfactant and/or the fatty acid which are reactants used
to form the biodegradable fabric softener active as discussed
herein before, or added as a separate component. The total level of
dispersibility aid includes any amount that may be present as part
of component (I).
(1) Mono-Alkyl Cationic Quaternary Ammonium Compound
[0292] When the mono-alkyl cationic quaternary ammonium compound is
present, it is typically present at a level of from 2% to 25%,
preferably from 3% to 17%, more preferably from 4% to 15%, and even
more preferably from 5% to 13% by weight of the composition, the
total mono-alkyl cationic quaternary ammonium compound being at
least at an effective level.
[0293] Such mono-alkyl cationic quaternary ammonium compounds
useful in the present invention are, preferably, quaternary
ammonium salts of the general formula:
[R.sup.4N.sup.+(R.sup.5).sub.3]X.sup.- wherein [0294] R.sup.4 is
C.sub.8-C.sub.22 alkyl or alkenyl group, preferably
C.sub.10-C.sub.18 alkyl or alkenyl group; more preferably
C.sub.10-C.sub.14 or C.sub.16-C.sub.18 alkyl or alkenyl group;
[0295] each R.sup.5 is a C.sub.1-C.sub.6 alkyl or substituted alkyl
group (e.g., hydroxy alkyl), preferably C.sub.1-C.sub.3 alkyl
group, e.g., methyl (most preferred), ethyl, propyl, and the like,
a benzyl group, hydrogen, a polyethoxylated chain with from 2 to 20
oxyethylene units, preferably from 2.5 to 13 oxyethylene units,
more preferably from 3 to 10 oxyethylene units, and mixtures
thereof; and [0296] X.sup.- is as defined herein before for
(Formula (I)).
[0297] Especially preferred dispersibility aids are monolauryl
trimethyl ammonium chloride and monotallow trimethyl ammonium
chloride available from Witco under the trade names Adogen.RTM. 412
and Adogen.RTM. 471, monooleyl or monocanola trimethyl ammonium
chloride available from Witco under the tradename Adogen.RTM. 417,
monococonut trimethyl ammonium chloride available from Witco under
the trade name Adogen.RTM. 461, and monosoya trimethyl ammonium
chloride available from Witco under the trade name Adogen.RTM.
415.
[0298] The R.sup.4 group can also be attached to the cationic
nitrogen atom through a group containing one, or more, ester,
amide, ether, amine, etc., linking groups which can be desirable
for increased concentratability of component (I), etc. Such linking
groups are preferably within from one to three carbon atoms of the
nitrogen atom.
[0299] Mono-alkyl cationic quaternary ammonium compounds also
include C.sub.8-C.sub.22 alkyl choline esters.
[0300] The preferred dispersibility aids of this type have the
formula: R.sup.1C(O)--O--CH.sub.2CH.sub.2N.sup.+(R).sub.3X.sup.-
wherein R.sup.1, R and X.sup.- are as defined previously.
[0301] Highly preferred dispersibility aids include
C.sub.12-C.sub.14 coco choline ester and C.sub.16-C.sub.18 tallow
choline ester.
[0302] Suitable biodegradable single-long-chain alkyl
dispersibility aids containing an ester linkage in the long chains
are described in U.S. Pat. No. 4,840,738, said patent being
incorporated herein by reference.
[0303] When the dispersibility aid comprises alkyl choline esters,
preferably the compositions also contain a small amount, preferably
from 2% to 5% by weight of the composition, of organic acid.
Organic acids are described in EP.404,471, which is herein
incorporated by reference. Preferably the organic acid is selected
from the group consisting of glycolic acid, acetic acid, citric
acid, and mixtures thereof.
[0304] Ethoxylated quaternary ammonium compounds which can serve as
the dispersibility aid include ethylbis(polyethoxy
ethanol)alkylammonium ethyl-sulfate with 17 moles of ethylene
oxide, available under the trade name Variquat.RTM. 66 from Witco
Corporation; polyethylene glycol (15) oleammonium chloride,
available under the trade name Ethoquad.RTM. 0/25 from Akzo; and
polyethylene glycol (15) cocomonium chloride, available under the
trade name Ethoquad.RTM. C/25 from Akzo.
[0305] Quaternary compounds having only a single long alkyl chain,
can protect the cationic softener from interacting with anionic
surfactants and/or detergent builders that are carried over into
the rinse from the wash solution.
(2) Nonionic Surfactant (Alkoxylated Materials)
[0306] Suitable nonionic surfactants to serve as the
viscosity/dispersibility modifier include addition products of
ethylene oxide and, optionally, propylene oxide, with fatty
alcohols, fatty acids, fatty amines, etc. They are referred to
herein as ethoxylated fatty alcohols, ethoxylated fatty acids, and
ethoxylated fatty amines.
[0307] Any of the alkoxylated materials of the particular type
described hereinafter can be used as the nonionic surfactant. In
general terms, the nonionics herein, when used alone, in liquid
compositions are at a level of from 0% to 5%, preferably from 0. 1%
to 5%, more preferably from 0.2% to 3%. Suitable compounds are
substantially water-soluble surfactants of the general formula:
R.sup.2--Y--(C.sub.2H.sub.4O).sub.z--C.sub.2H.sub.4OH wherein
R.sup.2 for both solid and liquid compositions is selected from the
group consisting of primary, secondary and branched chain alkyl
and/or acyl hydrocarbyl groups; primary, secondary and branched
chain alkenyl hydrocarbyl groups; and primary, secondary and
branched chain alkyl- and alkenyl-substituted phenolic hydrocarbyl
groups; said hydrocarbyl groups having a hydrocarbyl chain length
of from 8 to 20, preferably from 10 to 18 carbon atoms. More
preferably the hydrocarbyl chain length for liquid compositions is
from 16 to 18 carbon atoms and for solid compositions from 10 to 14
carbon atoms. In the general formula for the ethoxylated nonionic
surfactants herein, Y is typically --O--, --C(O)O--, --C(O)N(R)--,
or --C(O)N(R)R--, preferably --O--, and in which R.sup.2,and R,
when present, have the meanings given herein before, and/or R can
be hydrogen, and z is at least 8, preferably at least 10-11.
Performance and, usually, stability of the softener composition
decrease when fewer ethoxylate groups are present.
[0308] The nonionic surfactants herein are characterized by an HLB
(hydrophilic-lipophilic balance) of from 7 to 20, preferably from 8
to 15. Of course, by defining R.sup.2 and the number of ethoxylate
groups, the HLB of the surfactant is, in general, determined.
However, it is to be noted that the nonionic ethoxylated
surfactants useful herein, for concentrated liquid compositions,
contain relatively long chain R.sup.2 groups and are relatively
highly ethoxylated. While shorter alkyl chain surfactants having
short ethoxylated groups can possess the requisite HLB, they are
not as effective herein.
[0309] Nonionic surfactants as the viscosity/dispersibility
modifiers are preferred over the other modifiers disclosed herein
for compositions with higher levels of perfume.
[0310] Examples of nonionic surfactants follow. The nonionic
surfactants of this invention are not limited to these examples. In
the examples, the integer defines the number of ethoxy (EO) groups
in the molecule.
(3) Amine Oxides
[0311] Suitable amine oxides include those with one alkyl or
hydroxyalkyl moiety of 8 to 22 carbon atoms, preferably from 10 to
18 carbon atoms, more preferably from 8 to 14 carbon atoms, and two
alkyl moieties selected from the group consisting of alkyl groups
and hydroxyalkyl groups with 1 to 3 carbon atoms.
[0312] Examples include dimethyloctylamine oxide, diethyldecylamine
oxide, bis-(2-hydroxyethyl)dodecyl-amine oxide,
dimethyldodecylamine oxide, dipropyl-tetradecylamine oxide,
methylethylhexadecylamine oxide, dimethyl-2-hydroxyoctadecylamine
oxide, and coconut fatty alkyl dimethylamine oxide.
[0313] (C) Stabilizers
[0314] Stabilizers can be present in the compositions of the
present invention. The term "stabilizer," as used herein, includes
antioxidants and reductive agents. These agents are present at a
level of from 0% to 2%, preferably from 0.01% to 0.2%, more
preferably from 0.035% to 0.1% for antioxidants, and more
preferably from 0.01% to 0.2% for reductive agents. These assure
good odor stability under long term storage conditions.
Antioxidants and reductive agent stabilizers are especially
critical for unscented or low scent products (no or low
perfume).
[0315] Examples of antioxidants that can be added to the
compositions of this invention include a mixture of ascorbic acid,
ascorbic palmitate, propyl gallate, available from Eastman Chemical
Products, Inc., under the trade names Tenox.RTM. PG and Tenox.RTM.
S-1; a mixture of BHT (butylated hydroxytoluene), BHA (butylated
hydroxyanisole), propyl gallate, and citric acid, available from
Eastman Chemical Products, Inc., under the trade name Tenox.RTM.-6;
butylated hydroxytoluene, available from UOP Process Division under
the trade name Sustane.RTM. BHT; tertiary butylhydroquinone,
Eastman Chemical Products, Inc., as Tenox.RTM. TBHQ; natural
tocopherols, Eastman Chemical Products, Inc., as Tenox.RTM.
GT-1/GT-2; and butylated hydroxyanisole, Eastman Chemical Products,
Inc., as BHA; long chain esters (C.sub.8-C.sub.22) of gallic acid,
e.g., dodecyl gallate; Irganox.RTM. 1010; Irganox.RTM. 1035;
Irganox.RTM. B 1171; Irganox.RTM. 1425; Irganox.RTM. 3114;
Irganox.RTM. 3125; and mixtures thereof; preferably Irganox.RTM.
3125, Irganox.RTM. 1425, Irganox.RTM. 3114, and mixtures thereof;
more preferably Irganox.RTM. 3125 alone or mixed with citric acid
and/or other chelators such as isopropyl citrate, Dequest.RTM.
2010, available from Monsanto with a chemical name of
1-hydroxyethylidene-1, 1-diphosphonic acid (etidronic acid), and
Tiron.RTM., available from Kodak with a chemical name of
4,5-dihydroxy-m-benzene-sulfonic acid/sodium salt, and DTPA.RTM.,
available from Aldrich with a chemical name of
diethylenetriaminepentaacetic acid.
[0316] (D) Soil Release Agent
[0317] In the present invention, an optional soil release agent can
be added. Typical levels of incorporation in the composition are
from 0% to 10%, preferably from 0.2% to 5%, of a soil release
agent. Preferably, such a soil release agent is a polymer.
[0318] Soil Release agents are desirably used in fabric softening
compositions of the instant invention. Any polymeric soil release
agent known to those skilled in the art can optionally be employed
in the compositions of this invention. Polymeric soil release
agents are characterized by having both hydrophilic segments, to
hydrophilize the surface of hydrophobic fibers, such as polyester
and nylon, and hydrophobic segments, to deposit upon hydrophobic
fibers and remain adhered thereto through completion of washing and
rinsing cycles and, thus, serve as an anchor for the hydrophilic
segments. This can enable stains occurring subsequent to treatment
with the soil release agent to be more easily cleaned in later
washing procedures.
[0319] If utilized, soil release agents will generally comprise
from about 0.01% to about 10.0%, by weight, of the detergent
compositions herein, typically from about 0.1% to about 5%,
preferably from about 0.2% to about 3.0%.
[0320] The following, all included herein by reference, describe
soil release polymers suitable for use in the present invention.
U.S. Pat. No. 3,959,230 Hays, issued May 25, 1976; U.S. Pat. No.
3,893,929 Basadur, issued Jul. 8, 1975; U.S. Pat. No. 4,000,093,
Nicol, et al., issued Dec. 28, 1976; U.S. Pat. No. 4,702,857
Gosselink, issued Oct. 27, 1987; U.S. Pat. No. 4,968,451, Scheibel
et al., issued Nov. 6; U.S. Pat. No. 4,702,857, Gosselink, issued
Oct. 27, 1987; U.S. Pat. No. 4,711,730, Gosselink et al., issued
Dec. 8, 1987; U.S. Pat. No. 4,721,580, Gosselink, issued Jan. 26,
1988; U.S. Pat. No. 4,877,896, Maldonado et al., issued Oct. 31,
1989; U.S. Pat. No. 4,956,447, Gosselink et al., issued Sep. 11,
1990; U.S. Pat. No. 5,415,807 Gosselink et al., issued May 16,
1995; European Patent Application 0 219 048, published Apr. 22,
1987 by Kud, et al.
[0321] Further suitable soil release agents are described in U.S.
Pat. No. 4,201,824, Violland et al.; U.S. Pat. No. 4,240,918
Lagasse et al.; U.S. Pat. No. 4,525,524 Tung et al.; U.S. Pat. No.
4,579,681, Ruppert et al.; U.S. Pat. No. 4,240,918; U.S. Pat. No.
4,787,989; U.S. Pat. No. 4,525,524; EP 279,134 A, 1988, to
Rhone-Poulenc Chemie; EP 457,205 A to BASF (1991); and DE 2,335,044
to Unilever N.V., 1974 all incorporated herein by reference.
[0322] Commercially available soil release agents include the
METOLOSE SM100, METOLOSE SM200 manufactured by Shin-etsu Kagaku
Kogyo K.K., SOKALAN type of material, e.g., SOKALAN HP-22,
available from BASF (Germany), ZELCON 5126 (from Dupont) and
MILEASE T (from ICI).
[0323] (E) Scum Dispersant
[0324] In the present invention, the premix can be combined with an
optional scum dispersant, other than the soil release agent, and
heated to a temperature at or above the melting point(s) of the
components.
[0325] The preferred scum dispersants herein are formed by highly
ethoxylating hydrophobic materials. The hydrophobic material can be
a fatty alcohol, fatty acid, fatty amine, fatty acid amide, amine
oxide, quaternary ammonium compound, or the hydrophobic moieties
used to form soil release polymers. The preferred scum dispersants
are highly ethoxylated, e.g., more than 17, preferably more than
25, more preferably more than 40, moles of ethylene oxide per
molecule on the average, with the polyethylene oxide portion being
from 76% to 97%, preferably from 81% to 94%, of the total molecular
weight.
[0326] The level of scum dispersant is sufficient to keep the scum
at an acceptable, preferably unnoticeable to the consumer, level
under the conditions of use, but not enough to adversely affect
softening. For some purposes it is desirable that the scum is
nonexistent. Depending on the amount of anionic or nonionic
detergent, etc., used in the wash cycle of a typical laundering
process, the efficiency of the rinsing steps prior to the
introduction of the compositions herein, and the water hardness,
the amount of anionic or nonionic detergent surfactant and
detergency builder (especially phosphates and zeolites) entrapped
in the fabric (laundry) will vary. Normally, the minimum amount of
scum dispersant should be used to avoid adversely affecting
softening properties. Typically scum dispersion requires at least
2%, preferably at least 4% (at least 6% and preferably at least 10%
for maximum scum avoidance) based upon the level of softener
active. However, at levels of 10% (relative to the softener
material) or more, one risks loss of softening efficacy of the
product especially when the fabrics contain high proportions of
nonionic surfactant which has been absorbed during the washing
operation.
[0327] Preferred scum dispersants are: Brij 700.RTM.; Varonic
U-250.RTM.; Genapol T-500.RTM., Genapol T-800.RTM.; Plurafac
A-79.RTM.; and Neodol 25-50.RTM..
[0328] (F) Bactericides
[0329] Examples of bactericides used in the compositions of this
invention include glutaraldehyde, formaldehyde,
2-bromo-2-nitro-propane-1,3-diol sold by Inolex Chemicals, located
in Philadelphia, Pa., under the trade name Bronopol.RTM.,and a
mixture of 5-chloro-2-methyl-4-isothiazoline-3-one and
2-methyl-4-isothiazoline-3-one sold by Rohm and Haas Company under
the trade name Kathon 1 to 1,000 ppm by weight of the agent.
[0330] (G) Perfume
[0331] The present invention can contain any softener compatible
perfume. Suitable perfumes are disclosed in U.S. Pat. No.
5,500,138, said patent being incorporated herein by reference.
[0332] As used herein, perfume includes fragrant substance or
mixture of substances including natural (i.e., obtained by
extraction of flowers, herbs, leaves, roots, barks, wood, blossoms
or plants), artificial (i.e., a mixture of different nature oils or
oil constituents) and synthetic (i.e., synthetically produced)
odoriferous substances. Such materials are often accompanied by
auxiliary materials, such as fixatives, extenders, stabilizers and
solvents. These auxiliaries are also included within the meaning of
"perfume", as used herein. Typically, perfumes are complex mixtures
of a plurality of organic compounds.
[0333] Examples of perfume ingredients useful in the perfumes of
the present invention compositions include, but are not limited to,
hexyl cinnamic aldehyde; amyl cinnamic aldehyde; amyl salicylate;
hexyl salicylate; terpineol; 3,7-dimethyl-cis-2,6-octadien-1-ol;
2,6-dimethyl-2-octanol; 2,6-dimethyl-7-octen-2-ol;
3,7-dimethyl-3-octanol; 3,7-dimethyl-trans-2,6-octadien-1-ol;
3,7-dimethyl-6-octen-1-ol; 3,7-dimethyl-1-octanol;
2-methyl-3-(para-tert-butylphenyl)-propion-aldehyde;
4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbox-aldehyde;
tri-cyclodecenyl propionate; tricyclodecenyl acetate; anisaldehyde;
2-methyl-2-(para-iso-propylphenyl)-propionaldehyde;
ethyl-3-methyl-3-phenyl glycidate;
4-(parahydroxyphenyl)-butan-2-one;
1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one;
para-methoxyacetophenone; para-methoxy-alpha-phenylpropene;
methyl-2-n-hexyl-3-oxo-cyclopentane carboxylate; undecalactone
gamma. Additional examples of fragrance materials include, but are
not limited to, orange oil; lemon oil; grapefruit oil; bergamot
oil; clove oil; dodecalactone gamma;
methyl-2-(2-pentyl-3-oxo-cyclopentyl) acetate; beta-naphthol
methylether; methyl-beta-naphthylketone; coumarin; decylaldehyde;
benzaldehyde; 4-tert-butylcyclohexyl acetate;
alpha,alpha-dimethylphenethyl acetate; methylphenylcarbinyl
acetate; Schiff's base of
4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde and
methyl anthranilate; cyclic ethyleneglycol diester of tridecandioic
acid; 3,7-dimethyl-2,6-octadiene-1-nitrile; ionone gamma methyl;
ionone alpha; ionone beta; petitgrain; methyl cedrylone;
7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl-naphthalene;
ionone methyl; methyl-1,6,10-trimethyl-2,5,9-cyclododecatrien-1-yl
ketone; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin;
4-acetyl-6-tert-butyl-1,1-dimethyl indane; benzophenone;
6-acetyl-1,1,2,3,3,5-hexamethyl indane;
5-acetyl-3-isopropyl-1,1,2,6-tetramethyl indane; 1-dodecanal;
7-hydroxy-3,7-dimethyl octanal; 10-undecen-1-al; iso-hexenyl
cyclohexyl carboxaldehyde; formyl tricyclodecan;
cyclopentadecanolide; 16-hydroxy-9-hexadecenoic acid lactone;
1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyran-
e; ambroxane; dodecahydro-3a,6,6,9a-tetramethylnaphtho-[2,1b]furan;
cedrol; 5-(2,2,3-trimethylcyclopent-3-enyl)-3-methylpentan-2-ol;
2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol;
caryophyllene alcohol; cedryl acetate; para-tert-butylcyclohexyl
acetate; patchouli; olibanum resinoid; labdanum; vetivert; copaiba
balsam; fir balsam; and condensation products of:
hydroxycitronellal and methyl anthranilate; hydroxycitronellal and
indol; phenyl acetaldehyde and indol; 4-(4-hydroxy-4-methyl
pentyl)-3-cyclohexene-1-carboxaldehyde and methyl anthranilate.
[0334] More examples of perfume components are geraniol; geranyl
acetate; linalool; linalyl acetate; tetrahydrolinalool;
citronellol; citronellyl acetate; dihydromyrcenol; dihydromyrcenyl
acetate; tetrahydromyrcenol; terpinyl acetate; nopol; nopyl
acetate; 2-phenylethanol; 2-phenylethyl acetate; benzyl alcohol;
benzyl acetate; benzyl salicylate; benzyl benzoate; styrallyl
acetate; dimethylbenzylcarbinol; trichloromethylphenylcarbinyl
methylphenylcarbinyl acetate; isononyl acetate; vetiveryl acetate;
vetiverol; 2-methyl-3-(p-tert-butylphenyl)-propanal;
2-methyl-3-(p-isopropylphenyl)-propanal;
3-(p-tert-butylphenyl)-propanal;
4-(4-methyl-3-pentenyl)-3-cyclohexenecarbaldehyde;
4-acetoxy-3-pentyltetrahydropyran; methyl dihydrojasmonate;
2-n-heptylcyclopentanone; 3-methyl-2-pentyl-cyclopentanone;
n-decanal; n-dodecanal; 9-decenol-1; phenoxyethyl isobutyrate;
phenylacetaldehyde dimethylacetal; phenylacetaldehyde
diethylacetal; geranonitrile; citronellonitrile; cedryl acetal;
3-isocamphylcyclohexanol; cedryl methylether; isolongifolanone;
aubepine nitrile; aubepine; heliotropine; eugenol; vanillin;
diphenyl oxide; hydroxycitronellal ionones; methyl ionones;
isomethyl ionomes; irones; cis-3-hexenol and esters thereof; indane
musk fragrances; tetralin musk fragrances; isochroman musk
fragrances; macrocyclic ketones; macrolactone musk fragrances;
ethylene brassylate.
[0335] The perfumes useful in the present invention compositions
are substantially free of halogenated materials and nitromusks.
[0336] Suitable solvents, diluents or carriers for perfumes
ingredients mentioned above are for examples, ethanol, isopropanol,
diethylene glycol, monoethyl ether, dipropylene glycol, diethyl
phthalate, triethyl citrate, etc. The amount of such solvents,
diluents or carriers incorporated in the perfumes is preferably
kept to the minimum needed to provide a homogeneous perfume
solution. Perfume can be present at a level of from 0% to 10%,
preferably from 0.1% to 5%, and more preferably from 0.2% to 3%, by
weight of the finished composition. Fabric softener compositions of
the present invention provide improved fabric perfume
deposition.
[0337] (H) Chelating Agents
[0338] The compositions and processes herein can optionally employ
one or more copper and/or nickel chelating agents ("chelators").
Such water-soluble chelating agents can be selected from the group
consisting of amino carboxylates, amino phosphonates,
polyfunctionally-substituted aromatic chelating agents and mixtures
thereof, all as hereinafter defined. The whiteness and/or
brightness of fabrics are substantially improved or restored by
such chelating agents and the stability of the materials in the
compositions are improved. Without intending to be bound by theory,
it is believed that the benefit of these materials is due in part
to their exceptional ability to remove iron and manganese ions from
washing solutions by formation of soluble chelates.
[0339] Amino carboxylates useful as optional chelating agents
include ethylenediaminetetracetates,
N-hydroxyethylethylenediaminetriacetates, nitrilo-triacetates,
ethylenediamine tetraproprionates,
triethylenetetra-aminehexacetates, diethylenetriaminepentaacetates,
and ethanoldiglycines, alkali metal, ammonium, and substituted
ammonium salts therein and mixtures therein.
[0340] Amino phosphonates are also suitable for use as chelating
agents in the compositions of the invention when at least low
levels of total phosphorus are permitted in detergent compositions,
and include ethylenediaminetetrakis (methylenephosphonates) as
DEQUEST. Preferred, these amino phosphonates do not contain alkyl
or alkenyl groups with more than about 6 carbon atoms.
[0341] Polyfunctionally-substituted aromatic chelating agents are
also useful in the compositions herein. See U.S. Pat. No.
3,812,044, issued May 21, 1974, to Connor et al. Preferred
compounds of this type in acid form are dihydroxy-disulfobenzenes
such as 1,2-dihydroxy-3,5-disulfobenzene.
[0342] A preferred biodegradable chelator for use herein is
ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer
as described in U.S. Pat. No. 4,704,233, November 3, 1987, to
Hartman and Perkins.
[0343] The compositions herein may also contain water-soluble
methyl glycine diacetic acid (MGDA) salts (or acid form) as a
chelant or co-builder useful with, for example, insoluble builders
such as zeolites, layered silicates and the like.
[0344] Preferred chelating agents include DETMP, DETPA, NTA, EDDS
and mixtures thereof.
[0345] If utilized, these chelating agents will generally comprise
from about 0.1% to about 15% by weight of the fabric care
compositions herein. More preferably, if utilized, the chelating
agents will comprise from about 0.1% to about 3.0% by weight of
such compositions.
[0346] (I) Crystal Growth Inhibitor Component
[0347] The compositions of the present invention can further
contain a crystal growth inhibitor component, preferably an
organodiphosphonic acid component, incorporated preferably at a
level of from 0.01% to 5%, more preferably from 0.1% to 2% by
weight of the compositions.
[0348] By organo diphosphonic acid it is meant herein an organo
diphosphonic acid which does not contain nitrogen as part of its
chemical structure. This definition therefore excludes the organo
aminophosphonates, which however may be included in compositions of
the invention as heavy metal ion sequestrant components.
[0349] The organo diphosphonic acid is preferably a C.sub.1-C.sub.4
diphosphonic acid, more preferably a C.sub.2 diphosphonic acid,
such as ethylene diphosphonic acid, or most preferably ethane
1-hydroxy-1,1-diphosphonic acid (HEDP) and may be present in
partially or fully ionized form, particularly as a salt or
complex.
[0350] Still useful herein as crystal growth inhibitor is the
organic monophosphonic acid. Organo monophosphonic acid or one of
its salts or complexes is also suitable for use herein as a
CGI.
[0351] By organo monophosphonic acid it is meant herein an organo
monophosphonic acid which does not contain nitrogen as part of its
chemical structure. This definition therefore excludes the organo
aminophosphonates, which however may be included in compositions of
the invention as heavy metal ion sequestrants.
[0352] The organo monophosphonic acid component may be present in
its acid form or in the form of one of its salts or complexes with
a suitable counter cation. Preferably any salts/complexes are water
soluble, with the alkali metal and alkaline earth metal
salts/complexes being especially preferred.
[0353] A prefered organo monophosphonic acid is
2-phosphonobutane-1,2,4-tricarboxylic acid commercially available
from Bayer under the tradename of Bayhibit.
[0354] (J)-Enzyme
[0355] The compositions and processes herein can optionally employ
one or more enzymes such as lipases, proteases, cellulase, amylases
and peroxidases. A preferred enzyme for use herein is a cellulase
enzyme. Indeed, this type of enzyme will further provide a color
care benefit to the treated fabric. Cellulases usable herein
include both bacterial and fungal types, preferably having a pH
optimum between 5 and 9.5. U.S. Pat. No. 4,435,307 discloses
suitable fungal cellulases from Humicola insolens or Humicola
strain DSM1800 or a cellulase 212-producing fungus belonging to the
genus Aeromonas, and cellulase extracted from the hepatopancreas of
a marine mollusk, Dolabella Auricula Solander. Suitable cellulases
are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and
DE-OS-2.247.832. CAREZYME.RTM. and CELLUZYME.RTM. (Novo) are
especially useful. Other suitable cellulases are also disclosed in
WO 91/17243 to Novo, WO 96/34092, WO 96/34945 and EP-A-0,739,982.
In practical terms for current commercial preparations, typical
amounts are up to 5 mg by weight, more typically 0.01 mg to 3 mg,
of active enzyme per gram of the detergent composition. Stated
otherwise, the compositions herein will typically comprise from
0.001% to 5%, preferably 0.01%-1% by weight of a commercial enzyme
preparation. In the particular cases where activity of the enzyme
preparation can be defined otherwise such as with cellulases,
corresponding activity units are preferred (e.g. CEVU or cellulase
Equivalent Viscosity Units). For instance, the compositions of the
present invention can contain cellulase enzymes at a level
equivalent to an activity from 0.5 to 1000 CEVU/gram of
composition. Cellulase enzyme preparations used for the purpose of
formulating the compositions of this invention typically have an
activity comprised between 1,000 and 10,000 CEVU/gram in liquid
form, around 1,000 CEVU/gram in solid form.
[0356] (K) Liquid Carrier
[0357] Another optional, but preferred, ingredient is a liquid
carrier. The liquid carrier employed in the instant compositions is
preferably at least primarily water due to its low cost, relative
availability, safety, and environmental compatibility. The level of
water in the liquid carrier is preferably at least 50%, most
preferably at least 60%, by weight of the carrier. Mixtures of
water and low molecular weight, e.g., <200, organic solvent,
e.g., lower alcohols such as ethanol, propanol, isopropanol or
butanol are useful as the carrier liquid. Low molecular weight
alcohols include monohydric, dihydric (glycol, etc.) trihydric
(glycerol, etc.), and higher polyhydric (polyols) alcohols.
[0358] (L) Other Optional Ingredients
[0359] The present invention can include optional components
conventionally used in textile treatment compositions, for example:
colorants; preservatives; surfactants; anti-shrinkage agents;
fabric crisping agents; spotting agents; germicides; fungicides;
anti-oxidants such as butylated hydroxy toluene, anti-corrosion
agents, enzyme stabilisers, materials effective for inhibiting the
transfer of dyes from one fabric to another during the cleaning
process (i.e., dye transfer inhibiting agents), hydrotropes,
processing aids, dyes or pigments, and the like.
[0360] The present invention can also include other compatible
ingredients, including those as disclosed in WO96/02625,
WO96/21714, and WO96/21715.
Form of the Composition
[0361] The composition of the invention may take a variety of
physical form including liquid, gel, foam in either aqueous or
non-aqueous form, granular and tablet forms.
[0362] When in a liquid form, the composition may also be dispensed
by a dispensing means such as a spray dispenser, or aerosol
dispenser.
Spray Dispenser
[0363] The present invention also relates to such compositions
incorporated into a spray dispenser to create an article of
manufacture that can facilitate treatment of fabric articles and/or
surfaces with said compositions containing the amine reaction
product and other ingredients (examples are cyclodextrins,
polysaccharides, polymers, surfactant, perfume, softener) at a
level that is effective, yet is not discernible when dried on the
surfaces. The spray dispenser comprises manually activated and
non-manual powered (operated) spray means and a container
containing the treating composition. Typical disclosure of such
spray dispenser can be found in WO 96/04940 page 19 line 21 to page
22 line 27. The articles of manufacture preferably are in
association with instructions for use to ensure that the consumer
applies sufficient ingredient of the composition to provide the
desired benefit. Typical compositions to be dispensed from a
sprayer contain a level of amine reaction product of from about
0.01% to about 5%, preferably from about 0.05% to about 2%, more
preferably from about 0.1% to about 1%, by weight of the usage
composition.
Method of Use
[0364] Also provided herein is a method for providing a delayed
release of an active ketone or aldehyde which comprises the step of
contacting the surface to be treated with a compound or composition
of the invention, and thereafter subjecting the treated surface
with a material, preferably an aqueous medium like moisture or any
other means susceptible of releasing the active from the amine
reaction product.
[0365] By "surface", it is meant any surface onto which the
compound can deposit. Typical examples of such material are
fabrics, hard surfaces such as dishware, floors, bathrooms, toilet,
kitchen, skin, and other surfaces in need of a delayed release of
an active ketone or aldehyde such as that with litter like animal
litter. Preferably, the surface is a fabric.
[0366] By "delayed release" is meant release of the active
component (e.g perfume) over a longer period of time than by the
use of the active (e.g., perfume) itself.
Abbreviations Used in the Following Invention Composition
Examples
[0367] In the composition examples, the abbreviated component
identifications have the following meanings: [0368] DEQA:
Di-(tallowyl-oxy-ethyl) dimethyl ammonium chloride [0369] DTDMAC:
Ditallow dimethylammonium chloride [0370] DEQA (2):
Di-(soft-tallowyloxyethyl) hydroxyethyl methyl ammonium
methylsulfate. [0371] DTDMAMS: Ditallow dimethyl ammonium
methylsulfate. [0372] SDASA: 1:2 ratio of stearyldimethyl
amine:triple-pressed stearic acid. [0373] Fatty acid: Stearic acid
of IV=0 [0374] Electrolyte: Calcium chloride [0375] PEG:
Polyethylene Glycol 4000 [0376] Neodol 45-13: C14-C15 linear
primary alcohol ethoxylate, sold by Shell Chemical CO. [0377]
Cellulase: Cellulytic enzyme sold under the tradename Carezyme,
Celluzyme and/or Endolase by Novo Nordisk A/S. [0378] Silicone
antifoam: Polydimethylsiloxane foam controller with
siloxane-oxyalkylene copolymer as dispersing agent with a ratio of
said foam controller to said dispersing agent of 10:1 to 100:1.
[0379] PEI: Polyethyleneimine with an average molecular weight of
1800 and an average ethoxylation degree of 7 etholeneoxy residues
per nitrogen [0380] HEDP: 1,1-hydroxyethane diphosphonic acid
[0381] ARP1: Amine reaction product of ethyl 4-aminobenzoate with
2,4-dimethyl-3-cyclohexen-1-carboxaldehyde as made from Synthesis
example I [0382] ARP2: Amine reaction product of aminobenzoic acid
with 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde made according to
Synthesis example I [0383] ARP3: Amine reaction product of Lupasol
P with .alpha.-Damascone as made from Synthesis example III [0384]
ARP4: Amine reaction product of D-glucamine with Citronellal as
made from Synthesis example II [0385] ARP5: Amine reaction product
of LupasolHF with .delta.-Damascone as made from Synthesis example
III [0386] Polymer: Polyvinylpyrrolidone K90 available from BASF
under the tradename Luviskol K90 [0387] Dye fixative: Dye fixative
commercially available from Clariant under the tradename Cartafix
CB [0388] Polyamine: 1,4-Bis-(3-aminopropyl)piperazine [0389]
Bayhibit AM: 2-Phosphonobutane-1,2,4-tricarboxylic acid
commercially available from Bayer [0390] Fabric softener active:
Di-(canoloyl-oxy-ethyl)hydroxyethyl methyl ammonium methylsulfate
[0391] HPBDC: Hydroxypropyl beta-cyclodextrin [0392] RAMEB:
Randomly methylated beta-cyclodextrin [0393] Bardac 2050: Dioctyl
dimethyl ammonium chloride, 50% solution [0394] Bardac 22250:
Didecyl dimethyl ammonium chloride, 50% solution [0395] Genamin
C100: Coco fatty amine ethoxylated with 10 moles ethylene oxide and
commercially available from Clariant [0396] Genapol V4463: Coco
alcohol ethoxylated with 10 moles ethylene oxide and commercially
available from Clariant [0397] Silwet 7604: Polyalkyleneoxide
polysiloxanes of MW 4000 of formula
R--(CH.sub.3).sub.2SiO--[(CH.sub.3).sub.2SiO].sub.a--[(CH.sub.3)(R)SiO].s-
ub.b--Si(CH.sub.3).sub.2--R, wherein average a+b is 21, and
commercially available from Osi Specialties, Inc., Danbury, Conn.
[0398] Silwet 7600: Polyalkyleneoxide polysiloxanes of MW 4000, of
formula
R--(CH.sub.3).sub.2SiO--[(CH.sub.3).sub.2SiO].sub.a--[(CH.sub.3)(R)SiO].s-
ub.b--Si(CH.sub.3).sub.2--R, wherein average a+b is 11, and
commercially available from Osi Specialties, Inc., Danbury,
Conn.
[0399] The following are synthesis examples of compounds according
to the invention:
I-Synthesis of Ethyl 4-Aminobenzoate with
2,4-Dimethyl-3-Cyclohexen-1-Carboxaldehyde
[0400] To an ice cooled stirred solution of 10 g of
2,4-dimethyl-3-cyclohexen-1-carboxaldehyde (0.07 mol) in 35 mL EtOH
and molecular sieves (4 .ANG., 20 g) 1 eq of the amine was added
via an addition funnel. The reaction mixture was stirred under
nitrogen atmosphere and protected from light. After 6 days the
mixture was filtrated and the solvent was removed. The yield of
imine formation is about 90%.
[0401] Similar results were obtained where the
2,4-dimethyl-3-cyclohexen-1-carboxaldehyde was replaced by
bourgeonal, or trans-2-nonenal. Additionally, similar results were
obtained where the ethyl-4-aminobenzoate was replaced by 4-amino
benzoic acid.
II-Synthesis of D-Glucamine with
2,4-Dimethyl-3-Cyclohexen-1-Carboxaldehyde
[0402] To an ice cooled solution of 1 mmol D-glucamine in about 30
mL EtOH and molecular sieves (4 .ANG., 5 g) 1 eq of the
2,4-dimethyl-3-cyclohexen-1-carboxaldehyde was added. The reaction
was stirred under nitrogen atmosphere and protected from light.
After 3 to 4 days, the molecular sieves and the solvent were
removed by filtration and evaporation respectively. The solid imine
was obtained in 85 to 90% yield.
[0403] Similar results were obtained where the
2,4-dimethyl-3-cyclohexen-1-carboxaldehyde was replaced by
citronellal, trans-2-nonenal, or decanal.
III-Synthesis of Lupasol with Damascone
[0404] The .beta.-amino ketone from Lupasol G100 (commercial
available by BASF content 50% water, 50% Lupasol G100 (Mw. 5000))
and .alpha.-Damascone was prepared using any one of these three
different procedures described as follows: [0405] 1. Commercially
available Lupasol G100 was dried using the following procedure: 20
g of the Lupasol solution was dried at the rotating evaporator
during several hours. The obtained residue, still containing about
4.5 g of H.sub.2O, was azeotropically distilled at the rotating
evaporator using toluene. The residue was then placed in the
desiccator dried at 60.degree. C. (using P.sub.2O.sub.5 as water
absorbing material). On basis of the obtained weight we concluded
that the oil contained less then 10% H.sub.2O. On basis of the
NMR-spectra we concluded that this is probably less then 5%. This
dried sample was then used in the preparation of .beta.-amino
ketones.
[0406] 1.38 g of the dried Lupasol G100 was dissolved in 7 ml.
ethanol. The solution was stirred gently with a magnetic stirrer
during a few minutes before 2 g Na.sub.2SO.sub.4 (anhydrous) was
added. After stirring again for a few minutes 2.21 g
.alpha.-Damascone was added over a period of 1 minute. After two
days reaction, the mixture was filtrated over a Celite filter (vide
supra), and the residue washed thoroughly with ethanol. About 180
ml. of a light foaming filtrate was obtained. This was concentrated
until dryness using a rotating evaporator and dried over
P.sub.2O.sub.5 in an desiccator at room temperature. About 3.5 of a
colorless oil was obtained. [0407] 2. 4.3 g Lupasol G100 solution
was (without drying) dissolved in 10 ml. ethanol. The solution was
stirred with a magnetic stirrer during a few minutes before 3.47 g
.alpha.-Damascone was added over a 1.5 minutes period. After two
days reaction at room temperature the reaction mixture was
filtrated over Celite (vide supra) and the residue washed
thoroughly with ethanol. The filtrate (200 ml., light foaming) was
concentrated at the evaporator and dried in an desiccator
(P.sub.2O.sub.5 as drying agent) at room temperature. About 6.0 g
of a colorless oil was obtained. [0408] 3. To about 3.0 g of
Lupasol G100 solution (used as such) was added 2.41 g
a.alpha.-Damascone. The mixture was stirred without using solvent.
After stirring for 4 days the obtained oil was dissolved in 100 ml.
THF, dried with MgSO.sub.4, filtrated and the filtrate concentrated
at the rotating evaporator. After drying in the exsiccator
(P.sub.2O.sub.5) at room temperature, about 4.1 g of a colorless
oil was obtained. This oil still contained about 13% (w/w) of THF,
even after a prolonged drying (3 days).
[0409] The product obtained from the three procedures had identical
NMR-spectra.
[0410] The .beta.-amino ketone from Lupasol P and .alpha.-Damascone
was prepared using the procedure described as follows:
[0411] About 1.8 g Lupasol P solution (50% H.sub.2O, 50% Lupasol
Mw. 750000, as obtained from BASF) was dissolved in 7 ml ethanol,
the solution was stirred for a few minutes with a magnetic stirrer
before 1.44 g .alpha.-Damascone was added. After three days the
reaction mixture was filtrated over a celite filter (vide supra)
and the residue washed thoroughly with ethanol. After concentrating
of the filtrate and drying of the obtained oil in the desiccator
(P.sub.2O.sub.5) at room temperature, about 3 g of the reaction
product between Lupasol and .alpha.-Damascone was obtained.
[0412] In the following formulation examples all levels are quoted
as % by weight of the composition unless otherwise stated, and
incorporation of the amine reaction product so called herein after
"ARP" in the fully formulated composition is carried out by dry
addition (d), encapsulation in starch (es) as described in
GB-1,464,616 or cyclodextrin (ec) or as is in the composition as
defined herein before. The term in bracket for the ARP in the
formulation examples refers to the means of incorporation. When
none is provided, the incorporation is made as it is. The levels
given for the ARP, whether processed or not, refer to the level of
ARP as is and not to the processed ARP.
EXAMPLE 1
[0413] The following fabric softening compositions are in
accordance with the present invention TABLE-US-00004 Component A B
C D E F G H DTDMAC -- -- -- -- -- 4.5 15.0 15.0 DEQA 2.6 2.9 18.0
18.0 19.0 -- -- -- Fatty acid 0.3 -- 1.0 1.0 -- -- -- -- HCl 0.02
0.02 0.02 0.02 0.02 0.02 0.02 0.02 PEG -- -- 0.6 0.6 0.6 -- 0.6 0.6
Perfume 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Silicone 0.01 0.01 0.01
0.01 0.01 0.01 0.01 0.01 antifoam ARP 5 0.3 -- 0.2 0.2 -- -- -- 0.2
ARP 3 -- 0.05 -- -- 0.2 -- 0.4 0.4 ARP 4 -- -- -- 0.02 -- 0.05 --
-- Electrolyte -- -- 600 600 1200 -- 1200 1200 (ppm) Dye (ppm) 10
10 50 50 50 10 50 50 Water and minors to balance to 100%
EXAMPLE 2
[0414] The following rinse added fabric softener composition was
prepared according to the present invention: TABLE-US-00005 A B C D
E DEQA (2) 20.0 20.0 20.0 20.0 20.0 ARP 1 0.5 -- -- -- -- ARP 2 --
0.3 -- 0.04 ARP 3 -- 0.1 0.1 -- -- ARP 4 -- -- -- 0.1 0.1 Cellulase
0.001 0.001 0.001 0.001 0.001 HCL 0.03 0.03 0.03 0.03 0.03 Silicon
Antifoam 0.01 0.01 0.01 0.01 0.01 Blue dye 25 ppm 25 ppm 25 ppm 25
ppm 25 ppm Electrolyte 0.20 0.20 0.20 0.20 0.20 Perfume 0.90 0.90
0.90 0.90 0.90 Miscellaneous Up to 100% and water
EXAMPLE 3
[0415] The following rinse added fabric softener composition was
prepared according to the present invention: TABLE-US-00006 A B C D
E F G H DEQA 2.6 2.6 2.6 2.6 19.0 19.0 19.0 19.0 Fatty acid 0.3 0.3
0.3 0.3 -- -- -- -- Hydrochloride 0.02 0.02 0.02 0.02 0.02 0.02
0.02 0.02 acid ARP 1 0.02 -- -- -- -- 0.1 0.23 0.2 ARP 5 -- 0.2 0.2
-- -- -- -- 0.1 ARP 3 -- -- 0.2 0.05 0.3 0.2 -- 0.2 Perfume 1.0 1.0
1.0 1.0 1.0 1.0 1.0 1.0 PEI -- 0.5 0.3 0.3 -- 2.0 1.5 1.5 HEDP --
-- 0.05 0.05 -- -- 0.3 0.3 Silicone 0.01 0.01 0.01 0.01 0.01 0.01
0.01 0.01 antifoam Electrolyte -- -- -- -- 0.1 0.1 0.1 0.1 Dye 10
10 10 10 25 25 25 25 ppm ppm ppm ppm ppm ppm ppm ppm Water and 100%
100% 100% 100% 100% 100% 100% 100% minors
EXAMPLE 4
[0416] The following dryer added fabric conditioner compositions
were prepared according to the present invention: TABLE-US-00007 A
B C D E F G DEQA(2) -- -- -- -- 51.8 51.8 51.8 DTMAMS -- -- 26.0
26.0 -- -- -- SDASA 70.0 70.0 42.0 42.0 40.2 40.2 40.2 Neodol 45-13
13.0 13.0 -- -- -- -- -- Ethanol 1.0 1.0 -- -- -- -- -- ARP 1(es)
0.1 -- -- 0.1 0.2 -- -- ARP 2(ec) -- 0.1 -- -- -- -- -- ARP 3(es)
-- -- 0.05 -- -- 0.2 -- ARP 5(d) -- -- -- -- -- -- 0.3 Perfume 0.75
0.75 1.0 1.0 1.5 1.5 1.5 Glycoperse S-20 -- -- -- -- 15.4 15.4 15.4
Glycerol -- -- 26.0 26.0 -- -- -- monostearate Digeranyl Succinate
0.38 0.38 -- -- -- -- -- Clay -- -- 3.0 3.0 -- -- -- Dye 0.01 0.01
-- -- -- -- --
EXAMPLE 5
[0417] The following are non-limiting examples of pre-soak fabric
conditioning and/or fabric enhancement compositions according to
the present invention which can be suitably used in the laundry
rinse cycle: TABLE-US-00008 Ingredients A B C D E F Polymer 3.5 3.5
3.5 3.5 3.5 3.5 Dye fixative 2.3 2.3 2.4 2.4 2.5 2.5 Polyamine 15.0
15.0 17.5 17.5 20.0 20.0 Bayhibit AM 1.0 1.0 1.0 1.0 1.0 1.0
C.sub.12-C.sub.14 -- 5.0 5.0 -- -- -- dimethyl hydroxyethyl
quaternary ammonium chloride Fabric -- -- 2.5 2.5 -- -- softener
active Genamin 0.33 -- 0.33 0.33 0.33 -- C100 Genapol 0.2 -- 0.2
0.2 0.2 -- V4463 ARP1 1.0 2.0 0.1 0.5 0.05 0.08 Water & balance
balance balance balance balance balance minors
EXAMPLE 6
[0418] The following are non-limiting examples of odor-absorbing
compositions suitable for spray-on applications: TABLE-US-00009
Examples A B C D E Ingredients Wt. % Wt. % Wt. % Wt. % Wt. % HPBCD
1.0 -- 1.0 -- 1.2 RAMEB -- 1.0 -- 0.8 -- Tetronic -- -- 0.1 -- --
901 Silwet -- -- -- 0.1 -- L-7604 Silwet 0.1 -- -- -- 0.1 L-7600
Bardac -- -- -- 0.03 -- 2050 Bardac -- 0.2 -- -- 0.1 2250
Diethylene -- 1.0 -- -- 0.2 glycol Triethylene -- -- 0.1 -- --
glycol Ethanol -- -- -- -- 2.5 Perfume 1 0.1 -- -- -- -- Perfume 2
-- 0.05 -- 0.1 -- Perfume 3 -- -- 0.1 -- 0.1 Kathon 3 ppm 3 ppm 3
ppm 3 ppm -- HCl to pH 4.5 to pH 4.5 to pH 3.5 to pH 3.5 to pH 3.5
ARP1 5.0 1.0 -- -- -- ARP3 -- -- 0.5 0.1 0.08 Distilled Bal. Bal.
Bal. Bal. Bal. water
[0419] The perfume 1, 2, and 3 have the following compositions:
TABLE-US-00010 Perfume 1 2 3 Perfume Ingredients Wt. % Wt. % Wt. %
Anisic aldehyde -- -- 2 Benzophenone 3 5 -- Benzyl acetate 10 15 5
Benzyl salicylate 5 20 5 Cedrol 2 -- -- Citronellol 10 -- 5
Coumarin -- -- 5 Cymal -- -- 3 Dihydromyrcenol 10 -- 5 Flor acetate
5 -- 5 Galaxolide 10 -- -- Lilial 10 15 20 Linalyl acetate 4 -- 5
Linalool 6 15 5 Methyl dihydro jasmonate 3 10 5 Phenyl ethyl
acetate 2 5 1 Phenyl ethyl alcohol 15 15 20 alpha-Terpineol 5 -- 8
Vanillin -- -- 1 Total 100 100 100
* * * * *