U.S. patent application number 12/280114 was filed with the patent office on 2009-01-22 for surfactant mixture containing short-chain and also long-chain components.
This patent application is currently assigned to BASF SE. Invention is credited to Richard Baur, James S. Dailey, Sridhar G. Iyer, Christoffer Kieburg, Ernst Lippert, Ulrich Steinbrenner, Jurgen Tropsch, Soeren Zimdahl.
Application Number | 20090023820 12/280114 |
Document ID | / |
Family ID | 38002640 |
Filed Date | 2009-01-22 |
United States Patent
Application |
20090023820 |
Kind Code |
A1 |
Dailey; James S. ; et
al. |
January 22, 2009 |
SURFACTANT MIXTURE CONTAINING SHORT-CHAIN AND ALSO LONG-CHAIN
COMPONENTS
Abstract
The present invention relates to a surfactant mixture comprising
(A) a short-chain component comprising the alkoxylation product of
alkanols, where the alkanols have 8 to 12 carbon atoms and the
average number of alkoxy groups per alkanol group in the
alkoxylation product assumes a value from 3 to 30 and the alkoxy
groups are chosen from the group consisting of ethoxy, propoxy,
butoxy and pentoxy groups and the alkanols have an average degree
of branching of at least 1; and (B) a long-chain component
comprising the alkoxylation product of alkanols where the alkanols
have 13 to 20 carbon atoms and the average number of alkoxy groups
per alkanol group in the alkoxylation product assumes a value from
3 to 30 and the alkoxy groups are chosen from the group consisting
of ethoxy, propoxy, butoxy and pentoxy groups and the alkanols have
an average degree of branching of from 0.0 to 0.3; and phosphate
esters, sulfate esters and ether carboxylates thereof. In addition,
the present invention relates to a formulation comprising such
surfactant mixtures, and to the use of these, for example for the
cleaning of hard surfaces.
Inventors: |
Dailey; James S.; (Grosse
Ile, MI) ; Lippert; Ernst; (Oak Ridge, NJ) ;
Iyer; Sridhar G.; (Matthews, NC) ; Steinbrenner;
Ulrich; (Neustadt, DE) ; Kieburg; Christoffer;
(Maxdorf, DE) ; Tropsch; Jurgen; (Romerberg,
DE) ; Baur; Richard; (Mutterstadt, DE) ;
Zimdahl; Soeren; (Schriesheim, DE) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
BASF SE
LUDWIGSHAFEN
DE
|
Family ID: |
38002640 |
Appl. No.: |
12/280114 |
Filed: |
February 15, 2007 |
PCT Filed: |
February 15, 2007 |
PCT NO: |
PCT/EP2007/051463 |
371 Date: |
August 20, 2008 |
Current U.S.
Class: |
516/204 |
Current CPC
Class: |
C11D 1/37 20130101; D06M
15/53 20130101; A01N 25/30 20130101; C11D 1/8255 20130101; C11D
1/345 20130101; C11D 1/8305 20130101; C11D 3/0026 20130101; D06M
13/17 20130101; C11D 1/72 20130101; C11D 1/29 20130101 |
Class at
Publication: |
516/204 |
International
Class: |
B01F 17/38 20060101
B01F017/38 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 22, 2006 |
EP |
06110269.5 |
Claims
1. A surfactant mixture comprising (A) a short-chain component
comprising the alkoxylation product of alkanols, where the alkanols
have 8 to 12 carbon atoms and the average number of alkoxy groups
per alkanol group in the alkoxylation product assumes a value from
3 to 30 and the alkoxy groups are chosen from the group consisting
of ethoxy, propoxy, butoxy and pentoxy groups and the alkanols have
an average degree of branching of at least 1; and (B) a long-chain
component comprising the alkoxylation product of alkanols where the
alkanols have 13 to 20 carbon atoms and the average number of
alkoxy groups per alkanol group in the alkoxylation product assumes
a value from 3 to 30 and the alkoxy groups are chosen from the
group consisting of ethoxy, propoxy, butoxy and pentoxy groups and
the alkanols have an average degree of branching of from 0.0 to
0.3; and phosphate, sulfate esters and ether carboxylates
thereof.
2. The surfactant mixture according to claim 1, wherein for the
short-chain component (A) and/or the long-chain component (B), the
fraction of ethoxy groups relative to the total number of alkoxy
groups for the particular alkoxylation product is at least 0.5.
3. The surfactant mixture according to one of claims 1 to 2,
wherein the at least one alkanol of the long-chain component (B)
has 16 to 20 carbon atoms.
4. The surfactant mixture according to one of claims 1 to 3,
wherein the at least one alkanol of the short-chain component (A)
has an average degree of branching of from 1.0 to 2.0.
5. The surfactant mixture according to one of claims 1 to 4,
wherein the ratio of the weight fraction of the short-chain
component (A) in the surfactant mixture to the weight fraction of
the long-chain component (B) in the surfactant mixture assumes a
value in the range from 99:1 to 1:99.
6. The surfactant mixture according to one of claims 1 to 5, which
has a HLB value according to Griffin in the range from 10 to
15.
7. A formulation comprising a surfactant mixture according to one
of claims 1 to 6.
8. A method of producing a surfactant mixture according to one of
claims 1 to 6, comprising the steps: (a) alkoxylation of an alkanol
mixture, where the alkanol mixture has 8 to 12 carbon atoms and the
average number of alkoxy groups per alkanol group in the
alkoxylation product assumes a value from 3 to 30 and the alkoxy
groups are chosen from the group consisting of ethoxy, propoxy,
butoxy and pentoxy groups and the alkanol mixture has an average
degree of branching of at least 1; (b) alkoxylation of an alkanol
mixture, where the alkanol mixture has 13 to 20 carbon atoms and
the average number of alkoxy groups per alkanol group in the
alkoxylation product assumes a value from 3 to 30 and the alkoxy
groups are chosen from the group consisting of ethoxy, propoxy,
butoxy and pentoxy groups and the alkanol mixture has an average
degree of branching of from 0.0 to 0.3; and (c) mixing the
alkoxylation products obtained in step (a) and (b).
9. A method of producing a surfactant mixture according to one of
claims 1 to 6, comprising the steps (a) mixing a first alkanol
mixture which has 8 to 12 carbon atoms and an average degree of
branching of at least 1 with at least one second alkanol mixture
which has 13 to 20 carbon atoms and an average degree of branching
of from 0.0 to 0.3; and (b) alkoxylation of the mixture of the
first and second mixture, where the number of alkoxy groups per
alkanol group in the alkoxylation product assumes an average value
of from 3 to 30 and the alkoxy groups are chosen from the group
consisting of ethoxy, propoxy, butoxy and pentoxy groups.
10. The use of a surfactant mixture according to one of claims 1 to
6 or of a formulation according to claim 7 as emulsifier, foam
regulator, wetting agent, in particular for hard surfaces,
humectant.
11. The use according to claim 10 in detergents, for the cleaning
of hard surfaces, in cosmetic, pharmaceutical and crop protection
formulations, paints, coating compositions, adhesives,
leather-degreasing compositions, for the textile industry, fiber
processing, metal processing, food industry, water treatment, paper
industry, fermentation or mineral processing and in emulsion
polymerizations.
Description
[0001] The present invention relates to a surfactant mixture, to
formulations comprising such surfactant mixtures, to methods of
producing the surfactant mixtures, and to their use.
[0002] Surfactants are amphiphilic interface-active compounds which
comprise a hydrophobic molecular moiety and also a hydrophilic
molecular moiety and, in addition, can have charged or uncharged
groups. Surfactants are orientedly adsorbed at interfaces and
thereby reduce the interfacial tension so that these can form, in
solution, association colloids above the critical micelle-formation
concentration, meaning that substances which are per se
water-insoluble in aqueous solutions are solubilized.
[0003] On account of these properties, surfactants are used, for
example, for wetting solids such as fibers or hard surfaces. Here,
surfactants are often used in combinations with one another and
with further auxiliaries. Typical fields of application are
detergents and cleaners for textiles and leather, as formulation of
paints and coatings and, for example, in the recovery of
petroleum.
[0004] Interesting surfactants are in particular those which
represent alkoxylation products of alcohols. Here, it has been
shown that it is particularly favorable to provide such compounds
in various mixtures.
[0005] JP-A 2004/091686 describes the mixture of surfactants, where
an alkoxylated branched aliphatic alcohol having 8 to 11 carbon
atoms is mixed with a further aliphatic alcohol having 12 to 20
carbon atoms, which is likewise alkoxylated.
[0006] JP-A 2003/336092 likewise describes polyalkoxylene alkyl
ethers which have to satisfy certain conditions.
[0007] JP-A 2004/035755 describes a nonionic surface-active
composition which has alkyleneoxy adducts of an aliphatic alcohol
with a HLB value of from 6 to 14.5, and of an aliphatic alcohol
with a HLB value of from 11 to 16.
[0008] WO-A 94/11330 describes alkoxylates of 2-propylheptanol and
their use for cleaning textile materials.
[0009] The same alkoxylates are described in WO-A 94/11331 for
degreasing hard surfaces.
[0010] Finally, DE-A 19921330 describes the use of branched fatty
alcohol ethoxylates having 8 to 22 carbon atoms which can be used
as wool detergents.
[0011] Despite numerous surfactants which are described in the
prior art, there continues to be a need for surfactants or
surfactant mixtures which have, at least in part, better properties
than those from the prior art. Such properties refer in particular
to their wetting behavior, salt tolerance, foam formation, low
tendency to form gels, their washing performance and their emulsion
stability.
[0012] An object of the present invention is therefore to provide a
surfactant mixture which, at least in relation to one of the
properties listed above, has behavior which is superior to
surfactants of the prior art.
[0013] The object is achieved by a surfactant mixture comprising
[0014] (A) a short-chain component comprising the alkoxylation
product of alkanols, where the alkanols have 8 to 12 carbon atoms
and the average number of alkoxy groups per alkanol group in the
alkoxylation product assumes a value from 3 to 30 and the alkoxy
groups are chosen from the group consisting of ethoxy, propoxy,
butoxy and pentoxy groups and the alkanols have an average degree
of branching of at least 1; and [0015] (B) a long-chain component
comprising the alkoxylation product of alkanols where the alkanols
have 13 to 20 carbon atoms and the average number of alkoxy groups
per alkanol group in the alkoxylation product assumes a value from
3 to 30 and the alkoxy groups are chosen from the group consisting
of ethoxy, propoxy, butoxy and pentoxy groups and the alkanols have
an average degree of branching of from 0.0 to 0.3.
[0016] The degree of branching of the alkanols (of the alkanol
mixture) here is defined as follows:
[0017] The degree of branching of an alcohol arises from the
branches of the carbon backbone. For each alcohol molecule, it is
defined as the number of carbon atoms which are bonded to three
further carbon atoms, plus two times the number of carbon atoms
which are bonded to four further carbon atoms. The average degree
of branching of an alcohol mixture arises from the sum of all
degrees of branching of the individual molecules divided by the
number of individual molecules. The degree of branching is
determined, for example, by means of NMR methods. This can be
carried out through analysis of the carbon backbone with suitable
coupling methods (COSY, DEPT, INADEQUATE), followed by a
quantification via .sup.13C NMR with relaxation reagents. However,
other NMR methods or GC-MS methods are also possible.
[0018] The average number of alkoxy groups arises from the sum of
all alkoxy groups of the individual molecules divided by the number
of individual molecules.
[0019] Mainly, it has been found that a surfactant mixture, as
described in more detail above, of short-chain and long-chain
component can have particularly good properties, particularly with
regard to the abovementioned properties.
[0020] The surfactant mixture according to the present invention
comprises a short-chain component (A) which has the alkoxylation
product of branched alkanols, where the alkanols have 8 to 12
carbon atoms. More preferably, the alkanols have 9 to 11 carbon
atoms, it being particularly preferred if the alkanols have 10
carbon atoms.
[0021] The short-chain component (A) of the surfactant mixture
according to the invention can also comprise only one such alkanol,
but typically a mixture of such alkanols.
[0022] If two or more alkanols are used for the short-chain
component (A) if the alkanol has 10 carbon atoms, it is preferred
that this mixture is a C.sub.10 Guerbet alcohol mixture. Here, the
main components are 2-propylheptanol and 5-methyl-2-propyl-hexanol.
Preferably, the short-chain component (A) consists of at least 90%,
preferably 95%, of such a mixture.
[0023] In addition, it is preferred that the short-chain component
comprises no isodecanol.
[0024] The degree of alkoxylation of the alkanol(s) for the
short-chain component (A) according to the present invention
assumes, on average, values from 3 to 30 alkoxy groups per
alkanol.
[0025] The alkoxy groups may be ethoxy, propoxy, butoxy and pentoxy
groups. It is possible for the alkoxylation to take place in random
distribution or blockwise, meaning that correspondingly blockwise
groups chosen from ethoxy, propoxy, butoxy and pentoxy groups can
arise.
[0026] However, it is preferred that the alkoxylation product for
the short-chain component (A) has a fraction of ethoxy groups
relative to the total number of alkoxy groups which is at least 0.5
for the particular alkoxylation product. More preferably, this is
at least 0.75 and it is especially preferred if the alkoxylation
product comprises exclusively ethoxy groups as alkoxy groups.
[0027] It is preferred if the alkanol mixture of the short-chain
component (A) has an average degree of branching of from 1.0 to
2.0. More preferably, the alkanol mixture of the short-chain
component (A) has an average degree of branching in the range from
1 to 1.5.
[0028] Besides alkoxylation products of branched alkanols which
form the short-chain component of the surfactant mixture, it is
likewise possible that alkoxylation products of unsaturated
aliphatic alcohols are present, where these can have the same
number of carbon atoms as the alkanols for the short-chain
component (A). However, it is preferred if this group of compounds
has a weight fraction, based on the total weight of the surfactant
mixture, below 10% by weight, preferably less than 5% by
weight.
[0029] In addition, the surfactant mixture can have alkoxylation
products, where alkanols form these products which do not have the
number of carbon atoms stated above. These are in particular
alkanols having 1 to 7 carbon atoms, and alkanols having more than
12 carbon atoms. However, it is preferred if this group of
compounds has a weight fraction of at most 10% by weight,
preferably of less than 5% by weight, based on the total weight of
the surfactant mixture.
[0030] Moreover, alkoxylation products of branched alkanols can
arise which have a lower or higher degree of alkoxylation. Mention
is to be made here in particular of a degree of alkoxylation of 1,
2, and 31 and more alkoxy groups. It is preferred if this group of
compounds has less than 30% by weight, preferably less than 15% by
weight, based on the total weight of the surfactant mixture. Less
than 10% by weight are more preferred, in particular less than 5%
by weight.
[0031] In addition, the surfactant mixture of the present invention
comprises a long-chain component (B) which has the alkoxylation
product of alkanols which have an average degree of branching of
from 0.0 to 0.3 and at least 13 to 20 carbon atoms. Preferably, the
alkanol mixture of the long-chain component (B) has 16 to 20 carbon
atoms and in particular 16 to 18 carbon atoms.
[0032] The long-chain component (B) can also be the alkoxylation
product of a single alkanol, although this typically has two or
more such alkanols.
[0033] If mixtures are used, C.sub.12-14-coconut fatty alcohols,
native alcohols or alkanols obtained from the Ziegler-ALFOL
process, for example, are conceivable. Tallow fatty alcohol can
likewise be used. This tallow fatty alcohol can be produced, for
example, from cotton oil, linseed oil, corn oil, olive oil, peanut
oil, rapeseed oil, rice bran oil, dyer's safflower oil, soybean
oil, sunflower oil or beef fat, pork fat, poultry fat, fish fat.
Preferably, the long-chain component (B) consists of at least 90%
by weight, preferably of at least 95% by weight, of such a
mixture.
[0034] The average degree of alkoxylation of the alkanol mixture
for the long-chain component (B) according to the present invention
assumes values from 3 to 30 alkoxy groups per alkanol.
[0035] The alkoxy groups can be ethoxy, propoxy, butoxy and pentoxy
groups. It is possible for the alkoxylation to take place in random
distribution or blockwise, meaning that correspondingly blockwise
groups chosen from ethoxy, propoxy, butoxy and pentoxy groups can
arise.
[0036] However, it is preferred that the alkoxylation product for
the long-chain component (B) has a fraction of ethoxy groups
relative to the total number of alkoxy groups which is at least 0.5
for the particular alkoxylation product. More preferably, this is
at least 0.75 and it is particularly preferred if the alkoxylation
product comprises exclusively ethoxy groups as alkoxy groups.
[0037] The alkanol mixture of the long-chain component (B) has an
average degree of branching of from 0.0 to 0.3.
[0038] Besides alkoxylation products of such alkanols which form
the long-chain component (B) of the surfactant mixture, it is
likewise possible that alkoxylation products of unsaturated
aliphatic alcohols are present, where these can have the same
number of carbon atoms as the alkanols for the long-chain component
(B). However, it is preferred if this group of compounds has a
weight fraction, based on the total weight of the surfactant
mixture, below 30% by weight, preferably less than 15% by weight.
More preferably, the fraction is less than 10% by weight, in
particular less than 5% by weight.
[0039] In addition, the surfactant mixture can have alkoxylation
products, where alkanols form these products which do not have the
number of carbon atoms stated above. In particular, these are
alkanols having 1 to 12 carbon atoms, and alkanols having more than
20 carbon atoms. However, it is preferred if this group of
compounds has a weight fraction of at most 10% by weight,
preferably at most 5% by weight, based on the total weight of the
surfactant mixture.
[0040] Moreover, alkoxylation products of alkanols with branching
from 0 to 0.3 can arise which have a lower or higher degree of
alkoxylation. Here, mention is to be made in particular of a degree
of alkoxylation of 1, 2, and 31 and more alkoxy groups. It is
preferred if this group of compounds has less than 30% by weight,
preferably less than 15% by weight, based on the total weight of
the surfactant mixture. More preferably, the fraction is below 10%
by weight, in particular below 5% by weight.
[0041] Preferably, the ratio of the weight fraction of the
short-chain component (A) in the surfactant mixture to the weight
fraction of the long-chain component (B) in the surfactant mixture
is a value range from 99:1 to 1:99. More preferably, this range is
97:3 to 30:70, in addition more preferably 95:5 to 50:50 and
especially preferably 90:10 to 70:30.
[0042] The respective fraction of components (A) and (B) based on
the total fraction of the surfactant mixture is preferably in each
case at least 50% by weight, more preferably at least 60% by
weight, further more preferably at least 75% by weight, in addition
more preferably 90% by weight, based on the total weight of the
surfactant mixture.
[0043] Preferably, the HLB value according to Griffin is in the
range from 10 to 15 for the surfactant mixture according to the
present invention.
[0044] The surfactant mixture of the present invention comprises
components (A) and (B) which each comprise at least one
alkoxylation product of alcohols. The surfactant mixture according
to the invention can also still comprise residues of the unreacted
alcohols. However, it is preferred if their fraction is less than
15% by weight, particularly preferably less than 10% by weight,
based on the total weight of the surfactant mixture.
[0045] The alkoxylation products can be used as they are, or their
phosphates, sulfate esters or ether carboxylates (carbonates) are
used. These can be neutral or in the form of a salt. Suitable
counterions are alkali metal and alkaline earth metal cations or
ammonium ions, and also alkyl- and alkanolammonium ions.
[0046] The present invention further relates to a formulation
comprising a surfactant mixture according to the invention.
[0047] The formulation can, for example, comprise 0.01 to 90% by
weight of water. Moreover or alternatively, the formulation can
have further surfactants or hydrotropes or mixtures thereof. For
example, mention may be made here of alcohol alkoxylates of the
formula P(O-R-Ao.sub.n).sub.m-H, where P is a saturated,
unsaturated or aromatic carbon backbone to which m alcohol
functions are joined which have in turn been etherified with, on
average, in each case n alkylene oxide units. n here has a value
from 1 to 4 and m a value from 1 to 10. R is an alkylene group
having 1 to 10 carbon atoms, Ao is a C.sub.2-C.sub.5-alkylene
oxide. Examples thereof are methylethylene glycols, butylethylene
glycols, pentylethylene glycols, hexylethylene glycols,
butylpropylene glycols, trimethylolpropane ethoxylates, glycerol
ethoxylates, pentaerythritol ethoxylates, ethoxylates and
propoxylates of bisphenol A.
[0048] The present invention further relates to a method of
producing a surfactant mixture, comprising the steps: [0049] (a)
alkoxylation of an alkanol mixture, where the mixture has 8 to 12
carbon atoms and the average number of alkoxy groups per alkanol
group in the alkoxylation product assumes a value from 3 to 30 and
the alkoxy groups are chosen from the group consisting of ethoxy,
propoxy, butoxy and pentoxy groups and the alkanol mixture has an
average degree of branching of at least 1, preferably 1.0 to 2,
more preferably 1.0 to 1.5; [0050] (b) alkoxylation of an alkanol
mixture, where the alkanol mixture has 13 to 20 hydrocarbon atoms
and the average number of alkoxy groups per alkanol group in the
alkoxylation product assumes a value from 3 to 30 and the
alkoxylation groups are chosen from the group consisting of ethoxy,
propoxy, butoxy and pentoxy groups and the alkanol mixture has an
average degree of branching of from 0.0 to 0.3; and [0051] (c)
mixing the alkoxylation products obtained in step (a) and (b).
[0052] Besides the method described above for producing a
surfactant mixture, the corresponding alkanols for the short-chain
component (A) and long-chain component (B) can also be mixed before
the alkoxylation and then the mixture can subsequently be subjected
to an alkoxylation.
[0053] Consequently, the present invention further relates to a
method of producing a surfactant mixture according to the present
invention, comprising the steps [0054] (a) mixing a first alkanol
mixture which has 8 to 12 carbon atoms and an average degree of
branching of at least 1 with at least one second alkanol mixture
which has 13 to 20 carbon atoms and an average degree of branching
of from 0.0 to 0.3; and [0055] (b) alkoxylation of the mixture of
the first and second mixture from step (a), where the number of
alkoxy groups per alkanol group in the alkoxylation product assumes
an average value of from 3 to 30 and the alkoxy group is chosen
from the group consisting of ethoxy, propoxy, butoxy and pentoxy
groups.
[0056] The surfactant mixtures or formulations according to the
invention can be used, for example, as surfactant formulations for
cleaning hard surfaces. Suitable surfactant formulations for which
the surfactant mixtures according to the invention can be provided
as additives are described, for example, in Formulating Detergents
and Personal Care Products by Louis Ho Tan Tai, AOCS Press,
2000.
[0057] As further components, they comprise, for example, soap,
anionic surfactants, such as LAS (linear alkyl benzenesulfonate) or
paraffinsulfonates or FAS (fatty alcohol sulfate) or FAES (fatty
alcohol ethersulfate), acid, such as phosphoric acid, amidosulfonic
acid, citric acid, lactic acid, acetic acid, other organic and
inorganic acids, solvents, such as ethylene glycol, isopropanol,
complexing agents, such as EDTA
(N,N,N',N'-ethylenediaminetetraacetic acid), NTA
(N,N,N-nitrilotriacetic acid), MGDA (2-methylglycine-N,N-diacetic
acid), phosphonates, polymers, such as polyacrylates, copolymers
maleic acid-acrylic acid, alkali donors, such as hydroxides,
silicates, carbonates, perfume oils, oxidizing agents, such as
perborates, peracids or trichloroisocyanuric acid, Na or K
dichloroisocyanurates, enzymes; see also Milton J. Rosen, Manilal
Dahanayake, Industrial Utilization of Surfactants, AOCS Press, 2000
and Nikolaus Sch6nfeldt, Grenzflachenaktive Ethylenoxyaddukte
[Interface-active ethyleneoxy adducts]. These also discuss
formulations for the other specified uses in principle. These may
be household cleaners, such as all-purpose cleaners, dishwashing
detergents for manual and automatic dishwashing, metal degreasing,
industrial applications, such as cleaners for the food industry,
bottlewashing, etc. They may also be printing roll and printing
plate cleaners in the printing industry. Suitable further
ingredients are known to the person skilled in the art.
[0058] Uses of a surfactant mixture according to the invention or
of a formulation according to the invention are: [0059] Humectants,
in particular for the printing industry. [0060] Cosmetic,
pharmaceutical and crop protection formulations. Suitable crop
protection formulations are described, for example, in EP-A 0 050
228. Further ingredients customary for crop protection compositions
may be present. [0061] Paints, coating compositions, dyes, pigment
preparations and adhesives in the coatings and polymer film
industry. [0062] Leather-degreasing compositions. [0063]
Formulations for the textile industry, such as leveling agents or
formulations for yarn cleaning. [0064] Fiber processing and
auxiliaries for the paper and pulp industry. [0065] Metal
processing, such as metal finishing and electroplating sector.
[0066] Food industry. [0067] Water treatment and production of
drinking water. [0068] Fermentation. [0069] Mineral processing and
dust control. [0070] Building auxiliaries. [0071] Emulsion
polymerization and preparation of dispersions. [0072] Coolants and
lubricants.
[0073] Such formulations usually comprise ingredients such as
surfactants, builders, fragrances and dyes, complexing agents,
polymers and other ingredients. Typical formulations are described,
for example in WO 01/32820. Further ingredients suitable for
various applications are described in EP-A 0 620 270, WO 95/27034,
EP-A 0 681 865, EP-A 0 616 026, EP-A 0 616 028, DE-A 42 37 178 and
U.S. Pat. No. 5,340,495 and in Schonfeldt, see above, for
example.
[0074] In general, the compositions according to the invention can
be used in all areas where the effect of interface-active
substances is necessary.
[0075] The present invention therefore also relates to detergents,
cleaners, wetting agents, coatings, adhesives, leather-degreasing
compositions, humectants or textile-treatment compositions or
cosmetic, pharmaceutical or crop protection formulations comprising
a composition according to the invention or a composition prepared
by a method according to the invention. The products here
preferably comprise 0.1 to 80% by weight of the compositions.
[0076] The customary constituents of the detergents according to
the invention, in particular textile detergents, include, for
example, builders, surfactants, bleaches, enzymes and further
ingredients, as described below.
Builders
[0077] Inorganic builders (A') suitable for combination with the
surfactants according to the invention are primarily crystalline or
amorphous alumosilicates with ion-exchanging properties, such as,
in particular, zeolites. Various types of zeolites are suitable, in
particular zeolites A, X, B, P, MAP and HS in their Na form or in
forms in which Na is partially exchanged for other cations such as
Li, K, Ca, Mg or ammonium. Suitable zeolites are described, for
example, in EP-A 0 038 591, EP-A 0 021 491, EP-A 0 087 035, U.S.
Pat. No. 4,604,224, GB-A 2 013 259, EP-A 0 522 726, EP-A 0 384 070
and WO-A 94/24251.
[0078] Suitable crystalline silicates (A') are, for example,
disilicates or sheet silicates, e.g. SKS-6 (manufacturer: Hoechst).
The silicates can be used in the form of their alkali metal,
alkaline earth metal or ammonium salts, preferably as Na, Li and Mg
silicates.
[0079] Amorphous silicates, such as, for example, sodium
metasilicate, which has a polymeric structure, or Britesil.RTM. H20
(manufacturer: Akzo) can likewise be used.
[0080] Suitable inorganic builder substances based on carbonate are
carbonates and hydrogencarbonates. These can be used in the form of
their alkali metal, alkaline earth metal or ammonium salts.
Preferably, Na, Li and Mg carbonates or hydrogencarbonates, in
particular sodium carbonate and/or sodium hydrogencarbonate, are
used.
[0081] Customary phosphates as inorganic builders are
polyphosphates, such as, for example, pentasodium triphosphate.
[0082] The specified components (A') can be used individually or in
mixtures with one another. Of particular interest as inorganic
builder component is a mixture of alumosilicates and carbonates, in
particular of zeolites, primarily zeolite A, and alkali metal
carbonates, primarily sodium carbonate, in the weight ratio 98:2 to
20:80, in particular from 85:15 to 40:60. Besides this mixture,
other components (A') can also be present.
[0083] In a preferred embodiment, the textile detergent formulation
according to the invention comprises 0.1 to 20% by weight, in
particular 1 to 12% by weight, of organic cobuilders (B') in the
form of low molecular weight, oligomeric or polymeric carboxylic
acids, in particular polycarboxylic acids, or phosphonic acids or
salts thereof, in particular Na or K salts.
[0084] Suitable low molecular weight carboxylic acids or phosphonic
acids for (B') are, for example:
[0085] C.sub.4-C.sub.20-di-, -tri- and -tetracarboxylic acids, such
as, for example, succinic acid, propanetricarboxylic acid,
butanetetracarboxylic acid, cyclopentanetetracarboxylic acid and
alkyl- and alkenylsuccinic acids with C.sub.2-C.sub.16-alkyl or
-alkenyl radicals;
[0086] C.sub.4-C.sub.20-hydroxycarboxylic acids, such as, for
example, malic acid, tartaric acid, gluconic acid, glutaric acid,
citric acid, lactobionic acid and sucrose mono-, di- and
tricarboxylic acid;
[0087] aminopolycarboxylic acids, such as, for example,
nitrilotriacetic acid, .beta.-alanine-diacetic acid,
ethylenediaminetetraacetic acid, serinediacetic acid,
isoserine-diacetic acid, methylglycinediacetic acid and
alkylethylenediamine triacetates;
[0088] salts of phosphonic acids, such as, for example,
hydroxyethanediphosphonic acid.
[0089] Suitable oligomeric or polymeric carboxylic acids for (B')
are, for example:
[0090] oligomaleic acids, as are described, for example, in EP-A
451 508 and EP-A 396 303;
[0091] co- and terpolymers of unsaturated
C.sub.4-C.sub.8-dicarboxylic acids, where the comonomers may be
copolymerized monoethylenically unsaturated monomers
[0092] from the group (i) in amounts of up to 95% by weight,
[0093] from the group (ii) in amounts of up to 60% by weight
and
[0094] from the group (iii) in amounts of up to 20% by weight.
[0095] Suitable unsaturated C.sub.4-C.sub.8-dicarboxylic acids here
are, for example, maleic acid, fumaric acid, itaconic acid and
citraconic acid. Preference is given to maleic acid.
[0096] The group (i) comprises monoethylenically unsaturated
C.sub.3-C.sub.8-monocarboxylic acids, such as, for example, acrylic
acid, methacrylic acid, crotonic acid and vinylacetic acid. From
group (i), preference is given to using acrylic acid and
methacrylic acid.
[0097] Group (ii) comprises monoethylenically unsaturated
C.sub.2-C.sub.22-olefins, vinyl alkyl ethers with
C.sub.1-C.sub.8-alkyl groups, styrene, vinyl esters of
C.sub.1-C.sub.8-carboxylic acids, (meth)acrylamide and
vinylpyrrolidone. From group (ii), preference is given to using
C.sub.2-C.sub.6-olefins, vinyl alkyl ethers with
C.sub.1-C.sub.4-alkyl groups, vinyl acetate and vinyl
propionate.
[0098] Group (iii) comprises (meth)acrylic esters of
C.sub.1-C.sub.8-alcohols, (meth)acrylonitrile, (meth)acrylamides of
C.sub.1-C.sub.8-amines, N-vinylformamide and vinylimidazole.
[0099] If the polymers of group (ii) comprise vinyl esters in
copolymerized form, these may also be present in partially or
completely hydrolyzed form to give vinyl alcohol structural units.
Suitable copolymers and terpolymers are known, for example, from
U.S. Pat. No. 3,887,806 and DE-A 43 13 909.
[0100] Suitable copolymers of dicarboxylic acids for (B') are
preferably:
[0101] copolymers of maleic acid and acrylic acid in the weight
ratio 100:90 to 95:5, particularly preferably those in the weight
ratio 30:70 to 90:10 with molar masses from 100 000 to 150 000;
[0102] terpolymers of maleic acid, acrylic acid and a vinyl ester
of a C.sub.1-C.sub.3-carboxylic acid in the weight ratio 10 (maleic
acid):90 (acrylic acid+vinyl ester) to 95 (maleic acid):10 (acrylic
acid +vinyl ester), where the weight ratio of acrylic acid to the
vinyl ester can vary in the range from 30:70 to 70:30;
[0103] copolymers of maleic acid with C.sub.2-C.sub.8-olefins in
the molar ratio 40:60 to 80:20, where copolymers of maleic acid
with ethylene, propylene or isobutene in the molar ratio 50:50 are
particularly preferred.
[0104] Graft polymers of unsaturated carboxylic acids based on low
molecular weight carbohydrates or hydrogenated carbohydrates, cf.
U.S. Pat. No. 5,227,446, DE-A 44 15 623 and DE-A 43 13 909, are
likewise suitable as (B').
[0105] Suitable unsaturated carboxylic acids here are, for example,
maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic
acid, methacrylic acid, crotonic acid and vinylacetic acid, and
mixtures of acrylic acid and maleic acid, which are grafted on in
amounts of from 40 to 95% by weight, based on the component to be
grafted.
[0106] For the modification, additionally up to 30% by weight,
based on the component to be grafted, of further monoethylenically
unsaturated monomers are present in copolymerized form. Suitable
modifying monomers are the abovementioned monomers of groups (ii)
and (iii).
[0107] Suitable graft bases are degraded polysaccharides, such as,
for example, acidically or enzymatically degraded starches, inulins
or cellulose, protein hydrolysates and reduced (hydrogenated or
reductively aminated) degraded polysaccharides, such as, for
example, mannitol, sorbitol, aminosorbitol and N-alkylglucamine,
and also polyalkylene glycols with molar masses up to M.sub.w=5000,
such as, for example, polyethylene glycols, ethylene
oxide/propylene oxide or ethylene oxide/butylene oxide or ethylene
oxide/propylene oxide/butylene oxide block copolymers and
alkoxylated mono- or polyhydric C.sub.1-C.sub.22-alcohols, cf. U.S.
Pat. No. 5,756,456.
[0108] From this group, preference is given to using grafted
degraded or degraded reduced starches and grafted polyethylene
oxides, where 20 to 80% by weight of monomers, based on the graft
component, are used in the graft polymerization. For the grafting,
a mixture of maleic acid and acrylic acid in the weight ratio from
90:10 to 10:90 is preferably used.
[0109] Polyglyoxylic acids suitable as (B') are described, for
example, in EP-B 001 004, U.S. Pat. No. 5,399,286, DE-A 41 06 355
and EP-A 0 656 914. The end groups of the polyglyoxylic acids can
have various structures.
[0110] Polyamidocarboxylic acids and modified polyamidocarboxylic
acids suitable as (B') are known, for example, from EP-A 454 126,
EP-B 511 037, WO-A 94/01486 and EP-A 581 452.
[0111] As (B'), use is made in particular also of polyaspartic
acids or cocondensates of aspartic acid with further amino acids,
C.sub.4-C.sub.25-mono- or -dicarboxylic acids and/or
C.sub.4-C.sub.25-mono- or -diamines. Particular preference is given
to using polyaspartic acids modified with C.sub.6-C.sub.22-mono- or
-dicarboxylic acids or with C.sub.6-C.sub.22-mono- or -diamines
produced in phosphorus-containing acids.
[0112] Condensation products of citric acid with hydroxycarboxylic
acids or polyhydroxy compounds suitable as (B') are known, for
example, from WO-A 93/22362 and WO-A 92/16493. Such condensates
comprising carboxyl groups usually have molecular masses up to 10
000, preferably up to 5000.
[0113] Further suitable as (B') are ethylenediaminedisuccinic acid,
oxydisuccinic acid, aminopolycarboxylates, aminopolyalkylene
phosphonates and polyglutamates.
[0114] Furthermore, in addition to (B'), oxidized starches can be
used as organic cobuilders.
Surfactants
[0115] Besides the surfactant mixture according to the invention,
further surfactants can be used.
[0116] Suitable inorganic surfactants (C) are, for example, fatty
alcohol sulfates of fatty alcohols having 8 to 22, preferably 10 to
18, carbon atoms, e.g. C.sub.9-C.sub.11-alcohol sulfates,
C.sub.12-C.sub.14-alcohol sulfates, cetyl sulfate, myristyl
sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol
sulfate.
[0117] Further suitable anionic surfactants are alkanesulfonates,
such as C.sub.8-C.sub.24-, preferably
C.sub.10-C.sub.18-alkylsulfonates, and soaps, such as, for example,
the Na and K salts of C.sub.8-C.sub.24-carboxylic acids.
[0118] Further suitable anionic surfactants are C.sub.9-C.sub.20
linear alkylbenzenesulfonates (LAS) and C.sub.9-C.sub.20 linear
alkyltoluenesulfonates.
[0119] Further suitable anionic surfactants (C) are also
C.sub.8-C.sub.24-olefinsulfonates and -disulfonates, which can also
constitute mixtures of alkene- and hydroxyalkane-sulfonates or
-disulfonates, alkyl ester sulfonates, sulfonated polycarboxylic
acids, alkyl glyceryl sulfonates, fatty acid glycerol ester
sulfonates, alkylphenol polyglycol ether sulfates,
paraffinsulfonates having about 20 to about 50 carbon atoms (based
on paraffin or paraffin mixtures obtained from natural sources),
alkyl phosphates, acyl isethionates, acyl taurates, acyl methyl
taurates, alkylsuccinic acids, alkenylsuccinic acids or half-esters
or half-amides thereof, alkylsulfo-succinic acids or amides
thereof, mono- and diesters of sulfosuccinic acids, acyl
sarcosinates, sulfated alkyl polyglucosides, alkyl polyglycol
carboxylates, and hydroxyalkyl sarcosinates.
[0120] The anionic surfactants are preferably added to the
detergent in the form of salts. Suitable cations in these salts are
alkali metal ions, such as sodium, potassium and lithium and
ammonium salts, such as, for example, hydroxyethylammonium,
di(hydroxyethyl)ammonium and tri(hydroxyethyl)ammonium salts.
[0121] Component (C) is present in the textile detergent
formulation according to the invention preferably in an amount of
from 3 to 30% by weight, in particular 5 to 20% by weight. If
C.sub.9-C.sub.20 linear alkylbenzenesulfonates (LAS) are used,
these are usually used in an amount up to 25% by weight, in
particular up to 20% by weight. It is possible to use only one
class of anionic surfactants on its own, for example only fatty
alcohol sulfates or only alkylbenzenesulfonates, although it is
also possible to use mixtures from different classes, e.g. a
mixture of fatty alcohol sulfates and alkylbenzenesulfonates.
Within the individual classes of anionic surfactants, mixtures of
different species can also be used.
[0122] A further class of suitable surfactants to be mentioned are
nonionic surfactants (D), in particular alkylphenol alkoxylates,
such as alkylphenol ethoxylates with C.sub.6-C.sub.14-alkyl chains
and 5 to 30 mol of alkylene oxide units.
[0123] Another class of nonionic surfactants are alkyl
polyglucosides or hydroxyalkyl polyglucosides having 8 to 22,
preferably 10 to 18, carbon atoms in the alkyl chain. These
compounds comprise mostly 1 to 20, preferably 1.1 to 5, glucoside
units. Another class of nonionic surfactants are N-alkylglucamides
with C.sub.6-C.sub.22-alkyl chains. Compounds of this type are
obtained, for example, by acylation of reductively aminated sugars
with corresponding long-chain carboxylic acid derivatives.
[0124] Further suitable as nonionic surfactants (D) are also block
copolymers of ethylene oxide, propylene oxide and/or butylene oxide
(Pluronic and Tetronic brands from BASF), polyhydroxy or polyalkoxy
fatty acid derivatives, such as polyhydroxy fatty acid amides,
N-alkoxy- or N-aryloxy-polyhydroxy fatty acid amides, fatty acid
amide ethoxylates, in particular terminally capped, and also fatty
acid alkanolamide alkoxylates.
[0125] Component (D) is present in the textile detergent
formulation according to the invention preferably in an amount of
from 1 to 20% by weight, in particular 3 to 12% by weight. It is
possible to use only one class of nonionic surfactants on its own,
in particular only alkoxylated C.sub.8-C.sub.22-alcohols, but it is
also possible to use mixtures from different classes. Within the
individual classes of nonionic surfactants, mixtures of different
species can also be used.
[0126] Since the balance between the specified types of surfactant
is of importance for the effectiveness of the detergent formulation
according to the invention, anionic surfactants (C) and nonionic
surfactants (D) are preferably in the weight ratio from 95:5 to
20:80, in particular from 80:20 to 50:50. Here, the surfactant
constituents of the surfactant mixture according to the invention
should also be taken into consideration.
[0127] Furthermore, cationic surfactants (E) can also be present in
the detergents according to the invention.
[0128] Suitable cationic surfactants are, for example,
interface-active compounds comprising ammonium groups, such as, for
example, alkyldimethylammonium halides and compounds of the general
formula
RR'R''R'''N.sup.+X.sup.-
[0129] in which the radical R to R''' are alkyl, aryl radicals,
alkylalkoxy, arylalkoxy, hydroxyalkyl(alkoxy), hydroxyaryl(alkoxy)
groups and X is a suitable anion.
[0130] The detergents according to the invention can, if
appropriate, also comprise ampholytic surfactants (F), such as, for
example, aliphatic derivatives of secondary or tertiary amines
which comprise an anionic group in one of the side chains,
alkyldimethylamine oxides or alkyl- or alkoxymethylamine
oxides.
[0131] Components (E) and (F) can be present in the detergent
formulation up to 25%, preferably 3-15%.
Bleaches
[0132] In a further preferred embodiment, the textile detergent
formulation according to the invention additionally comprises 0.5
to 30% by weight, in particular 5 to 27% by weight, especially 10
to 23% by weight, of bleaches (G). Examples are alkali metal
perborates or alkali metal carbonate perhydrates, in particular the
sodium salts.
[0133] One example of an organic peracid which can be used is
peracetic acid, which is preferably used during commercial textile
washing or commercial cleaning.
[0134] Bleach or textile detergent compositions to be used
advantageously comprise C.sub.1-12-percarboxylic acids,
C.sub.8-16-dipercarboxylic acids, imidopercaproic acids, or
aryldipercaproic acids. Preferred examples of acids which can be
used are peracetic acid, linear or branched octane-, nonane-,
decane- or dodecanemono-peracids, decane- and dodecanediperacid,
mono- and diperphthalic acids, -isophthalic acids and -terephthalic
acids, phthalimidopercaproic acid and terephthaloyldipercaproic
acid. It is likewise possible to use polymeric peracids, for
example those which comprise acrylic acid basic building blocks in
which a peroxy function is present. The percarboxylic acids can be
used as free acids or as salts of the acids, preferably alkali
metal or alkaline earth metal salts. These bleaches (G) are used,
if appropriate, in combination with 0 to 15% by weight, preferably
0.1 to 15% by weight, in particular 0.5 to 8% by weight, of bleach
activators (H). In the case of color detergents, the bleach (G) (if
present) is usually used without bleach activator (H), otherwise
bleach activators (H) are also usually present.
[0135] Suitable bleach activators (H) are: [0136] polyacylated
sugars, e.g. pentaacetylglucose; [0137] acyloxybenzenesulfonic
acids and alkali metal and alkaline earth metal salts thereof, e.g.
sodium p-isononanoyloxybenzenesulfonate or sodium
p-benzoyloxybenzenesulfonate; [0138] N,N-diacetylated and
N,N,N',N'-tetraacylated amines, e.g.
N,N,N',N'-tetra-acetylmethylenediamine and -ethylenediamine (TAED),
N,N-diacetylaniline, N,N-diacetyl-p-toluidine or 1,3-diacylated
hydantoins, such as 1,3-diacetyl-5,5-dimethylhydantoin; [0139]
N-alkyl-N-sulfonylcarboxamides, e.g. N-methyl-N-mesylacetamide or
N-methyl-N-mesylbenzamide; [0140] N-acylated cyclic hydrazides,
acylated triazoles or urazoles, e.g. monoacetylmaleic acid
hydrazide; [0141] O,N,N-trisubstituted hydroxylamines, e.g.
O-benzoyl-N,N-succinylhydroxyl-amine,
O-acetyl-N,N-succinylhydroxylamine or
O,N,N-triacetylhydroxyl-amine; [0142] N,N'-diacylsulfurylamides,
e.g. N,N'-dimethyl-N,N'-diacetylsulfurylamide or
N,N'-diethyl-N,N'-dipropionylsulfurylamide; [0143] triacyl
cyanurates, e.g. triacetyl cyanurate or tribenzoyl cyanurate;
[0144] carboxylic anhydrides, e.g. benzoic acid anhydride,
m-chlorobenzoic anhydride or phthalic anhydride; [0145]
1,3-diacyl-4,5-diacyloxyimidazolines, e.g.
1,3-diacetyl-4,5-diacetoxy-imidazoline; [0146]
tetraacetylglycoluril and tetrapropionylglycoluril; [0147]
diacylated 2,5-diketopiperazines, e.g.
1,4-diacetyl-2,5-diketopiperazine; [0148] acylation products of
propylenediurea and 2,2-dimethylpropylenediurea, e.g.
tetraacetylpropylenediurea; [0149]
.alpha.-acyloxypolyacylmalonamides, e.g.
.alpha.-acetoxy-N,N'-diacetylmalonamide; [0150]
diacyldioxohexahydro-1,3,5-triazines, for example
1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine; [0151]
benz(4H)-1,3-oxazin-4-ones with alkyl radicals, e.g. methyl, or
aromatic radicals, e.g. phenyl, in the 2 position.
[0152] The described bleaching system of bleaches and bleach
activators can, if appropriate, also comprise bleach catalysts.
Suitable bleach catalyst are, for example, quaternized imines and
sulfonimines, which are described, for example, in U.S. Pat. No.
5,360,569 and EP-A 0 453 003. Particularly effective bleach
catalysts are manganese complexes which are described, for example,
in WO-A 94/21777. In the case of their use in the detergent
formulations, such compounds are incorporated at most in amounts up
to 1.5% by weight, in particular up to 0.5% by weight.
[0153] Besides the described bleaching system of bleaches, bleach
activators and, if appropriate, bleach catalysts, the use of
systems with enzymatic peroxide release or of photoactivated bleach
systems is also conceivable for the textile detergent formulation
according to the invention.
Enzymes
[0154] In a further preferred embodiment, the textile detergent
formulation according to the invention additionally comprises 0.05
to 4% by weight of enzymes (J). Enzymes preferably used in
detergents are proteases, amylases, lipases and cellulases. Of the
enzymes, preferably amounts of 0.1-1.5% by weight, particularly
preferably 0.2 to 1.0% by weight, of the formulated enzyme are
added. Suitable proteases are, for example, savinase and esperase
(manufacturer: Novo Nordisk). A suitable lipase is, for example,
lipolase (manufacturer: Novo Nordisk). A suitable cellulase is, for
example, celluzym (manufacturer: Novo Nordisk). The use of
peroxidases for activating the bleaching system is also possible.
It is possible to use individual enzymes or a combination of
different enzymes. If appropriate, the textile detergent
formulation according to the invention can also comprise enzyme
stabilizers, e.g. calcium propionate, sodium formate or boric acids
or salts thereof, and/or oxidation inhibitors.
Further Ingredients
[0155] Besides the specified main components (A) to (J), the
textile detergent formulation according to the invention can also
comprise the following further customary additives in the amounts
customary for this purpose: [0156] Graying inhibitors and soil
release polymers
[0157] Suitable soil release polymers and/or graying inhibitors for
detergents are, for example:
[0158] polyesters of polyethylene oxides with ethylene glycol
and/or propylene glycol and aromatic dicarboxylic acids or aromatic
and aliphatic dicarboxylic acids;
[0159] polyesters of polyethylene oxides terminally capped at one
end with di- and/or polyhydric alcohols and dicarboxylic acid.
[0160] Such polyesters are known, for example from U.S. Pat. No.
3,557,039, GB-A 1 154 730, EP-A 0 185 427, EP-A 0 241 984, EP-A 0
241 985, EP-A 0 272 033 and U.S. Pat. No. 5,142,020.
[0161] Further suitable soil release polymers are amphiphilic graft
polymers or copolymers of vinyl esters and/or acrylic esters onto
polyalkylene oxides (cf. U.S. Pat. No. 4,746,456, U.S. Pat. No.
4,846,995, DE-A 37 11 299, U.S. Pat. No. 4,904,408, U.S. Pat. No.
4,846,994 and U.S. Pat. No. 4,849,126) or modified celluloses, such
as, for example, methyl-cellulose, hydroxypropylcellulose or
carboxymethylcellulose. [0162] color transfer inhibitors, for
example homopolymers and copolymers of vinylpyrrolidone, of
vinylimidazole, of vinyloxazolidone or of 4-vinylpyridine N-oxide
having molar masses of from 15 000 to 100 000, and crosslinked
finely divided polymers based on these monomers; [0163]
nonsurfactant-like foam suppressants or foam inhibitors, for
example organopolysiloxanes and mixtures thereof with microfine, if
appropriate silanized, silica, and paraffins, waxes,
microcrystalline waxes and mixtures thereof with silanized silica;
[0164] complexing agents (also in the function of organic
cobuilders); [0165] optical brighteners; [0166] polyethylene
glycols; polypropylene glycols [0167] perfumes or fragrances;
[0168] fillers; [0169] inorganic extenders, e.g. sodium sulfate,
[0170] formulation auxiliaries; [0171] solubility improvers; [0172]
opacifiers and pearlizing agents; [0173] dyes; [0174] corrosion
inhibitors; [0175] peroxide stabilizers; [0176] electrolytes.
[0177] The detergent formulation according to the invention is
preferably solid, i.e. is usually in powder or granule form or in
the form of an extrudate or tablet.
[0178] The powder- or granule-formed detergents according to the
invention can comprise up to 60% by weight of inorganic extenders.
Sodium sulfate is usually used for this purpose. Preferably,
however, the detergents according to the invention have a low
content of extenders and comprise only up to 20% by weight,
particularly preferably only up to 8% by weight, of extenders,
particularly in the case of compact or ultracompact detergents. The
solid detergents according to the invention can have various bulk
densities in the range from 300 to 1300 g/l, in particular from 550
to 1200 g/l. Modern compact detergents generally have high bulk
densities and exhibit a granule structure. The methods customary in
the art can be used for the desired compaction of the
detergents.
[0179] The detergent formulation according to the invention can be
produced by customary methods and, if appropriate, be
formulated.
[0180] Typical compositions of compact standard detergents and
color detergents are given below (the percentages refer, in the
text below and also in the examples, to the weight; the data in
brackets in the case of compositions (a) and (b) are preferred
ranges):
(a) Composition of Compact Standard Detergent (Powder or Granule
Form)
[0181] 1-60% (8-30%) of a surfactant mixture according to the
invention and, if appropriate, at least one anionic surfactant (C)
in combination with a nonionic surfactant (D) [0182] 5-50% (10-45%)
of at least one inorganic builder (A) [0183] 0.1-20% (0.5-15%) of
at least one organic cobuilder (B) [0184] 5-30% (10-25%) of an
inorganic bleach (G) [0185] 0.1-15% (1-8%) of a bleach activator
(H) [0186] 0-1% (at most 0.5%) of a bleach catalyst [0187] 0.05-5%
(0.1-2.5%) of a color transfer inhibitor [0188] 0.3-1.5% of a soil
release polymer [0189] 0.1-4% (0.2-2%) enzyme or enzyme mixture
(J)
[0190] Further customary additives:
[0191] Sodium sulfate, complexing agent, phosphonates, optical
brighteners, perfume oils, foam suppressants, graying inhibitors,
bleach stabilizers
(b) Composition of Color Detergent (Powder or Granule Form)
[0192] 3-50% (8-30%) of a surfactant mixture according to the
invention and, if appropriate, at least one anionic surfactant (C)
in combination with a nonionic surfactant (D) [0193] 10-60%
(20-55%) of at least one inorganic builder (A) [0194] 0-15% (0-5%)
of an inorganic bleach (G) [0195] 0.05-5% (0.2-2.5%) of a color
transfer inhibitor [0196] 0.1-20% (1-8%) of at least one organic
cobuilder (B) [0197] 0.2-2% enzyme or enzyme mixture (J) [0198]
0.2-1.5% soil release polymer
[0199] Further customary additives:
[0200] Sodium sulfate, complexing agent, phosphonates, optical
brighteners, perfume oils, foam suppressants, graying inhibitors,
bleach stabilizers.
[0201] The invention is illustrated in more detail by reference to
the examples below.
EXAMPLES
Example 1 "Surfactant 1"
[0202] A mixture of 2-propylheptanol and 5-methyl-2-propylhexanol,
which is sold as technical-grade 2-propylheptanol (2-PH) by BASF,
as short-chain component (A) (average degree of branching of 1.15)
and tallow fatty alcohol (C.sub.16-C.sub.18-alcohol) as long-chain
component (B) (average degree of branching of approximately 0) are
mixed in various mass ratios (A:B=2-PH: C.sub.16-C.sub.18-alcohol)
and then ethoxylated by means of KOH catalysis, with various HLB
values according to Griffin (20 times the mass fraction of ethylene
oxide in the product) being established.
Comparative Example 2 (="Surfactant 2")
[0203] A mixture of isodecanol (Exxal 10N, Exxon) (average degree
of branching of 2.2) and C.sub.13-C.sub.15-oxo alcohol (average
degree of branching of 0.6) (C.sub.13-C.sub.15 alcohol, BASF) is
reacted analogously to example 1 with ethylene oxide to give
"surfactant 2". The mass ratio A:B refers here to the ratio of
isodecanol to C.sub.13-C.sub.15-oxo alcohol.
Tests
1) Wetting of Cotton According to EN 1772
[0204] The tables below show the wetting times (according to EN
1772, 2 g/l soda) of the surfactant mixture according to the
invention ("surfactant 1") and of the reference mixture
("surfactant 2")
TABLE-US-00001 Surfactant 1 Surfactant 2 Wetting 0.5 g/l,
23.degree. C. Wetting 0.5 g/l, 23.degree. C. A:B [g:g] A:B [g:g]
HLB 1:0 9:1 8:2 7:3 HLB 1:0 9:1 8:2 7:3 11.6 60 40 40 60 11.6 70 70
70 80 12.5 60 60 60 --)* 12.5 100 90 100 -- 14.3 100 100 -- 200
14.3 200 150 -- 160 Wetting 1.0 g/l, 23.degree. C. Wetting 1.0 g/l,
23.degree. C. Ratio Ratio HLB 1:0 9:1 8:2 7:3 HLB 1:0 9:1 8:2 7:3
11.6 10 10 10 20 11.6 20 20 20 30 12.5 10 20 20 -- 12.5 25 25 30 --
14.3 20 20 -- 60 14.3 70 70 -- 80 Wetting 2.0 g/l, 23.degree. C.
Wetting 2.0 g/l, 23.degree. C. Ratio Ratio HLB 1:0 9:1 8:2 7:3 HLB
1:0 9:1 8:2 7:3 11.6 10 5 5 5 11.6 5 5 5 5 12.5 5 5 5 -- 12.5 5 5 5
-- 14.3 5 10 -- 20 14.3 15 15 -- 30 *not measured. Summary: It is
clear to see that the wetting power of surfactant 1 is better than
that of surfactant 2, particularly at higher dilutions.
2) Stability Against Lyotropic Salts (Example NaOH)
[0205] 2% surfactant mixture is mixed with aqueous NaOH solutions
(0%, 1%, 2%, 3% etc.), and after storage for 24 h at 23.degree. C.,
it is tested whether the mixture is stable (clear or cloudy) or
whether phase separation or creaming has taken place. The highest
concentration of NaOH at which the formulation appears still
optically one-phase (clear or cloudy) after 24 h at 23.degree. C.
is given.
TABLE-US-00002 Surfactant 1 Surfactant 2 % NaOH, 23.degree. C. %
NaOH, 23.degree. C. A:B [g:g] A:B [g:g] HLB 9:1 8:2 7:3 HLB 9:1 8:2
7:3 11.0 --)* 2 -- 11.0 -- 2 -- 11.6 3 -- 5 11.6 -- -- -- 12.5 -- 3
-- 12.5 -- 3 -- 14.0 -- 5 -- 14.0 -- 5 -- 14.3 5 -- 5 14.3 -- -- --
*not measured. Summary: Surfactant 1 and surfactant 2 behave
similarly.
3) Formation of Gel Phases with Water
[0206] Surfactant 1 is combined with water and homogenized well.
The mixture is then left to rest for 24 h at 23.degree. C. Then, a
Brookfield rheometer (spindle 2-7, 60 rpm, 23.degree. C.) is used
to determine the viscosity of the mixture.
TABLE-US-00003 Concen- A:B = 9:1, A:B = 9:1 A:B = 7:3 A:B = 7:3
tration (%) HLB = 11.6 HLB = 14.3 HLB = 11.6 HLB = 14.3 90 70 120
90 200 80 80 140 120 210 70 140 150 5400 240 60 7100 180 7000 4700
50 35 000 190 520 >100 000 40 300 140 130 210 30 260 50 110 40
20 260 20 100 10 10 70 10 20 5
4) Determination of the Emulsion Stability
[0207] The emulsion stability is determined by means of the marker
method, as described in DE 10247086. In two 600 ml beakers, 1% by
weight of surfactant is mixed with 69% by weight of water and then
30% by weight of oil--dyed yellow or blue--are added. Then, using a
propeller stirrer for 15 minutes, an input of about 10 kW/m.sup.3
is introduced. The emulsions obtained are mixed, and the droplet
size distribution is measured by means of statistical laser
scattering. The following tables give the d.sub.50, the median of
the droplets.
[0208] The emulsions are then stored at 23.degree. C. At periodic
intervals, the emulsions are shaken, a sample is taken and the
fraction of green drops, formed by coalescence, is determined by
means of microscopy and electronic image analysis. The measured
green fractions are then plotted against the storage time and
fitted by the following function by the least squares method:
Green(t)=100% $ (1-exp(-a$t)).
[0209] The stability constant S is finally obtained from S=-log(a $
month).
[0210] The oils used are sunflower oil (56 mm.sup.2/s at 25.degree.
C.) and paraffin oil (30 mm.sup.2/s at 25.degree. C.).
TABLE-US-00004 A:B [g:g] HLB d 50 S Surfactant 1 Paraffin oil 9:1
11.6 40 0.3 9:1 14.3 54 0.8 7:3 11.6 52 1.0 7:3 14.3 56 0.9
Sunflower oil 9:1 11.6 99 1.2 9:1 14.3 68 1.2 7:3 11.6 75 1.4 7:3
14.3 71 1.1 Surfactant 2 Paraffin oil 8:2 11 171 -0.1 8:2 12.5 188
0.7 8:2 14 101 1.1 Sunflower oil 8:2 11 71 -0.1 8:2 12.5 74 -0.7
8:2 14 99 -0.1 Summary: In the case of paraffin oil, significantly
smaller emulsion droplets are found with surfactant 1 compared to
surfactant 2 for approximately identical emulsion stability. In the
case of sunflower oil, a drastically improved emulsion stability is
found with surfactant 1 compared to surfactant 2.
5) Determination of the Detergency During High-Temperature Cotton
Washing
[0211] About 10 g of WFK soiled fabric 10D are rolled up and placed
into a small laundry basket for a washing machine Ahiba Texomat.
200 ml of a wash liquor of softened water and 1 g/l of the
respective surfactant are poured into the glass container and
brought to 60.degree. C. in the dyeing and washing apparatus. The
device is started and heated from 60.degree. C. to 95.degree. C. in
15 min, at 95.degree. C., the temperature is held for 15 min. The
soiled fabric is then removed, and rinsed twice hot and once cold.
The fabric is squeezed, dried and mangled while hot. The degree of
whiteness on the soiled side of the fabric is assessed in Berger
units on a suitable spectrometer (Datacolor-spectrometer
Spectraflash 500).
TABLE-US-00005 Concentration A:B = 9:1, A:B = 9:1, A:B = 7:3 A:B =
7:3 HLB = 11.6 HLB = 14.3 HLB = 11.6 HLB = 14.3 Degree of 54 57 57
58 whiteness according to Berger
6) Determination of the Detergency Analogous to Household
Washing
[0212] The washing experiments were carried out under the following
conditions:
TABLE-US-00006 Washing conditions Primary wash Device
Launder-o-meter from Atlas, Chicago USA Wash liquor 250 ml Wash
time 30 min at stated temperature (including heating time)
Detergent dosing 5 g/l Water hardness 3 mmol/l Ca:Mg 4:1 Liquor
ratio 1:12.5
[0213] Test fabric from wfk Testgewebe GmbH, Bruggen, Germany
TABLE-US-00007 wfk 10 D Skin grease/pigment on cotton wfk 20 D Skin
grease/pigment on 65% polyester/35% cotton wfk 10 PF Plant
grease/pigment on cotton
Detergent Formulation
TABLE-US-00008 [0214] Zeolite A 30% Sodium carbonate 12% Sodium
silicate 3% Tylose CR 1500 p 1.2% Sodium perborate monohydrate
14.4% Tetraacetylethylenediamine 4% Acrylic acid/maleic acid
copolymer (MW 70 000) 5% Soap 0.5% Sodium sulfate 4% Water 20.9%
Surfactant 5%
[0215] After rinsing, spinning was carried out and the fabric was
hung up to dry individually. The fabric was measured using an
Elrepho 2000 from Data Color, Heidenheim, 6 measurement points per
item of fabric. The reflectance value was determined at 460 nm.
Large values for the reflectance here indicate good soil release
and high primary detergency.
[0216] The washed test fabrics are measured using a photometer from
Data Color (Elrepho 2000). The table below gives the reflectance
value (R at 460 nm) in percent. The higher the reflectance value,
the better the primary detergency.
[0217] For each run, a formulation comprising Lutensol AO7 as
surfactant ("Lutensol AO7"), and a formulation in which the
surfactant was replaced by water ("without surfactant") were also
washed as control experiments. These experiments serve to
standardize the washing results. Standardization was carried out
linearly, with "without surfactant" being set at 0% and "Lutensol
AO7" being set as 100%:
Calculation Formula:
[0218] % (Detergency)=100%[reflectance (surfactant 1 or
2)-reflectance ("without surfactant")]i[reflectance ("Lutensol
A07")-reflectance ("Without surfactant")]
TABLE-US-00009 Standardized: "without" = 0% "Lutensol AO7" = 100%
Reflectance % Detergency A:B WFK WFK Mean HLB [g/g] 10 D 20 D 10 PF
10 D 20 D 10 PF value Surfactant 1 Washing at 25.degree. C. without
surfactant 51.6 44.1 42.7 Lutensol AO7 57.0 58.1 48.7 Surfactant 1
10.5 9:1 59.0 51.4 47.2 136% 52% 75% 88% Surfactant 1 11.0 9:1 56.7
50.7 46.0 93% 47% 55% 65% Surfactant 1 11.6 9:1 56.1 49.7 45.0 83%
40% 38% 54% Surfactant 1 12.5 9:1 56.0 51.0 44.1 81% 49% 23% 51%
Surfactant 1 14.3 9:1 55.3 47.8 43.8 68% 26% 19% 38% Surfactant 1
10.5 7:3 60.3 53.3 48.8 160% 66% 102% 109% Surfactant 1 11.0 7:3
56.4 51.2 48.5 89% 51% 97% 79% Surfactant 1 11.6 7:3 52.9 50.1 45.9
24% 43% 53% 40% Surfactant 1 13.0 7:3 59.4 52.7 45.5 144% 61% 47%
84% Surfactant 1 14.3 7:3 51.9 48.0 43.5 7% 28% 14% 16% Washing at
40.degree. C. without surfactant 52.5 45.8 44.8 Lutensol AO7 61.7
65.7 54.3 Surfactant 1 10.5 9:1 62.0 53.0 52.5 103% 36% 81% 73%
Surfactant 1 11.0 9:1 59.7 52.3 51.0 78% 32% 65% 59% Surfactant 1
11.6 9:1 59.7 51.8 48.5 78% 30% 39% 49% Surfactant 1 12.5 9:1 62.8
50.7 53.6 111% 24% 93% 76% Surfactant 1 14.3 9:1 58.7 47.4 43.5 68%
8% -13% 21% Surfactant 1 10.5 7:3 61.5 57.4 53.3 97% 58% 89% 82%
Surfactant 1 11.0 7:3 61.1 57.4 51.5 93% 58% 71% 74% Surfactant 1
11.6 7:3 60.5 56.1 46.2 87% 51% 15% 51% Surfactant 1 13.0 7:3 62.7
54.9 51.6 111% 46% 72% 76% Surfactant 1 14.3 7:3 57.5 49.7 44.1 54%
19% -7% 22% Washing at 60.degree. C. without surfactant 55.0 46.3
47.8 Lutensol AO7 67.0 71.7 59.3 Surfactant 1 10.5 9:1 64.0 51.7
55.3 75% 21% 65% 54% Surfactant 1 11.0 9:1 68.2 52.4 55.3 110% 24%
65% 66% Surfactant 1 11.6 9:1 65.6 56.1 52.5 88% 39% 41% 56%
Surfactant 1 12.5 9:1 64.0 55.4 55.4 76% 36% 66% 59% Surfactant 1
14.3 9:1 59.6 55.3 49.8 38% 35% 17% 30% Surfactant 1 10.5 7:3 68.2
54.3 56.2 110% 31% 73% 71% Surfactant 1 11.0 7:3 67.0 61.0 55.7
100% 58% 69% 76% Surfactant 1 11.6 7:3 64.0 68.2 51.9 75% 86% 35%
66% Surfactant 1 13.0 7:3 66.9 62.2 59.4 99% 63% 101% 88%
Surfactant 1 14.3 7:3 57.0 57.3 53.5 17% 43% 50% 37% Surfactant 2
Washing at 25.degree. C. without surfactant 54.2 43.4 42.7 Lutensol
AO7 62.8 59.3 47.6 Surfactant 2 11.0 9:1 59.8 50.2 44.2 66% 42% 31%
46% Surfactant 2 12.5 9:1 58.2 47.7 44.0 47% 27% 27% 34% Surfactant
2 11.0 7:3 59.2 56.5 47.4 58% 82% 96% 79% Surfactant 2 13.0 7:3
61.9 50.9 47.1 90% 47% 90% 76% Washing at 40.degree. C. without
surfactant 55.2 43.0 44.9 Lutensol AO7 63.7 68.9 56.9 Surfactant 2
11.0 9:1 60.2 52.9 51.6 59% 38% 56% 51% Surfactant 2 12.5 9:1 62.2
52.7 49.1 82% 37% 35% 52% Surfactant 2 11.0 7:3 60.4 63.7 53.3 62%
80% 70% 71% Surfactant 2 13.0 7:3 61.7 61.7 50.7 77% 72% 49% 66%
Washing at 60.degree. C. without surfactant 57.8 42.9 45.5 Lutensol
AO7 67.0 73.1 63.1 Surfactant 2 11.0 9:1 65.9 55.7 53.4 87% 42% 45%
58% Surfactant 2 12.5 9:1 66.3 62.1 53.2 92% 63% 44% 66% Surfactant
2 11.0 7:3 64.3 62.1 54.2 71% 64% 49% 61% Surfactant 2 13.0 7:3
62.4 65.9 55.1 50% 76% 55% 60% Summary: On average, surfactant 1
achieves an approximately 11% point better detergency than
surfactant 2 over all 3 fabrics and over all 3 washing
temperatures.
7) Whipped Foam Test
[0219] A whipped foam test was carried out according to EN 12728 (2
g/l, 40.degree. C.). The results are summarized in the table
below.
TABLE-US-00010 Surfactant 1 Surfactant 2 A:B [g:g] HLB Foam in ml
Foam in ml 9:1 11.6 140 250 9:1 12.5 270 220 9:1 14.3 400 390 8:2
11.6 200 260 8:2 12.5 280 290 7:3 11.6 170 220 7:3 14.3 340 390
Summary: Surfactant 1 is a weaker foamer than surfactant 2.
[0220] Overall, surfactant 1 is clearly superior to surfactant 2 in
detergency, lack of foam, wetting rate and emulsion stability
without displaying disadvantages regarding salt stability.
* * * * *