Note: Descriptions are shown in the official language in which they were submitted.
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Hydrophobically modified polyalkylenimines for use as dye transfer inhibitors
Description
The invention relates to the use of hydrophobically modified polyalkylenimines
as dye
transfer inhibitors.
During the washing process, dye molecules are often detached from colored
textiles;
these can in turn attach to other textiles. In order to counteract this
undesired dye
transfer, so-called dye transfer inhibitors are often used. These are
frequently polymers
which comprise monomers with nitrogen-heterocyclic radicals in copolymerized
form.
Thus, for example, DE 4235798 describes copolymers of 1-vinylpyrrolidone,
1-vinylimidazole, 1-vinylimidazollum compounds or mixtures thereof; further
nitrogen-
containing, basic ethylenically unsaturated monomers; and, if appropriate,
other
monoethylenically unsaturated monomers and their use for inhibiting dye
transfer
during the washing process.
Similar copolymers are described for this purpose in DE 19621509 and WO
98/30664.
The copolymers described in these specifications are characterized in part by
good
inhibition of dye transfer in washing processes. However, they generally have
poor
compatibility with the other detergent constituents customarily used. Thus,
particularly
in the case of liquid detergents, there is the danger of incompatibilities,
for example in
the form of opacity or phase separations.
On several occasions, the use of hydrophobically modified polyalkylenimines in
detergent and cleaner formulations has been described.
DE 2025829 describes reaction products of fatty acid glycidyl esters with
polyethylenimines and their use as fabric softeners.
DE 2046304 describes reaction products of fatty acids or fatty acid esters
with
polyethylenimines and their use as fabric softeners.
DE 2165900 describes reaction products of alkyl glycidyl ethers with
polyethylenimines
and their use as graying inhibitors.
US 3,576341 describes alkylated polyethylenimines in which the alkyl groups
have 16
to 30 carbon atoms, and use as fabric softeners.
WO 2002/l095122 describes the use of hydrophobically modified
polyethylenimines as
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anticrease additives for detergent formulations.
An effect of the hydrophobically modified polyalkylenimines inhibiting dye
transfer
during washing is described in none of these citations.
It was an object of the present invention to provide substances with a good
dye
transfer-inhibiting effect during the washing process. These substances should
additionally have good compatibility with conventional detergent constituents,
especiaily in the case of liquid detergent formulations.
These and further objects are surprisingly achieved through hydrophobically
modified
poly-Cz-Ca-al kylenimines.
The invention therefore relates to the use of hydrophobically modified poly-
C2-C4-alkylenimines, in particular hydrophobically modified polyethylenimines,
as dye
transfer inhibitors in detergent compositions for textiles.
Here and in what follows, hydrophobically modified poly-Cz-Cq-alkylenimines
are to be
understood as meaning poly-Cz-Ca-alkylenimines in which the hydrogen atoms of
the
primary and secondary amino groups are partially or completely replaCed by
linear or
branched aliphatic, saturated or unsaturated hydrocarbon radicals such as
alkyl,
alkenyl, alkadienyl or hydroxyalkyl radicals. The hydrocarbon radicals
generally have at
least 8, e.g. 8 to 30, carbon atoms, preferably 10 to 22 carbon atoms, in
particular 10 to
18 carbon atoms.
Depending on the hydrophobicizing agent used in each case, the hydrocarbon
radicals
can be linked to the nitrogen atom of the poly-C2-CQ-alkylenimine directly or
via a
functional group, e.g. via a carbonyl group (*-C(=O)-#), via an oxycarbonyl
group
(*-O-C(=0)-#), via an aminocarbonyl group (*-NH-C(=0)-#), via a
carbonyloxyhydroxypropyl group (*-C(=0)-O-CH2-CH(OH)-CH2-#), via a
2-oxycarbonylethylenecarbonyl group (*-CH(COOH)-CHrCO-#), or via a radical of
the
formula *-CH2-C(=O)-CH '-C(=0)-# (in the formulae given above, * represents
the
linkage to the hydrocarbon radical and # represents the linkage to the
nitrogen atom of
the poly-C2-C4-alkylenimine). The hydrocarbon radical can also form an
aidimine or
ketimine group with the nitrogen of the poly-C2-C4-alkylenimine, or be linked
to
2 nitrogen atoms of the pofy-C2-C4-alkylenimine via the carbon atom of a
cyclic amidine
group.
Preference is given to those hydrophobically modified poly-C2-C4-alkylenimines
in
which the hydrocarbon radical is linked to one nitrogen atom of the poly-
C2-C4-alkylenimine directly or via a carbonyl group, the latter being
particularly
preferred.
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Preferably, the hydrocarbon radicals are iinear. Preferably, the hydrocarbon
radicals
are saturated.
Accordingly, the hydrocarbon radicals in the preferred hydrophobically
modified poly-
Ci-Ca-alkylenimines are present in the form of Ca-Cao-alkyl, Ca-Cao-
alkylcarbonyl,
Ca-Cao-alkenyl, C$-Cso-alkenylcarbonyl, Ca-Cao-alkadienyl, Ca-C3o-
alkadienylcarbonyl
and/or hydroxy-C$-Cao-alkyl groups, in particular in the form of C1o-C22-
alkyl,
CGo-C22-alkylcarbonyl, C,o-C22-alkenyl, C,o-Czz-alkenylcarbonyl, C,o-C22-
aikadienyi,
C1o-C22-alkadienylcarbonyl andlor hydroxy-C,o-C22-alkyl groups, particularly
preferably
in the form of Go-C,a-alkyl, C,o-C,a-alkyicarbonyl, C,o-C,a-alkenyl,
Cio-C,a-alkenylcarbonyl, C,o-C,a-alkadienyl, C,o-C,s-alkadienylcarbonyl and/or
hydroxy-
C,o-C,$-alkyl groups, where the alkyl, hydroxyalkyl, aikenyl, alkadienyl
radicals of the
aforementioned groups are preferably linear.
In the particularly preferred hydrophobically modified poly-C2-C4-
alkylenimines, the
hydrocarbon radicals are present in the form of Ca-Cao-alkytcarbonyi or
Cs-Cso-alkenylcarbonyl groups, in particular in the form of C,o-C22-
alkylcarbonyl or
C,o-C22-alkenylcarbonyl groups and specifically in the form of C,o-Cis-
alkylcarbonyl or
Cio-C,s-alkenylcarbonyl groups, where the alkyl und alkenyl radicals of the
aforementioned groups are preferably linear.
Preference is furthermore given to those hydrophobically modified poly-
C2-C4-alkylenimines in which at least 10 mol%, in particular at least 15 mol%
and
particularly preferably at least 20 mol%, e.g. 5 to 80 moI%, in particular 15
to 70 mol%
and specifically 20 to 60 mol%, of the nitrogen atoms of the paly-C2-C4-
alkylenimine
carry a hydrocarbon radical.
Correspondingly, the fraction of the hydrocarbon radicals constitutes
preferably 25 to
95% by weight, in particular 30 to 90% by weight and specifically 40 to 80% by
weight,
based on the total weight of the hydrophobicaEly modified poly-C2-C4-
alkylenimine.
The weight-average molecular weight Mw of hydrophobically modified poly-
C2-C4-alkylenimines suitable according to the invention is typically in the
range from
1000 to 1 000 000 Daltons. For the use according to the invention, it has
furthermore
proven advantageous if the hydrophobically modified poly-C2-Ca~-alkylenimine
has a
number-average molecular weight in the range from 3000 to 300 000 Daltons and
in
particular in the range from 6000 to 200 000 Daltons. The molecular weights
given here
refer to the molecular weights specified by means of dynamic light scattering
and
measured on dilute aqueous solutions at 25 C which correspond to the weight-
average
molecular weight.
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The hydrophobically modified poly-CrCa-alkylenimines used according to the
invention, in particular the hydrophobically modified polyethylenimines, can,
based on
the poly-C2-C4-alkylenimine on which they are based, be linear or branched,
preference
being given to those which are branched in the poly-C2-C4-alkylenimine mpiety.
Whereas linear poly-C2-C4-alkylenimines are composed exclusively of repeat
units of
formula A, in which Q is C2-C4-alkylene, branched poly-Cz-C4-alkylenimines
have,
besides the linear repeat units, tertiary nitrogen atoms according to the
structural unit
B:
*+H~---Q~-H-* N-Q~'N-*
* Q
A B
Preference is given to those branched, hydrophobically modified poly-
C2-C4 alkylenimines, in particular branched, hydrophobically modified
polyethylenimines, which, based on the poly-C2-C4-alkylenimine on which they
are
based, have, on average, per polyalkylenimine molecule at least one,
preferably at
least 5 or at least 10, branching points according to formula B. In
particular, at least
5%, in particular at least 10% and particularly preferably at least 15%, e.g.
5 to 40%
and specifically 15 to 35%, of the nitrogen atoms of the parent poly-C2-C4-
alkylenimine
are tertiary nitrogen atoms.
Particularly in the case of relatively high degrees of branching, i.e. if at
least 10%, in
particular at least 15%, e.g. 10 to 40%, in particular 15 to 35% of the
nitrogen atoms of
the parent poly-C2-C4-alkylenimine are tertiary nitrogen atoms, the
hydrophobically
modified poly-C2-C4-alkylenimines have a structure similar to a core-shell
structure,
where the poly-C2-C4-alkylenimine moieties form the core and the hydrophobic
radicals
form the shell.
The hydrophobically modified poly-CrCa-alkylenimines can be present in
uncrosslinked
or crosslinked form, and, besides the hydrophobic modification, may be
quaternized
and/or modified through reaction with alkylene oxides, di-Ci-C4-alkyl
carbonates,
C2-C4-alkylene carbonates or C,-C4-carboxyfic acids.
Preferably, the hydrophobically modified poly-C2-C4-alkylenimines are
uncrosslinked.
According to a first preferred embodiment of the invention, the
hydrophobically
modified poly-C2-C4-alkylenimines have no further modification besides the
hydrophobic modification.
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According to a second preferred embodiment of the invention, the
hydrophobically
modified poly-C2-C4-alkylenimines are quaternized in addition to the
hydrophobic
modification. Such quaternized hydrophobically modified poly-C2-C4-
alkylenimines
preferably have no further modffication. The degree of quaternization, i.e.
the number
5 of quaternized nitrogen atoms, based on the total amount of the nitrogen
atoms of the
hydrophobically modified poly-C2-C4-alkylenimine, is preferably not more than
80 mol%, in particular not more than 50 mol%, e.g. 1 to 80 mol%, in particular
5 to
50 mol%, based on the nitrogen atoms of the poly-CrCa-aikylenimine.
The hydrophobically modified poly-C2-C4-alkylenimines which are used according
to
the invention are in part known from the prior art cifed at the beginning or
can be
prepared analogously to the methods described there. As a nale,
hydrophobically
modified poly-Cz-Cd-alkylenimines are prepared by polymer-analogous reaction
of
unmodified poly-C2-C4-alkylenimines with a hydrophobicizing agent.
Accordingly, one
embodiment of the invention relates to the use of a hydrophobically modified
poly-
C2-C4-alkylenimine obtainable by a process which comprises the reaction of a
nonmodified poly-C2-C4-alkylenimine, in particular a nonmodified, branched
poly-
C2-C4-alkylenimine, and specifically a nonmodified, branched polyethylenimine,
with a
hydrophobicizing agent.
Examples of suitable hydrophobicizing agents are:
i) long-chain, linear or branched carboxylic acids having 8 to 30 carbon
atoms,
preferably 10 to 22 carbon atoms, in particular 10 to 18 carbon atoms, in the
alkyl
or alkenyl radical, such as caprylic acid, pelargonic acid, undecanoic acid,
lauric
acid, tridecanoic acid, myristic acid, pentadecanoic acid, paimitic acid,
margaric
acid, stearic acid, nonadecanoic acid, arachic acid, behenic acid, palmitoleic
acid,
oleic acid, linoleic acid, linolenic acid, arachidonic acid and mixtures
thereof,
preferably lauric acid, stearic acid, paimitic acid and oleic acid, or their
amide-
forming derivatives, such as acid chlorides, esters or anhydrides of the
specified
carboxylic acids and mixtures thereof,
ii) linear or branched alkyl halides having 8 to 30 carbon atoms, preferably
10 to
22 carbon atoms, in particular 10 to 18 carbon atoms, in the linear or
branched
alkyl radical, such as octyl chloride, nonyl chloride, decyl chloride, dodecyl
chloride, tetradecyl chloride, hexadecyl chloride, octadecyl chloride and
mixtures
thereof,
iii) alkyl epoxides having 8 to 30 carbon atoms, preferably 10 to 22 carbon
atoms, in
particular 10 to 18 carbon atoms in the linear or branched alkyl radical, such
as
hexadecenyl oxide, dodecenyl oxide and octadecenyl oxide and mixtures thereof,
iv) alkyl ketene dimers having 8 to 30 carbon atoms, preferably 10 to 22
carbon
atoms, in particular 10 to 18 carbon atoms in the linear or branched alkyl
radical,
such as lauryl ketene, paimityl ketene, stearyl ketene and oleyl ketene dimers
and mixtures thereof,
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v) cyclic dicarboxylic acid anhydrides, in particular alkyl-substituted
succinic
anhydrides having 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in
particular 10 to 18 carbon atoms, in the linear or branched alkyl radical,
such as
dodecenyisuccinic anhydride, tetradecylsuccinic anhydride, hexadecenyisuccinic
anhydride and mixtures thereof,
vi) alkyl isocyanates having 8 to 30 carbon atoms, preferably 10 to 22 carbon
atoms,
in particular 10 to 18 carbon atoms in the linear or branched alkyl radical,
such as
tetradecyl isocyanate, hexadecyl isocyanate, octadecyl isocyanate and mixtures
thereof,
vii) chtoroformic acid esters of linear or branched alkanols or alkenols
having 8 to
30 carbon atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18
carbon
atoms and mixtures thereof, and
viii) linear or branched aliphatic aldehydes having 8 to 30 carbon atoms,
preferably
10 to 22 carbon atoms, in particular 10 to 18 carbon atoms, and dialkyl
ketones
having in total 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in
particular 10 to 18 carbon atoms, in the two alkyl groups and mixtures
thereof.
Preferred hydrophobicizing agents are long-chain, linear or branched
carboxylic acids
having 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in particular
10 to
18 carbon atoms, in the alkyl or alkenyl radical and amide-forming derivatives
thereof,
in particular linear saturated carboxylic acids having 10 to 22 carbon atoms,
in
particular 10 to 18 carbon atoms in the alkyl radical.
Preferred hydrophobicizing agents are also alkyl epoxides having 8 to 30
carbon
atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18 carbon atorns.
The unmodified poly-CrC4-alkylenimines which form the basis of the
hydrophobically
modified poly-C2-Ca-alkylenimines used according to the invention comprise
homopolymers of ethylenimine (aziridine) and higher homologs thereof,
propylenimine
(methylaziridine) and butylenimines (1,2-dimethylaziridine, 1,1-
dimethylaziridine and
1-ethylaziridine), copolymers of ethylenimine with its higher homologs, and
the graft
polymers of polyamidoamines or polyvinylamines with ethylenimine and/or its
higher
homologs.
Also suitable are the graft polymers of C2-C4-alkylenimines described in
WO 02/095122, such as ethylenimine onto polyamidoamines or onto
polyvinylamines.'
Such graft polymers generally have a weight fraction of C2-G4-alkylenimines of
at least
10% by weight, in particular at least 30% by weight, e.g. 10 to 90% by weight
in
particular 10 to 85% by weight, based on the total weight of the unmodified
poly-
C2-C4-alkylenimine.
In particular, the unmodified poly-CrC4-alkylenimines are branched poly-
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C2-C4-alkylenimines, preferably polyethylenimines, in particular branched
polyethylenimines and specifically homopolymers of ethylenimine, which are in
particular branched.
Preferably, the unmodified poly-C2-Ca-aikylenimine used for the preparation is
branched, where, with regard to the degree of branching, that stated above for
hydrophobically modified poly-C2-C4-alkylenimines applies.
Preferably, the unmodified poly-CrCa-alkylenimine used for the preparation has
a
number-average molecular weight in the range from 1000 to 200 000 Daltons, in
particular in the range from 2000 to 100 000 Daltons.
The reaction of the unmodified poly-C2-Ca-alkylenimine with the
hydrophobicizing agent
can take place analogously to known processes in the prior art. The reaction
conditions
naturally depend on the type and functionality of the hydrophobicizing agent.
The reaction can take place without a diluent or in solution. The reaction is
preferably
carried out in a solvent suitable for the reaction. Examples of suitable
solvents are
hydrocarbons, in particular aromatic hydrocarbons, e.g. alkylbenzenes such as
xylenes, toluene, cumene, tert-butylbenzene and the like.
If appropriate, the reaction can be carried out in the presence of catalysts
which
improve the reactivity of the hydrophobicizing agent toward the poly-
C2-C4-alkylenimine. The type of catalyst depends in a manner known per se on
the
type and reactivity of the hydrophobicizing agent. The catalysts are usually
Lewis acids
or Bronstedt acids. Often, for example in the case of carboxylic acids, it is
possible to
dispense with the use of catalysts.
In the case of the carboxylic acids and carboxylic acid derivatives preferred
according
to the invention, it has proven advantageous to remove the low molecular
weight
products (water, alcohols or hydrogen chloride) which form during the reaction
from the
reaction mixture. For example, in the case of the carboxylic acids, the water
formed will
preferably be removed from the reaction mixture via an entrainer. Typical
entrainers
are hydrocarbons, in particular alkyl aromatics such as toluene or xylenes.
Preferably,
the reaction will then be carried out in an organic solvent suitable as
entrainer.
As a rule, the hydrophobicizing agent will be used in an amount which
corresponds to
the desired functionality, it also being possible to use the hydrophobicizing
agent in
excess. In this respect, that stated previously for the functionalization of
the
hydrophobicized polyalkylenimine applies analogously for the molar ratio of
hydrophobicizing agent to nitrogen atoms in the unmodified polyalkylenimine.
In
particular, the hydrophobicizing agent, calculated as the parts of the
hydrophobicizing
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agent remaining in the product (thus the amount of hydrophobicizing agent
minus any
low molecular weight products such as water), will be used in an amount of
from 0.35
to 20 parts by weight, in particular in an amount of from 0.5 to 10 parts by
weight, per
part by weight of unmodified poly-C2-C4-alkylenimine.
According to a preferred embodiment of the invention, the hydrophobically
modified
poly-C2-Ca-alkylenimines are quaternized. Accordingly, the preparation of the
hydrophobically modified poly-Cz-C4-alkylenimines additionally comprises a
quaternization. The quaternization can take place before or in parl:icular
after the
hydrophobicization.
For the quatemization, in particular alkylating agents such as alkyl halides
which
generally have 1 to 10 carbon atoms in the alkyl radical, or dialkyl sulfates,
which
generally comprise alkyl radicals having 1 to 10 carbon atoms, are used.
Examples of
suitable alkylating agents from these groups are methyl chloride, methyl
bromide,
methyl iodide, ethyl chloride, ethyl bromide, propyl chloride, hexyl chloride,
dodecyl
chloride, lauryl chloride, and dimethyl sulfate and diethyl sulfate. Further
suitable
alkylating agents are, for example, benzyl halides, in particular benzyl
chloride and
benzyl bromide; chloroacetic acid; fluorosulfuric acid methyl ester;
diazomethane;
oxonium compounds, such as trimethyloxonium tetrafluoroborate; alkylene
oxides,
such as ethylene oxide, propylene oxide and glycidol, which are used in the
presence
of acids; cationic epichlorohydrins. Preferred quaternizing agents are methyl
chloride,
dimethyl suffate and diethyl sulfate. During the quaternization, the secondary
or in
particular the tertiary nitrogen atoms of the parent poly-CrCa-alkylenimine
moiety are
converted into quatemary nitrogen atoms, ergo ammonium groups, as a result of
which
the hydrophobically modified poly-Cz-Ca-alkylenimine is given an overall
positive
charge.
The hydrophobically modified poly-C2-C4-alkylenimines are generally water-
soluble or
water-dispersible and can be used in solid and liquid detergents and in
laundry
aftertreatment compositions. They are characterized in particular by high
compatibility
with conventional detergent constituents, in particular with the constituents
of liquid
detergent formulations, specifically those which have a low content of anionic
surfactants.
The incorporation into the respective detergent or laundry aftertreatment
composition
formulation takes place in a manner known per se, the hydrophobically modified
polyalkylenimines often being used in liquid form, i.e. dissolved or dispersed
form. The
hydrophobically modified polyalkylenimines can also be used in powder or
granule
form.
The dye transfer onto fabric washed at the same time and the associated
undesired
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discoloration of this fabric is effectively inhibited. Even at concentrations
of from 10 to
150 ppm of the hydrophobically modified poly-C2-C4-alkylenimine in the wash or
rinse
liquor, good to very good dye transfer-inhibiting effects are achieved which
lie
significantly above the reference substances such as polyvinylpyrrolidone.
The solid detergent formulations comprise in particular the following
components:
(a) 0.05 to 20% by weight of at least one hydrophobically modified poly-
C2-C4-alkylenimine,
(b) 0.5 to 40% by weight of at least one nonionic, anionic and/or cationic
surfactant,
(c) 0.5 to 50% by weight of an inorganic builder,
(d) 0 to 10% by weight of an organic cobuilder and
(e) 0.1 to 60% by weight of other customary ingredients, such as extenders,
enzymes, perfume, complexing agents, corrosion inhibitors, bleaches, bleach
activators, bleach catalysts, further color protection additives and dye
transfer
inhibitors, graying inhibitors, soil release polyesters, fiber protection
additives,
silicones, dyes, bactericides and preservatives, dissolution improvers and/or
disintegrants, water;
where the sum of components (a) to (e) is 100% by weight.
The solid detergent formulations may be present in powder, granule, extrudate
or tablet
form.
The liquid detergent formulations preferably have the following composition:
(a) 0.05 to 20% by weight of at least one hydrophobically modified poly-
C2-Ca-aikylenimine,
(b) 0.5 to 70% by weight of at least one nonionic, anionic and/or cationic
surfactant,
(c) 0 to 20% by weight of an inorganic builder,
(d) 0 to 10% by weight of an organic cobuilder,
(e) 0.1 to 60% by weight of other customary ingredients, such as sodium
carbonate,
enzymes, perfume, complexing agents, corrosion inhibitors, bleaches, bleach
activators, bleach catalysts, further color protection additives and dye
transfer
inhibitors, graying inhibitors, soil release polyesters, fiber protection
additives,
silicones, dyes, bactericides and preservatives, organic solvents, solubility
promoters, hydrotropes, thickeners and/or alkanolamines and
(f) 0 to 99.35% by weight of water,
where the sum of the components (a) to (f) is 100% by weight.
The laundry aftertreatment compositions, in particular laundry care rinse
compositions,
preferably comprise
(a) 0.05 to 20% by weight of at least one hydrophobically modified poly-
C2-C4-alkylenimine,
(b) 0.1 to 40% by weight of at least one cationic surfactant,
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(c) 0 to 30% by weight of at least one nonionic surfactant,
(d) 0.1 to 30% by weight of other customary ingredients, such as silicones,
other
lubricants, wetting agents, film-forming polymers, fragrances and dyes,
stabilizers, fiber protection additives, further color protection additives
and dye
5 transfer inhibitors, complexing agents, viscosity modifiers, soil release
additives,
solubility promoters, hydrotropes, corrosion protection additives,
bactericides and
preservatives and
(e) 0 to 99.75% by weight of water,
where the sum of the components (a) to (e) is 100% by weight.
Suitable nonionic surfactants (B) here are primarily: -
- alkoxylated Cs-C22-alcohofs, such as fatty alcohol alkoxylates, oxo alcohol
=
alkoxylates and Guerbet alcohol ethoxylates: the alkoxylation can take place
with
ethylene oxide, propylene oxide and/or butylene oxide. Block copolymers or
random copolymers may be present. Per mole of alcohol, they usually comprise 2
to 50 mol, preferably 3 to 20 mol, of at least one alkylene oxide. A preferred
alkylene oxide is ethylene oxide. The alcohols preferably have 10 to 18 carbon
atoms;
- alkylphenol alkoxylates, in particular alkylphenol ethoxylates, which
comprise
C6-C14-alkyl chains and 5 to 30 mol of alkylene oxide/mol;
- alkyl polyglucosides which comprise Ca-C=-, preferably C,o-Cia-alkyl chains
and
as a rule 1 to 20, preferably 1.1 to 5, glucoside units;
- N-alkylglucamides, fatty acid amide alkoxylates, fatty acid alkanolamide
alkoxylates, long-chain amine oxides, polyhydroxy(alkoxy) fatty acid
'derivatives,
such as, for example, polyhydroxy fafty acid amides, gemini surfactants, and
block copolymers of ethylene oxide, propylene oxide and/or butylene oxide;
and their mixtures.
Suitable anionic surfactants are, for example:
- sulfates of (fatty) alcohols having 8 to 22, preferably 10 to 18, carbon
atoms, in
particular CsCõ-alcohol sulfates, C12C,4-alcohol sulfates, CV-C18-alcohot
sulfates,
lauryl sulfate, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl
sulfate and
tallow fatty alcohol sulfate;
- sulfated alkoxylated Ca-C22-alcohols (alkyl ether sulfates): compounds of
this type
are prepared, for example, by firstly alkoxylating a Ca-Cz2-, preferably a
C,o-C,s-alcohol, e.g. a fatty alcohol, and then sulfating the alkoxylation
product.
For the alkoxylation, ethylene oxide is preferably used;
- linear Ca-C2o-alkylbenzenesulfonates (LAS), preferably linear
Cs-C,3-alkylbenzenesulfonates and alkyftoluenesulfonates;
- alkanesulfonates, in particular Ca-C24-, preferably C,o-C,a-
afkanesulfonates;
- olefinsulfonates;
- faity acid and fatty acid ester sulfonates;
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11
- soaps, such as the Na and K safts of C8-C24-carboxylic acids,
and mixtures thereof.
The anionic surfactants are preferably added to the detergent in the form of
salts.
Suitable salts here are, for example, alkali metal salts, such as sodium,
potassium and
lithium salts, and ammonium salts, such as hydroxyethylammonium,
di(hydroxyethy!)ammonium and tri(hydroxyethyi)ammonium salts.
Particularly suitable cationic surFactants which may be mentioned are:
- C7-C25-alkylamines;
- N,N-dimethyi-N-(hydroxy-C7-C25-alkyl)ammonium salts;
- mono- and di(C7-C25-alkyl)dimethylammonium compounds quaternized with
alkylating agents;
- ester quats, in particular quatemary esterified mono-, di- and
trialkanolamines
which have been esterified with Ca-Crrcarboxylic acids;
- imidazoline quats, in particular 1-alkylimidazolinium salts of the formulae
II or III
R
R9 N Rs N+
N~
Rao/ Rt1 Rio/
II III
in which the variables have the following meaning:
R9 is C,-C2s-alkyl or C2-C25-alkenyl;
R'O is CI-Ca-alkyl or hydroxy-C1-C4-alkyl;
R" is CrCa-alkyl, hydroxy-CrCa-alkyl or a radical Rl-(CO)-X-(CH2)rn- (X: -0-
or -
NH-; m: 2 or 3),
where at least one radical R9 is C7-C22-alkyl.
Suitable amphoteric surfactants are, for example, alkylbetaines,
alkylamidobetaines,
aminopropionates, aminoglycinates and amphoteric imidazolium compounds.
The advantages according to the invention of the hydrophobically modified
polyalkylenimines come in useful especially in those detergent formulations
which
comprise only a small fraction of anionic surfactants. Preferably, the
fraction of anionic
surfactants, based on the total amount of surfactant in the detergent or
laundry
aftertreatment composition formulation, is not more than 50% by weight, in
particular
not more than 30% by weight and specifically not more than 10% by weight.
Preferably,
the anionic surfactant constitutes not more than 8% by weight, in particular
not more
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than 5% by weight, based on the total weight of the formulation.
Suitable inorganic builders are, in particular:
- crystalline and amorphous alumosilicates with ion-exchanging properties,
such as
in particular zeolites: various types of zeolites are suitable, in particular
the
zeolites A, X, B, P, MAP and HS in their Na form or in forms in which Na is
partially replaced by other cations such as Li, K, Ca, Mg or ammonium;
- crystalline silicates, such as in particular disilicates and sheet
silicates, e.g. S-
and (3-Na2Si2O5. The silicates can be used in the form of their alkali metal,
alkaline earth metal or ammonium salts, preference being given to the Na, Li
and
Mg silicates;
- amorphous silicates, such as sodium metasilicate and amorphous disilicate;
- carbonates and hydrogencarbonates: these can be used in the form of their
alkali
metal, alkaline earth metal or ammonium salts. Preference is given to Na, Li
and
Mg carbonates and hydrogencarbonates, in particular sodium carbonate and/or
sodium hydrogencarbonate; and
- polyphosphates, such as pentasodium triphosphate.
Suitable organic cobuilders are in particular:
- low molecular weight carboxylic acids, such as citric acid, hydrophobically
modified citric acid, e.g. agaricic acid, malic acid, tartaric acid, gluconic
acid,
glutaric acid, succinic acid, imidodisuccinic acid, oxydisuccinic acid,
propanetricarboxylic acid, butanetetracarboxylic acid,
cyclopentanetetracarboxylic acid, alkyl- and alkenylsuccinic acids and
aminopolycarboxylic acids, e.g. nitrilotriacetic acid, 0-alaninediacetic acid,
ethylenediaminetetraacetic acid, serinediacetic acid, isoserinediacetic acid,
N-(2-hydroxyethyl)iminoacetic acid, ethylenediaminedisuccinic acid and methyl-
and ethylglycinediacetic acid or alkali metal salts thereof;
- oligomeric and polymeric carboxylic acids, such as homopolymers of acrylic
acid
and aspartic acid, oligomaleic acids, copolymers of maleic acid with acrylic
acid,
methacrylic acid or Cz-Czz-olefins, e.g. isobutene or long-chain a-olefins,
vinyl
C1-C8-alkyl ethers, vinyl acetate, vinyl propionate, (meth)acrylic acid esters
of
C,-Ca-alcohols and styrene. Preference is given to the homopolymers of acrylic
acid and copolymers of acrylic acid with maleic acid. The oligomeric and
polymeric carboxylic acids are used in acid form or as sodium salt;
- phosphonic acids, such as, for example, 1-hydroxyethylene(1,1-diphosphonic
acid), aminotri(methylenephosphonic acid), ethylenediaminetetra(methylene-
phosphonic acid) and diethylenetriaminepenta(methylenephosphonic acid) and
alkali metal salts thereof.
Suitable graying inhibitors are, for example, carboxymethylcellulose and graft
polymers
of vinyl acetate onto polyethylene glycol.
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Suitable bleaches are, for example, adducts of hydrogen peroxide onto
inorganic salts,
such as sodium perboratemonohydrate, sodium perboratetetrahydrate and sodium
carbonate perhydrate, and percarboxylic acids, such as phthalimidopercaproic
acid.
Suitable bleach activators are, for example, N,N,N',N'-
tetraacetylethylenediamine
(TAED), sodium p-nonanoyloxybenzenesulfonate and N-methylmorpholinium
acetonitrile methyl sulfate.
Enzymes preferably used in detergents are proteases, lipases, amylases,
cellulases,
oxidases and peroxidases.
Suitable further dye transfer inhibitors are, for example, homopolymers,
copolymers
and graft polymers of 1-vinylpyrrolidone, 1-vinylimidazole or 4-vinylpyridine
N-oxide.
Homopolymers and copolymers of 4-vinylpyridine reacted with chloroacetic acid
are
also suitable as dye transfer inhibitors.
Detergent ingredients are otherwise generally known. Detailed descriptions can
be
found, for example, in WO-A-99/06524 and 99/04313; in Liquid Detergents,
Editor:
Kuo-Yann Lai, Surfactant Sci. Ser., Vol. 67, Marcel Decker, New York, 1997,
p. 272-304.
Application of hydrophobically modified poly-C2-C4-alkylenimines according to
the
invention.
Selected coiored fabric (EMPA 130, EMPA 132, EMPA 133 or EMPA 134) was washed
in the presence of white test fabric made of cotton and ballast fabric made of
cotton/polyester and also of polyester using a detergent at 60 C with the
addition of the
LCST polymers. After the washing cycle, the fabrics were rinsed, spun and
dried. In
order to determine the dye transfer-inhibiting effect, the coloration of the
white test
fabric was determined photometrically (Photometer: Elrepho 2000 from
Datacolor).
The reflectance values measured at the test fabric were used to determine the
color
intensity of the coloration in accordance with the method described in A. Kud,
Seifen,
Ole, Fette, Wachse, volume 119, pages 590-594 (1993). The color intensity for
the
experiment with the respective test substance, the color intensity for the
experiment
without test substance and the color intensity of the test fabric before
washing were
used to ascertain the dye transfer-inhibiting effect of the test substance
according to
the following formula in ~o.
DTI effect [%] = color intensity (without polymer) - color intensity (with
polymer) x 100
color intensity (without polymer) - color intensity (before washing)
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The washing conditions are given in Table 1. The composition of detergent A
used is
given in Table 2. The test results. for the dye transfer inhibition are listed
in Table 3.
Table 1
Washing conditions
Washing conditions main wash cycle
Machine Launder-o-meter from Atlas, Chicago, USA
Detergent dosing 5.0 g/l of liquor detergent A
Water hardness 3 mmol/i Ca : Mg 4: 1
Liquor ratio 1 :16
Wash temperature 60 C
Wash time 30 min
Polymer dosing 0.05 g/l liquor
Colored fabric 1 g EMPA 130 (C.I. Direct Red 83:1)
1 g EMPA 132 (C.I. Direct Black 22)
1 g EMPA 133 (C.I. Direct Blue 71)
0.5 g EMPA 134 (C.I. Direct Orange 39)
(all Swiss Federal Laboratories for Materials Testing, St. Gallen,
SwÃtzeriand)
Test fabric 5 g cotton fabric 221 (bleached)
Ballast fabric 5 g blended fabric 768 (65 : 35 polyester : cotton)
+
g polyester fabric 854
5
Table 2
Composition of detergent A (liquid detergent)
Ingredients [% by wt.]
C13C15-oXo alcohol x 7 EO 12
C -afcohoi x 5 EO 5
Citric acid 3
Propylene glycol 10
Ethanol 2
Diethylenetriaminepenta(methylenephosphonic acid) 1.0
Water ad 100
Adjust to pFf 9 with sodium hydroxide solution.
Preparation of hydrophobically modified polyethylenimine derivatives:
Starting materials:
Polyethylenimine A: Mw 25 000 g/mol; amine number: 20.14 mmol/g ratio of
primary:secondary:tertiary nitrogen atoms: 1.0:1.1:0.7, determined by means of
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13C-NMR.
Polyethylenimine B: Mw 5000 g/mol; amine number: 9.22 mmol/g ratio of
primary:secondary:tertiary nitrogen atoms: 1.0:1.0:0.7, determined by means of
13C-NMR.
5
Polymer 1
350 g of polyethylenimine A were initially introduced into toluene (300 mi).
Heating to
100 C was then carried out. After adding palmitic acid (179 g), the reaction
mixture was
brought to 120 C and, while stirring, the water which formed was distilled off
via a
10 water separator (7h). Toiuene was then removed under reduced pressure. The
product
was obtained as an orange, very viscous oil (503 g).
Polymer 2
210 g of polyethylenimine A were initially introduced into toluene (300 mi).
Heating to
15 100 C was then carried out. After adding palmitic acid (322 g), the
reaction mixture was
brought to 120 C and, while stirring, the water which formed was distilled off
via a
water separator (50h). Toluene was then removed under reduced pressure. The
product was obtained as an orange wax (501 g).
Polymer 3
200 g of polyethylenimine A were initially introduced into toluene (700 ml).
Heating to
100 C was then carried out. After adding palmitic acid (502 g), the reaction
mixture was
brought to 120 C and, while stirring, the water which formed was distilled off
via a
water separator (30h). 400 mi of toluene were removed from the reaction
mixture and
then water was distilled off for a further 12 h. The toluene was then removed
under
reduced pressure. The product was obtained as a brown wax (670 g).
Polymer 4
231 g of polyethylenimine A were initially introduced and heated to 100 C. The
C12
epoxide (Vikolox 12; 425 g) was added dropwise. The mixture was then stirred
at
100 C for 9 h. The yellow, highly viscous oil was obtained (656 g).
Polymer 5
199 g of polyethylenimine A were initially introduced into toluene (400 ml).
Heating to
100 C was then carried out. After adding dodecylic acid (396 g), the reaction
mixture
was brought to 120 C and, while stirring, the water which formed was distilled
off via a
water separator (30h). The toluene was then removed under reduced pressure. A
viscous reddish-brown product was obtained (558 g).
Polymer 6
149 g of polyethylenimine A were initially introduced into toluene (400 mi)
and heated
to 100 C. After adding stearic acid (424 g), the reaction mixture was brought
to 120 C
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and, while stirring, the water which formed was distilled off via a water
separator (30h).
The toluene was then removed under reduced pressure. The product was obtained
as
a yellow-pale brown wax (451 g).
Polymer 7
550 g of polyethylenimine B were initially introduced into toluene (500 mi).
Heating to
100 C was then carried out. After adding palmitic acid (258 g), the reaction
mixture was
brought to 120 C and, while stirring; the water which formed was distilled off
via a
water separator (3d). The toluene was then removed under reduced pressure. The
product was obtained as an orange wax (510 g).
Polymer 8
434 g of polyethylenimine B were initially introduced into toluene (400 ml).
Heating to
100 C was carried out. After adding paimitic acid (497 g), the reaction
mixture was
brought to 120 C and, while stirring, the water which formed was distilled off
via a
water separator (3d). The toluene was then removed under reduced pressure. The
product was obtained as an orange wax (680 g).
Polymer 9
Polymer 8 (666 g) was heated to 75 C. Dimethyl suifate was then metered in
(71.8 g;
Dosimat 2.5 milmin). The excess dimethyl sulfate was then removed under
reduced
pressure. The product was obtained as a brown amorphous substance (407.5 g).
Table 3: Application liquid detergent A
DTI effect [%]
EMPA 130 EMPA 132 EMPA 133 EMPA 134
Polymer 1 53.6 45.6 70.5 67.1
Polymer 2 84.3 64.7 89.1 83.1
Polymer 3 87.9 68.3 91.4 78.7
Polymer 4 66.1 30.8 80.3 68.0
Polymer 5 86.2 62.7 91.1 84.7
Polymer 6 86.9 72.9 90.9 84.7
Polymer 7 51.8 37.4 72.7 62.5
Polymer 8 85.3 63.5 90.1 75.0
Polymer 9 84.1 67.1 91.4 80.3
PEI 25 000 neg. effect 46.1 40.2 41.7
PE1 5000 neg. effect 54.3 25.8 53.2
PVP* 22.9 33.7 94.0 35.8
PVP = polyvinylpyrrolidone with K value 30
PEI 25 000 = polyethylenimine A
PEI 5000 = polyethylenimine B
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Negative effect: polymer does not exhibit inhibition of the dye transfer, but
favors it.
*Polyvinylpyrrolidone: reference substance
