BRPI0720573A2 - USE OF HYDROFOBICALLY MODIFIED POLYCHYLENEIMINS - Google Patents

Abstract

The invention relates to the use of hydrophobically modified polyalkylenimines as dye transfer inhibitors.

Description

I “USE OF OBCTIVELY MODIFIED POLYCHYLENOIMINS

description

The invention relates to the use of hydrophobically modified polyalkyleneimines as dye transfer inhibitors.

During the washing process, dye molecules are often detached from colored textiles; these can in turn bind to other textiles. In order to counterbalance this undesirable dye transfer, so-called dye transfer inhibitors are often used. These are often polymers, which comprise monomers with heterocyclic radicals - nitrogen, in copolymerized form.

Thus, for example, DE 4235798 describes copolymers of compounds of 1-vinyl pyrrolidone, 1-vinyl imidazole, 1-vinyl imidazolium or mixtures thereof; in addition to basic ethylenically unsaturated monomers containing nitrogen; and, if appropriate, other monoethylenically unsaturated monomers and their use to inhibit 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 reports are characterized in part by a good inhibition of dye transfer in the washing processes. However, they generally have poor compatibility with other conventionally used detergent constituents. Thus, in the case of liquid detergents, there is a risk of incompatibilities, for example in the form of opacity or phase separations.

On several occasions, the use of hydrophobically modified polyalkyleneimines in detergent and cleaning formulations has been described. DE 2025829 describes reaction products of glycidyl fatty acid esters with polyethylene imines and their use as fabric softeners.

DE 2046304 describes the reaction products of fatty acids or fatty acid esters with polyethyleneimines and their use as fabric softeners.

DE 2165900 describes the reaction products of alkyl glycidyl ethers with polyethylene imines and their use with greyness inhibitors.

US 3,576,341 describes alkylated polyethyleneimines, wherein the alkyl groups have from 16 to 30 carbon atoms, and their use as fabric softeners.

WO 2002/095122 describes the use of hydrophobically modified polyethylene imines as wrinkle additives for detergent formulations.

An effect of dye transfer for inhibition of hydrophobically modified polyalkyleneimines during washing is not described in any of these citations.

It has been considered an object of the present invention to provide substances with a good dye transfer inhibiting effect during the washing process. These substances should, in addition, be well compatible with conventional detergent constituents, in particular for liquid detergent formulations.

These and other objects were surprisingly achieved by hydrophobically modified C 2-4 polyalkylene imines.

The invention therefore relates to the use of hydrophobically modified C2-A polyalkyleneimines, in particular hydrophobically modified polyethyleneimines, as dye transfer inhibitors in textile detergent compositions.

Hereinafter, hydrophobically modified C2.4 polyalkylene imines are to be understood to mean 5 C2-4 polyalkylene imines, wherein the hydrogen atoms of primary and secondary amino groups are partially or completely substituted by aliphatic, saturated or unsaturated hydrocarbon radicals, straight or branched, such as alkyl, alkenyl, alkadienyl or hydroxyalkyl radicals. Hydrocarbon radicals generally have at least 8, for example from 8 to 30 carbon atoms, more preferably from 10 to 22 carbon atoms, and particularly from 10 to 18 carbon atoms. .

Depending on the hydrophobicizing agent used in each case, hydrocarbon radicals may be attached to the nitrogen atom of polyalkylene imine C2.4 directly or through a functional group, for example through a carbonyl group (* C (= 0) - # ), through an oxycarbonyl group (OC (= 0) -), through an aminocarbonyl group (-NH-C (= 0) -), through a carbonyloxyhydroxypropyl group (* -C (= 0) -0-CH 2) -CH (OH) -CH 2 -) via a 2-oxycarbonylethylenecarbonyl group (* -CH (COOH) -CH 2 -CO- #) or through a radical of the formula -CH 2 -C (= O) -CH * - C (= O) - (in the above formulas, * represents the bond of the hydrocarbon radical and # represents the bond to the nitrogen atom of the C 2-4 polyalkylene imine.) The hydrocarbon radical may also form an aldimine group or a ketimine group with C2_4 polyalkylene imine nitrogen, or can be attached to 2 C2-4 polyalkyleneimine nitrogen atoms through the carbon atom of a cyclic amidine group here.

Preferred are those hydrophobically modified C 2-4 polyalkyleneimines, wherein the hydrocarbon radical is bonded to the nitrogen atom of the C 2-4 polyalkyleneimine or via a carbonyl group, the latter being particularly preferred. Preferably the hydrocarbon radicals are linear. Preferably, the hydrocarbon radicals are saturated.

Thus, the hydrocarbon radicals in the preferred hydrophobically modified C2-4 polyalkyleneimines are present in the form of C8-30 alkyl, C8-30 alkylcarbonyl, C8-30 alkenyl, C8-30 alkenylcarbonate, C8-30 alkyienylcarbonyl and / or C8-30 hydroxyalkyl groups, in particular in the form of C10-22 alkyl, C10-22 alkylcarbonyl, C10-22 alkenyl, C10-22 alkenyl carbonyl, C10-22 alkadienyl, C10-22 alkadienyl carbonyl, and / or hydroxy groups C10-22 alkyl, particularly preferably as C10-18 alkyl alkyl C10-18 alkylcarbonyl, C10-18 alkenyl, C10-18 alkenylcarbonyl, C10-18 alkadienyl, Ckm8-alkadienylcarbonyl, and / or C10-18 hydroxyalkyl wherein the alkyl, hydroxyalkyl, alkenyl, and alkadeinyl radicals of the above-mentioned groups are preferably linear.

In hydrophobically modified C2-4 polyalkyleneimines

Particularly preferred hydrocarbon radicals are present as C8-30 alkylcarbonyl or C8.30 alkenylcarbonyl groups, in particular as C0.22 alkylcarbonyl or C10-22 alkenylcarbonyl groups, and specifically as C10-22 alkenylcarbonyl groups. C10-18 alkylcarbonyl or C10-18 alkenylcarbonyl, wherein the alkyl and alkenyl radicals of the aforementioned groups are preferably linear.

In addition, those hydrophobically modified C 2-4 polyalkyleneimines in which at least 10 mol%, in particular at least 15 mol% and particularly preferably at least 25 mol%, for example from 5 to 80 mol% are preferred. , in particular from 15 to 70 mol%, and specifically from 20 to 60 mol% of the nitrogen atoms of C2.4 polyalkyleneimine carry a hydrocarbon radical.

Correspondingly, the hydrocarbon radical moiety preferably comprises from 25 to 95% by weight, in particular from 30 to 90% by weight, and specifically from 40 to 80% by weight. based on the total weight of the hydrophobically modified C2.4 polyalkylenimine.

The weight average molecular weight Mw of the hydrophobically modified 5 C 2-4 polyalkyleneimines suitable according to the invention is typically in the range of 1000 to 1000,000 Daltons. For use according to the invention, it has further been found to be advantageous if the hydrophobically modified C 2-4 polyalkylene imine has an average molecular weight number in the range of 3000 to 300,000 Daltons and in particular in a range of 6000 to 200,000 Daltons. . Molecular weights provided herein refer to the molecular weights specified by dynamic light scattering and measured in aqueous solutions diluted at 25 ° C, which correspond to the weight average molecular weight.

The hydrophobically modified C2-4 polyalkyleneimines used according to the invention, in particular hydrophobically modified polyethyleneimines, may, based on the C2.4 polyalkyleneimine, on which they are based, be linear or branched, with preference being given to those which are branched to the C 2-4 polyalkyleneimine moiety. Whereas linear C2.4 polyalkyleneimines are composed exclusively of repeating units of formula A wherein Q is C2_4 alkylene, C2_4 polyalkyleneimines have, in addition to linear repeating units, tertiary nitrogen atoms according to structural unit B :

-N-Q-

H

-N- *

H

Qx

Yl-Q-

/

Q

■ Ν-

Α B

Preferred are those branched hydrophobically modified C 2 polyalkyleneimines, in particular those

■ 4 branched hydrophobically modified polyethyleneimines which, based on the C2.4 polyalkyleneimine, on which they are based, have on average one polyalkyleneimine molecule at least one, preferably at least 5, or at least 10 points according to formula 5B. Particularly at least 5%, in particular at least 10%, and particularly preferably at least 15%, for example from 5 to 40%, and of a Specifically, 15 to 35% of the nitrogen atoms of C2.4 polyalkylenimine are tertiary nitrogen atoms.

Particularly in the case of high degrees of branching, that is if at least 10%, in particular at least 15%, for example from 10 to 40%, in particular from 15 to 35% of the C2-6 polyalkyleneimine nitrogen groups.

4 of origin are tertiary nitrogen atoms, hydrophobically modified C2.4 polyalkylenomines have a structure similar to a shell-core structure, wherein the C2.4 polyalkyleneimine moieties form the nucleus and hydrophobic radicals form the shell.

Hydrophobically modified C2.4 polyalkyleneimines may be present in cross-linked or non-cross-linked form, and, in addition to hydrophobic modification, may be quaternized and / or modified by reaction with alkylene oxides, C1-4 dialkyl carbonates, C2 alkylene carbonates. 4 or C1-4 carboxylic acids.

Preferably the hydrophobically modified C 2-4 polyalkyleneimines are not crosslinked.

According to a first preferred embodiment of the invention, hydrophobically modified C2.4 polyalkylenomines have no further modification other than hydrophobic modification.

According to a second preferred embodiment of the invention the C2.4 polyalkyleneimines are quaternized in addition to the hydrophobic modification. Such hydrophobically quantified C2.4 polyalkylenomines preferably have no further modification. The degree of quatemization, that is, the number of quaternized nitrogen atoms, based on the total amount of hydrophobically modified polyalkyleneimine C2-4 nitrogen atoms, has no further modification. The degree of quatemization, that is, the number of quaternized nitrogen atoms 5 based on the total amount of nitrogen atoms of hydrophobically modified polyalkyleneimine C2.4, preferably not exceeding 80 mol%, in particular not exceeding 50 mol%, for example from 1 to 80 mol%, and in particular from 5 to 50 mol%, based on the nitrogen atoms of C 2-4 polyalkyleneimine.

Hydrophobically modified C2.4 polyalkyleneimines,

which are used according to the invention, form part of the prior art cited at the outset, or may be prepared in a manner analogous to the methods described herein. As a rule, hydrophobically modified C2.4 polyalkyleneimines are prepared by analogous reaction to unmodified C2-4 polyalkyleneimines polymer with a hydrophobicizing agent. Accordingly, one embodiment of the invention relates to the use of a hydrophobically modified C2.4 polyalkyleneimine obtainable by a process which comprises reacting an unmodified C2.4 polyalkyleneimine, in particular a branched C2.4 polyalkyleneimine. - modified, and specifically a non-modified branched polyethyleneimine with a hydrophobization agent.

Examples of other suitable hydrophobicizing agents

are :

i) long chain straight or branched carboxylic acids having from 8 to 30 carbon atoms, preferably from 10 to 22 carbon atoms, particularly from 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, palmitic 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, palmitic acid and oleic acid, and their amide-forming derivatives, such as the acid chlorides, anhydride esters of the specified carboxylic acids and mixtures thereof,

(ii) straight or branched alkyl halides having from 8 to 30 carbon atoms, preferably from 10 to 22 carbon atoms, in particular from 10 to 18 carbon atoms, in the linear 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 from 8 to 30 carbon atoms, preferably from 10 to 22 carbon atoms, in particular from 10 to 18

carbon atoms in the straight or branched alkyl radical such that hexadecenyl oxide, dodecenyl oxide, and octadecenyl oxide and mixtures thereof,

iv) alkyl ketene dimers having from 8 to 30 carbon atoms, preferably from 10 to 22 carbon atoms, in particular

of 10 to 18 carbon atoms in the straight or branched alkyl radical such as lauryl ketene, palmityl ketene, stearyl ketene and oleyl ketene dimers, and mixtures thereof,

(v) cyclic dicarboxylic acid anhydrides, in particular alkyl-substituted succinic anhydrides having from 8 to 30 carbon atoms;

preferably from 10 to 22 carbon atoms, in particular from 10 to 18 carbon atoms, in the straight or branched alkyl radical, such as dodecenyl succinic anhydride, tetradecyl succinic anhydride, hexadecenyl succinic anhydride and mixtures thereof,

vi) alkyl isocyanates having from 8 to 30 carbon atoms, preferably from 10 to 22 carbon atoms, in particular from 10 to 18 carbon atoms in the straight or branched alkyl radical, such as tetradecyl isocyanate, hexadecyl isocyanate , octadecyl isocyanate and mixtures thereof,

vii) chloroform acid esters of linear alkanols or

branched or alkenols having from 8 to 30 carbon atoms, preferably from 10 to 22 carbon atoms, in particular from 10 to 18 carbon atoms, and mixtures thereof, and

viii) linear or branched aliphatic aldehydes having from 8 to 30 10 carbon atoms, preferably from 10 to 22 carbon atoms, in particular from 10 to 18 carbon atoms, and dialkyl ketones having in total from 8 to 30 atoms preferably from 10 to 22 carbon atoms, and in particular from 10 to 18 carbon atoms, in the two alkyl groups and mixtures thereof.

Preferred hydrophobicizing agents are carboxylic acids

straight or branched long chain having from 8 to 30 carbon atoms, preferably from 10 to 22 carbon atoms, in particular from 10 to 18 carbon atoms, in the alkyl or alkenyl radical and amide-forming derivatives thereof in particular linear saturated carboxylic acids having from 10 to 22 carbon atoms, in particular from 10 to 18 carbon atoms in the alkyl radical.

Preferred hydrophobicizing agents are also alkyl epoxides having from 8 to 30 carbon atoms, preferably from 10 to 22 carbon atoms, and in particular from 10 to 18 carbon atoms.

Unmodified C2.4 polyalkyleneimines, which form the

The bases of the hydrophobically modified C 2-4 polyalkyleneimines used according to the invention comprise ethyleneimine (aziridine) and higher homologues thereof, propyleneimine (methylaziridine) and butyleneimines (1,2-dimethylaziridine, 1,1-dimethylaziridine and 1- ethylaziridine), ethyleneimine copolymers with their higher counterparts, and the ethyleneimine polyamidoamine or polyvinylamine graft polymers and / or their higher counterparts.

Also suitable are C2-4 alkyleneimine graft polymers described in WO 02/095122, such as ethyleneimine on polyamidoamines or polyvinylamines. Such graft polymers generally have a weight fraction of C 2-4 alkyleneimines of at least 10% by weight, in particular at least 30% by weight, for example from 10 to 90% by weight. in particular from 10 to 85% by weight based on the total weight of unmodified C 2-4 polyalkyleneimine.

In particular, the unmodified C 2-4 polyalkyleneimines are branched C 2-4 polyalkyleneimines, preferably branched polyethyleneimines, in particular branched polyethylenimines, and specifically branched ethyleneimine homopolymers.

Preferably, the unmodified C2.4 polyalkyleneimine used for its preparation is branched, with respect to the degree of branching as described above for hydrophobically modified C2-4 polyalkyleneimines.

Preferably, the unmodified C 2-4 polyalkyleneimine used for the preparation has an average molecular weight number in the range of 1000 to 200,000 Daltons, in particular in the range of 2000 to 100,000 Daltons.

The reaction of unmodified C 2-4 polyalkyleneimine with the hydrophobicizing agent may occur in a manner analogous to processes known in the prior art. The reaction conditions naturally depend on the type and functionality of the hydrophobicizing agent.

The reaction may occur without a diluent or in solution. The reaction is preferably performed in a suitable solvent for the reaction. Examples of suitable solvents are hydrocarbons, in particular aromatic hydrocarbons, for example alkyl benzenes, such as xylenes, toluene, cumene, tert-butyl benzene, and the like.

If appropriate, the reaction may be performed in the presence of 5 catalysts, which improve the reactivity of the hydrophobicization agent to C2-4 polyalkyleneimine. The type of catalyst depends in itself on the type and reactivity of the hydrophobicization agent. Catalysts are usually Lewis acids or Brönsted acids. Often, for example in the case of carboxylic acids, it is possible to dispense with the use of catalysts.

In the case of preferred carboxylic acids and carboxylic acid derivatives according to the invention, it has been found advantageous to remove the low molecular weight products (water, alcohols, or hydrogen chloride) which are formed during the reaction from the mixture. 15 of the reaction. For example, in the case of carboxylic acids, the water formed should preferably be removed from the reaction mixture by a carrier. Typical carrier agents are hydrocarbons, in particular alkyl aromatics, such as toluene or xylenes. Preferably, the reaction will be performed in an organic solvent suitable as a carrier.

As a rule, the hydrophobicizing agent will be used in an amount that corresponds to the desired functionality, and it is also possible to use the excess hydrophobicizing agent. In this regard, the foregoing for the functionalization of hydrophobicized polyalkyleneimine applies analogously to the molar ratio of hydrophobicization agent to nitrogen atoms in the unmodified polyalkyleneimine. In particular, the hydrophobicising agent, calculated as the remaining hydrophobicizing agent parts in the product (thus, the amount of hydrophobicizing agent minus any low molecular weight products such as water) will be used in an amount from from 0.35 to 20 parts by weight, in particular in an amount of 0.5 to 10 parts by weight, part by weight, of C2-A-polyalkyleneimine.

According to a preferred embodiment of the invention, the hydrophobically modified C2-A polyalkyleneimines are quaternized. Thus, the preparation of hydrophobically modified C 2-4 polyalkyleneimines is quaternized. Thus, the preparation of hydrophobically modified C 2-4 polyalkyleneimines comprises a quatemization. Quantization may occur before, or in particular after hydrophobicization.

For the quantification, in particular, alkylating agents, such as alkyl halides, which generally have from 1 to 10 carbon atoms in the alkyl radical, or dialkyl sulfates, which generally comprise Alkyl radicals having from 1 to 10 carbon atoms are used. Examples of suitable alkylating agents of 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. Other suitable alkylating agents are, for example, benzyl halides, particularly benzyl chloride and benzyl bromide; chloroacetic acid; fluorosulfuric acid methyl ester; diazomethane; oxon compounds such as trimethyl oxonium tetrafluorobate; alkylene oxides, such as ethylene oxide, propylene oxide and glycidol, which are used in the presence of acids; cationic epichloroidrins. Preferred quaternizing agents are methyl chloride, dimethyl sulfate and diethyl sulfate. During quaternization, secondary or in particular tertiary nitrogen atoms of the source C2-4 polyalkyleneimine moiety are converted to quaternary nitrogen atoms, ergo ammonium groups, as a result of which hydrophobically modified C2_4 polyalkyleneimine is supplied at full positive charge. .

Hydrophobically modified C2.4 polyalkyleneimines are generally soluble or dispersible in water, and may be used in solid and liquid detergents and in laundry post-treatment compositions. They are characterized in particular by their high compatibility with conventional detergent constituents, in particular with the constituents of liquid detergent formulations, specifically those having a low anionic surfactant content.

Incorporation into the respective detergent or composition for the

laundry after-treatment occurs in a manner known per se, hydrophobically modified polyalkyleneimines being used in liquid form, i.e. in a dissolved or dispersed form. Hydrophobically modified polyalkyleneimines may also be used in powder or granule form.

Dye transfer over the washed fabric, while the associated undesirable discoloration of this fabric are effectively inhibited. Even at concentrations of from 10 to 150 ppm of hydrophobically modified polyalkyleneimine in the wash or rinse liquid, good to very good dye transfer inhibition effects are achieved which are significantly above the reference substances such as than polyvinyl pyrrolidone.

Solid detergent formulations particularly comprise the following components:

(a) from 0,05 to 20% by weight of at least one

hydrophobically modified polyalkyleneimine C2-4,

(b) from 0.5 to 40% by weight of at least one nonionic, anionic and / or cationic surfactant;

(c) from 0.5 to 50% by weight of an inorganic reinforcer; (d) from 0 to 10% by weight of an organic co-reinforcer; and

(e) from 0.1 to 60% by weight of other customary ingredients such as extenders, enzymes, perfume, complexing agents, corrosion inhibitors, bleach, bleach activators, bleach catalysts, other

color protection additives and dye transfer inhibitors, grayish inhibitors, dirt release polyesters, fiber protection additives, silicones, dyes, bactericides and preservatives, dissolution enhancing agents and / or disintegration, water,

wherein the sum of the components (a) to (e) is 100% by weight. Solid detergent formulations may be present.

in powder, granule, extruded 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 C2.4 polyalkyleneimine;

(b) from 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 reinforcer,

(d) from 0 to 10% by weight of an organic co-reinforcer,

(e) from 0.1 to 60% by weight of other usual ingredients such as

Sodium carbonate, enzymes, perfume, complexing agents, corrosion inhibitors, bleach, bleach activators, bleach catalysts, other color protection additives and dye transfer inhibitors, greyish inhibitors, polyesters for release dirt, fiber protection additives, silicones, dyes, bactericides and preservatives, organic solvents, solubility promoters, hydrotopes, thickening agents and / or alkanolamines and

(f) from 0 to 99, 35% by weight of water,

wherein the sum of components (a) to (f) is 100% by weight. Suitable nonionic surfactants (B) in this case are primarily:

- C8.22 alkoxylated alcohols, such as fatty alcohol alkoxylates, oxo alcohol alkoxylates and Guerbet alcohol ethoxylates: alkoxylation

may occur with ethylene oxide, propylene oxide and / or butylene oxide. Block copolymers or random copolymers may be present. Per mol of alcohol they usually comprise from 2 to 50 mol, preferably from 3 to 20 mol, of at least one alkylene oxide. A preferred alkylene oxide is ethylene oxide. The alcohols 10 preferably have from 10 to 18 carbon atoms;

alkylphenol alkoxylates, in particular alkylphenol ethoxylates, which comprise C 1-6 alkyl chains and from 5 to 30 mol of alkylene oxide / mol;

polyglycoside alkyls, which comprise Cs-22 alkyl chains, preferably C1-10 alkyl chains, and as a rule of 1 to 20, preferably 1.1 to 5, glycoside units;

- N-alkyl glucamides, fatty acid amide alkoxylates, fatty acid alkanolamide alkoxylates, long chain amine oxides, polyhydroxy (alkoxy) fatty acid derivatives such as, for example, amides of the

fatty acid polyhydroxy, gemini surfactants, and block copolymers of ethylene oxide, propylene oxide and / or butylene oxide;

and their mixtures.

Suitable anionic surfactants are, for example:

- fatty alcohol sulphates having from 8 to 22, preferably from 10 to 18 carbon atoms, in particular Cç.n alcohol sulphates,

C12-14 alcohol sulfates, C12-18 alcohol sulfates,

lauryl sulfates, cetyl sulfate, myristyl sulfate, palmnityl sulfate, stearyl sulfate, and tallow fatty alcohol sulfate;

sulfated alkoxylated C8-22 alcohols (alkyl ether sulfates): Compounds of this type are prepared, for example, primarily by alkoxylation of a C8.22 alcohol, preferably C10-18, for example a fatty alcohol, and then sulfation of the product. of alkoxylation.

For alkoxylation, ethylene oxide is preferably used; linear C8-2O alkylbenzenesulfonates (LAS), preferably linear C9.13 alkylbenzenesulfonates and alkyltholuenesulfonates;

alkanesulfonates, in particular C8-24 alkanesulfonates, preferably C10-18 alkanesulfonates;

olefin sulfonates;

fatty acid and fatty acid ether sulfonates; soaps that the salts of Na and K of carboxylic acids

C8-24,

and mixtures thereof.

Anionic surfactants are preferably added to the detergent as salts. Salts in this case are, for example, alkali metal salts, such as sodium, potassium and lithium salts, and ammonium salts, such as hydroxyethyl ammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts .

Particularly suitable cationic surfactants which may be mentioned are:

- C7.25 alkylamines,

N, N-dimethyl-N- (hydroxy C7.25 alkyl) ammonium salts; mono- and di (C7.25 alkyl) ammonium compounds; mono- and di (C7-25 alkyl) dimethylammonium compounds quaternized with alkylating agents;

ester quats, in particular esterified mono-, di- and trialkanolamines, which have been esterified with C8.22 carboxylic acids, in particular 1-alkylimidazolium salts of formulas II or III: wherein the variables have the following meanings: R9 C 1-25 alkyl or C 2-25 alkenyl;

R10 is C1-4 alkyl or hydroxy C1-4 alkyl;

R11 is C1-4 alkyl, hydroxyC1 alkyl or a radical R1 - (CO) - X- (CH2) m - (X: -O- or -NH-; m: 2 or 3),

wherein the at least one radical R 9 is C 7,22 alkyl.

Suitable amphoteric surfactants are, for example, alkyl betaines, alkylamido betaines, aminopropionates, aminoglycinates and amphoteric imidazole compounds.

Advantages according to the invention of hydrophobically modified polyalkyleneimines may be 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 composition formulation or for the aftercare in the laundry, 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 no more than 8 wt%, in particular no more than 5 wt%, based on the total weight of the formulation.

Suitable inorganic reinforcers are in particular:

crystalline and amorphous aluminosilicates having ion exchange properties such that, in particular, zeolites: various types of zeolites are suitable, in particular zeolites A, X, B, P, MAP and HS in their Na or in their form. forms in which Na is partially substituted by other cations such as Li, K, Ca, Mg or ammonium; crystalline silicates such as, in particular, disilicates and sheet silicates, for example δ- and β-Na2Si2Os. Silicates may be used in the form of their alkali metal, alkaline earth metal or ammonium salts, with Na, Li and Mg silicates being preferred;

amorphous silicates such as sodium metasilicate and disilicate

amorphous;

- carbonates and hydrogen carbonates; These may be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Preferred are Na, Li and Mg carbonates and hydrogen carbonates, in particular sodium carbonate and / or sodium hydrogen carbon; and

polyphosphates, such as pentasodium triphosphate.

Suitable organic reinforcers are in particular:

- low molecular weight carboxylic acids such as citric acid, hydrophobically modified citric acid, for example agaric acid, malic acid, tartaric acid, gluconic acid, glutaric acid, succinic acid, imidodissuccinic acid, oxidisuccinic acid, propanotricarboxylic acid, butanotetracarboxylic acid, cyclopentanotetracarboxylic acid, alkyl- and alkenyl succinic acids and aminopolicarboxylic acids, for example nitriloacetic acid, β-alaninadiacetic acid, ethylenediamine acetic acid, serinadiacetic acid, isoserinadiacetic acid, N- (2-hydroxyacetic acid) methyl and ethylglycine diacetic or alkali metal salts thereof;

- oligomeric and polymeric carboxylic acids such as homopolymers of acrylic acid and aspartic acid, oligomalic acids, copolymers of maleic acid with acrylic acid, methacrylic acid or C2-22 olefins, for example isobutene or long chain α-olefins, vinyl ethers C 1-8 alkyls styrene. Homopolymers of acrylic acid and copolymers of acrylic acid with maleic acid are preferred. Oligomeric and polymeric carboxylic acids are used in acid form or as the sodium salt;

- phosphonic acids, for example 1-hydroxyethylene (1,1-

diphosphonic acid), aminotri (methylene phosphonic acid), ethylenediaminetetra (methylenephosphonic acid) and diethylenetriaminapenta (methylenephosphoric acid) and alkali metal salts thereof.

Suitable gray inhibitors are, for example, carboxymethyl cellulose and polyethylene glycol vinyl acetate graft polymers.

Suitable bleaches are, for example, hydrogen peroxide addition products in inorganic salts such as sodium perborate monohydrate, sodium perborate tetrahydrate and sodium carbonate pentahydrate, and percarboxylic acids such as phthalimidopercaproic acid.

Suitable bleach activators are, for example, N, N, N ', N'-tetraacetylenediamine (TAED), sodium p-nonanoyloxybenzene sulfonate and N-methylmorpholine acetonitrile methyl sulfate.

Enzymes, preferably used in

Washings are proteases, lipases, amylases, cellulases, oxidases and peroxidases.

Other suitable dye transfer inhibitors are, for example, 1-vinyl pyrrolidone, 1-vinyl imidazole or 4-vinyl pyridine N-oxide homopolymers, copolymers and graft polymers. 4-Vinyl pyridine homo- and copolymers have been reacted with chloroacetic acid and are also suitable dye transfer inhibitors.

The wash composition ingredients are, on the other hand, commonly 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 C2-A alkyleneimines according to the invention

Selected colored fabric (EMPA 130, EMPA 132, EMPA

133, or EMPA 134) was washed in the presence of white cotton test fabric and ballast fabric produced from cotton / polyester and polyester with a wash composition at 60 ° C with the addition of LCST polymers. After the wash cycle, the tissues were rinsed, centrifuged and dried. In order to determine the dye transfer inhibiting action, the staining of the white test tissue was determined photometrically (Photometer: Elrepho® 2000 from Datacolor). Reflectance values measured on the test tissue were used to determine the color intensity of the stain according to the method described in A. Kud, Seifen, Öle, Fette, Wachse, Volume 119, pages 590-594 (1993). The color intensity for the experiment with the particular test substance, the color intensity for the experiment without the test substance, and the color intensity of the test tissue before washing were used to determine the dye transfer inhibition action. by the test substance by the following formula in%.

DTI Action [%] = Color Intensity (without polymer ') x | 00

Color Intensity (with polymer)

Washing conditions were such as specified in Table I. The composition of detergent A used is given in Table 2. Test results for dye transfer inhibition are listed in Table 3.

25 Table I

Washing Conditions Washing Conditions of the Main Wash Cycle Atlas Launder-o-meter, Chicago, USA Detergent Dosage 5.0 g / l Liquid Detergent A Water Hardness 3 mmol / 1 Ca: Mg 4: 1 Ratio 1: 16 Washing temperature 60 ° C Washing time 30 minutes Polymer dosage 0.05 g / l liquid Colored fabric EMPA 130 Ig (CI Direct Red 83: 1) EMPA 132 Ig (CI Direct Black 22) 1 g EMPA 133 (CI Direct Blue 71) 0.5 g EMPA 134 (CI Direct Orange 39) ) (all from Swiss Federal Laboratoires for Materials Testing, St. Gallen, Switzerland) Test Fabric 5 g Cotton Fabric 221 (Bleached) Ballast Fabric 5 g Mixed Fabric 768 (65: 35 Polyester: Cotton) + 5 g of polyester fabric 854 Table 2:

Composition of detergent A (liquid detergent) Ingredients [% by weight] C3_5 oxo alcohol 5 x 7 EO 12 C6 x 5 alcohol EO 5 Citric acid 3 Propylene glycol 10 Ethanol 2 Diethylenetriaminapenta (methylenephosphoric acid) 1.0 Water to 100 Adjust to pH 9 with sodium hydroxide solution.

Preparation of hydrophobically polyethyleneimine derivatives

modified:

Starting Materials:

Polyethyleneimine A: Mw 25,000 g / mol; amino number: 20.14 mmol / g; ratio of primary nitrogen atoms: secondary: tertiary:

1.0: 1.1: 0.7, determined by 13 C NMR.

Polyethyleneimine B: Mw 5000 g / mol: Amine Number: 9, 22

mmol / g; ratio of primary nitrogen atoms: secondary: tertiary:

1.0: 1.0: 0.7, determined by 13 C NMR.

Polymer 1,350 g of polyethyleneimine A was initially introduced into toluene (300 ml). Heating to 100 ° C was then performed. After the addition of palmitic acid (179 g), the reaction mixture was brought to 120 ° C, and with stirring the water that was formed was distilled off by means of a separator.

of water (7 h). Toluene was then removed under reduced pressure. The product was obtained as a very viscous orange oil.

Polymer 2

210 g of polyethyleneimine A was initially introduced into toluene (300 ml). Heating to 100 ° C was then performed. After the addition of palmitic acid (322 g), the reaction mixture was brought to 120 ° C, and, with stirring, the water that was formed was distilled by means of a water separator (50 h). Toluene was then removed under reduced pressure. The product was obtained as an orange wax (501 g).

Polymer 3

200 g of polyethyleneimine A was initially introduced

in toluene (700 ml). Heating to 100 ° C was then performed. After the addition of palmitic acid (502 g), the reaction mixture was brought to 120 ° C, and, with stirring, the water that was formed was distilled by means of a water separator (30 h). 400 ml of toluene was removed from the reaction mixture and the water was distilled for an additional 12 h. Toluene was then removed under reduced pressure. The product was obtained as a brown wax (670 g).

Polymer 4

231 g of polyethyleneimine A was initially introduced and heated to 100 ° C.

C12 epoxide (Vikolox 12; 425 g) was added dropwise. The mixture was then stirred at 100 ° C for 9 hours. A highly viscous yellow oil was obtained (656 g).

Polymer 5,199 g of polyethyleneimine A was initially introduced into toluene (400 ml). Heating to 100 ° C was then performed. After addition of dodecylic acid (396 g), the reaction mixture was brought to 120 ° C and, while under stirring, the water that was formed was distilled through a water separator (30 h). Toluene was then removed under reduced pressure. A viscous reddish brown product was obtained (558 g).

Polymer 6

149 g of polyethyleneimine A was initially introduced into toluene (400 ml) and heated to 100 ° C. After addition of stearic acid (424 g), the reaction mixture was brought to 120 ° C and, while under stirring, the water that was formed was distilled by means of a water separator (30 h). Toluene was then removed under reduced pressure. The product was obtained as a pale yellow brown wax (451 g).

Polymer 7

550 g of polyethyleneimine B was initially introduced into toluene (500 ml). Heating at 100 ° C was then performed. After the addition of palmitic acid (258 g), the reaction mixture was brought to 120 ° C and, while under stirring, the water that was formed was distilled by means of a water separator (3 d). Toluene was then removed under reduced pressure. The product was obtained with an orange wax (510 g).

Polymer 8

434 g of polyethyleneimine B was initially introduced into toluene (400 ml). Heating to 100 ° C was then performed. After the addition of palmitic acid (497 g), the reaction mixture was brought to 120 ° C and while under stirring the water that was formed was distilled by means of a water separator (3d). Toluene was then removed under reduced pressure. The product was obtained as an orange wax (510 g).

Polymer 9

Polymer 8 (666 g) was heated to 75 ° C. Dimethyl sulfate was then dosed therein (71.8 g; Dosimat 2.5 ml / min). Excess dimethyl sulfate was then removed under reduced pressure. The product was obtained as a brown amorphous substance (407.5 g).

Table 3: Application of liquid detergent A

Effect of DTI \%] 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 Negative Effect 46.1 40, 2 41.7 PEI5000 Negative Effect 54.3 25.8 53.2 PVP * 22.9 33.7 94.0 35.8 PVP = K-value polyvinyl pyrrolidone 30

= polyethyleneimine A = polyethyleneimine B

Negative effect: polymer does not exhibit dye transfer layer inhibition, but provides this.

* Polyvinylpyrrolidone: reference substance.

Claims (15)

1. Use of hydrophobically modified C2.4 polyalkyleneimines, characterized in that they are as dye transfer inhibitors in textile detergent compositions. Use according to Claim 1, characterized in that, on average, at least 10 mol% of the nitrogen atoms of C2-4 polyalkyleneimine carry an aliphatic saturated or unsaturated hydrocarbon radical having at least 8 carbon atoms. Use according to claim 2, characterized in that the fraction of hydrocarbon radicals based on the total weight of C 2-4 polyalkyleneimine constitutes 25 to 95% by weight. Use according to claim 2 or 3, characterized in that the hydrocarbon radicals are present in the form of C8-30 alkyl, C8-30 alkylcarbonyl, C8-30 alkenyl, C8-30 alkenylcarbonate, C8-30 alkenylcarbonyl groups. .30 and / or C8.30 hydroxyalkyl. Use according to any one of the preceding claims, characterized in that the hydrophobically modified C 2-4 polyalkyleneimine has an average molecular weight number in the range of 3000 to 300,000 Daltons. Use according to any one of the preceding claims, characterized in that the C2-4 polyalkyleneimine is the branched C2-4 polyalkyleneimine. Use according to any one of the preceding claims, characterized in that the hydrophobically modified C2.4 polyalkyleneimine has quaternized nitrogen atoms. Use according to any one of the preceding claims, characterized in that the hydrophobically modified C2.4 polyalkyleneimine is obtainable by a process comprising reacting a C2.4 polyalkyleneimine with a hydrophobicization agent. Use according to claim 8, characterized in that the hydrophobicizing agent is selected from aliphatic, saturated, mono- or polyunsaturated C9.31 carboxylic acids, their amide-forming derivatives and C1-6 alkylene oxides. -3o · Use according to claim 8 or 9, characterized in that the hydrophobicising agent, calculated as the parts of the hydrophobicizing agent remaining in the product, is used in an amount of from 0.35 to 20 parts by weight. by part by weight of hydrophobically modified C 2-4 polyalkyleneimine. Use according to any one of claims 8 to 10, characterized in that the preparation of the hydrophobically modified C 2-4 polyalkyleneimine comprises a quaternization. Use according to any one of claims 8 to 11, characterized in that the hydrophobically modified polyalkyleneimine C2A used for the preparation is branched. Use according to any one of claims 8 to 12, characterized in that the hydrophobically modified C2.4 polyalkyleneimine used for the preparation has an average molecular weight number in the range 1000 to 200,000 Daltons. Use according to any one of the preceding claims, characterized in that the fraction of nonionic surfactants in the detergent composition, based on the total amount of surfactant in the detergent composition, is at least 50% by weight. . Use according to any one of the preceding claims, characterized in that the hydrophobically modified C 2-4 polyalkyleneimine is used at a concentration of 5 to 150 ppm in the washing liquid.