EP2126020A1

EP2126020A1 - Hydrophobically modified polyalkylenimines for use as dye transfer inhibitors

Info

Publication number: EP2126020A1
Application number: EP07858097A
Authority: EP
Inventors: Jürgen Detering; Heike Becker; Richard Baur; Gero Nordmann
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2006-12-22
Filing date: 2007-12-21
Publication date: 2009-12-02
Anticipated expiration: 2027-12-21
Also published as: CN101568630A; US20100017973A1; MX2009005829A; BRPI0720573A2; WO2008077952A1; ES2376369T3; CA2671878A1; ATE534722T1; PL2126020T3; JP2010513644A; CN101568630B; KR20090096723A; EP2126020B1

Abstract

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

Description

Hydrophobically modified polyalkyleneimines as color transfer inhibitors

description

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

During the washing process dyed textiles often replace dye molecules, which in turn can be applied to other textiles. To counteract this undesired color transfer, so-called color transfer inhibitors are often used. These are often polymers which contain monomers having nitrogen-heterocyclic radicals in copolymerized form.

So describes z. For example, DE 4235798 copolymers of 1-vinylpyrrolidone, 1-vinylimidazole, 1-vinylimidazolium compounds or mixtures thereof; further nitrogen-containing, basic ethylenically unsaturated monomers; and optionally other monoethylenically unsaturated monomers and their use to inhibit dye transfer during the wash.

Similar copolymers are described for this purpose in DE 19621509 and WO 98/30664.

The copolymers described in these documents are characterized in part by a good inhibition of color transfer in washing processes. However, they generally have a low compatibility with the other commonly used detergent ingredients. Thus, there is the danger of incompatibilities, for example in the form of turbidity or phase separations, especially in liquid detergents.

There have been various reports of the use of hydrophobically modified polyalkyleneimines in detergent formulations.

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 polyethyleneimines and their use as fabric softeners.

DE 2165900 describes reaction products of Alkylglyciylethern with Polyethy- leniminen and their use as grayness inhibitors. US Pat. No. 3,576,341 describes alkylated polyethyleneimines in which the alkyl groups have 16 to 30 C atoms and use as fabric softeners.

WO 2002/095122 describes the use of hydrophobically modified polyethyleneimines as anti-caking additives for detergent formulations.

An ink transfer inhibiting effect of the hydrophobically modified polyalkyleneimines is not described in any of these references.

It was an object of the present invention to provide substances with a good color transfer inhibiting effect during the washing process. These substances should also have good compatibility with conventional detergent ingredients, especially in liquid detergent formulations.

These and other objects are surprisingly achieved by hydrophobically modified poly-C 2 -C 4 -alkyleneimines.

The invention therefore relates to the use of hydrophobically modified P0IV-C 2 -C 4 -alkyleneimines, in particular hydrophobically modified polyethyleneimines, as color transfer inhibitors in detergent compositions for textiles.

Hydrophobically modified poly-C 2 -C 4 -alkyleneimines are understood here and below to mean poly-C 2 -C 4 -alkyleneimines in which the hydrogen atoms of the primary and secondary amino groups are partially or completely saturated by linear or branched aliphatic, saturated or unsaturated hydrocarbon radicals, such as Alkyl, alkenyl, alkadienyl or hydroxyalkyl radicals are replaced. The hydrocarbon radicals usually have at least 8, e.g. 8 to 30 C-atoms, preferably 10 to 22 C-atoms, in particular 10 to 18 C-atoms.

The hydrocarbon radicals may, depending on the particular used

Hydrophobizing agent, directly or via a functional group, eg via a carbonyl group ( ^* -C (OO) - ^# ), via an oxycarbonyl group ( ^* -OC (OO) - ^# ), via an amino carbonyl group ( ^* - NH-C (= O) - ^# ), via a carbonyloxyhydroxypropyl group ( ^* -C (= O) -O-CH ₂ -CH (OH) -CH ₂ - ^# ) via a 2-oxycarbonylethylenecarbonyl group ( ^* -CH (COOH) -CH ₂ -CO- ^# ) or via a radical of the formula ^* -CH ₂ -C (= O) -CH ^* -C (= O) - ^{# be} linked to the nitrogen atom of the poly-C ₂ -C 4 -alkyleneimine ( ^* represents in the formulas given above the linkage with the hydrocarbon radical and # the linkage with the nitrogen atom of the poly-C2-C4-alkylenimine). The hydrocarbon radical can also form an aldimine or ketimine group with the nitrogen of the poly-C 2 -C 4 -alkylenimine or can be linked to 2-nitrogen atoms of the poly-C 2 -C 4 -alkylenimine via the carbon atom of a cyclic amidine group. Preference is given to those hydrophobically modified poly-C 2 -C 4 -alkyleneimines in which the hydrocarbon radical is linked directly or via a carbonyl group to a nitrogen atom of the poly-C 2 -C 4 -alkyleneimine, the latter being particularly preferred.

The hydrocarbon radicals are preferably linear. The hydrocarbon radicals are preferably saturated.

Accordingly, the hydrocarbon radicals in the preferred hydrophobically modified poly-C 2 -C 4 -alkyleneimines are in the form of C ₆ -C 5 -alkyl-, C ₅ -C ₈ -alkylcarbonyl, C ₅ -C ₈ -alkenyl, C ₆ -C ₈ -alkenylcarbonyl, C ₈ -C ₃ o-alkadienyl, Cs-Cso-alkadienyl-carbonyl and / or hydroxy-Cs-Cso-alkyl groups, in particular in the form of C10-C22-alkyl, Cio-C22-alkylcarbonyl, Cio-C22-alkenyl, Cio -C 22 -alkenylcarbonyl, C 10 -C 22 -alkadienyl, Cio-C 22 -alkadienylcarbonyl and / or hydroxy-C 10 -C 22 -alkyl groups, particularly preferably in the form of C 1 -C 6 -alkyl-, C 1 -C 6 -alkylcarbonyl, Cio -Cis-alkenyl, C10-Cis-alkenylcarbonyl, Cio-Cis-alkadienyl, Cio-Cis-Alkadienylcarbonyl- and / or hydroxy-Cio-Cis-alkyl groups, wherein the alkyl, hydroxyalkyl, alkenyl Alkadienyl radicals of the aforementioned groups are preferably linear.

In the particularly preferred hydrophobically modified poly-C 2 -C 4 -alkyleneimines, the hydrocarbon radicals are in the form of C 5 -C 8 -alkylcarbonyl or C 5 -C 8 -alkenylcarbonyl groups, in particular in the form of C 10 -C 22 -alkylcarbonyl or C 10 -C 22 -alkenylcarbonyl groups and especially in the form of Cio-Cis-alkylcarbonyl or C-io-C-is-alkenylcarbonyl groups, wherein the alkyl and alkenyl radicals of the abovementioned groups are preferably linear.

Preference is furthermore given to those hydrophobically modified poly-C 2 -C 4 -alkyleneimines in which at least 10 mol%, in particular at least 15 mol% and particularly preferably at least 20 mol%, e.g. 5 to 80 mol%, in particular 15 to 70 mol% and especially 20 to 60 mol% of the nitrogen atoms of the poly-C 2 -C 4 -alkylenimine carry a hydrocarbon radical.

Accordingly, the proportion of hydrocarbon radicals preferably makes up from 25 to 95% by weight, in particular from 30 to 90% by weight and especially from 40 to 80% by weight, based on the total weight of the hydrophobically modified poly-C 2 -C 4 -alkylenimine.

The weight-average molecular weight Mw of hydrophobically modified poly-C 2 -C 4 -alkyleneimines which is suitable according to the invention is typically in the range from 1000 to 1,000,000 daltons. For the inventive use, it has also proven to be advantageous if the hydrophobically modified poly-C2-C4-alkylenimine has a number average molecular weight in the range of 3000 to 300,000 daltons and in particular in the range of 6000 to 200,000 daltons. The molecular weights given here relate to those indicated by dynamic light scattering. aqueous solutions at 25 ° C measured molecular weights corresponding to the weight average molecular weight.

The hydrophobically modified poly-C 2 -C 4 -alkyleneimines used according to the invention, in particular the hydrophobically modified polyethyleneimines, may be linear or branched, based on the poly-C 2 -C 4 -alkylenimine on which they are based, preference being given to those which are present in the poly-C 2 -C 4 -alkyleneimines. Alkylenimin part are branched. Whereas linear poly-C 2 -C 4 -alkyleneimines are composed exclusively of repeating units of the formula A in which Q is C 2 -C 4 -alkylene, branched P 0IV-C 2 -C 4 -alkyleneimines have, in addition to the linear repeating units, tertiary nitrogen atoms according to the structural unit B:

B

Preference is given to such branched, hydrophobically modified poly-C 2 -C 4 -alkyleneimines, in particular branched, hydrophobically modified polyethyleneimines which, based on the poly-C 2 -C 4 -alkyleneimine on which they are based, have on average per polyalkylenimine molecule at least one, preferably at least 5 or at leastiO branch points according to formula B. In particular, at least 5%, more preferably at least 10, and most preferably at least 15%, e.g. 5 to 40% and especially 15 to 35% of the nitrogen atoms of the underlying poly-C2-C4-alkylenimine tertiary nitrogen atoms.

Especially at higher 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 underlying poly-C 2 -C 4 -alkylenimine are tertiary nitrogen atoms, the hydrophobically modified poly-C 2 -C 4 -alkyleneimines have a core-shell-like structure, the polymer C2-C4-alkylenimine moieties form the core and the hydrophobic moieties form the shell.

The hydrophobically modified poly-C 2 -C 4 -alkylenimines can be present in uncrosslinked or crosslinked form and, in addition to the hydrophobic modification, are quaternized and / or modified by reaction with alkylene oxides, di-C 1 -C 4 -alkyl carbonates, C 2 -C 4 -alkylene carbonates or C 1 -C 4 -carboxylic acids be.

The hydrophobically modified poly-C 2 -C 4 -alkyleneimines are preferably uncrosslinked. According to a first preferred embodiment of the invention, the hydrophobically modified poly-C 2 -C 4 -alkyleneimines have no further modification in addition to the hydrophobic modification.

According to a second preferred embodiment of the invention, the hydrophobically modified poly-C 2 -C 4 -alkyleneimines are quaternized in addition to the hydrophobic modification. Such quaternized hydrophobically modified poly-C 2 -C 4 -alkyleneimines preferably have no further modification. The degree of quaternization, i. the number of quaternized nitrogen atoms, based on the total amount of nitrogen atom of the hydrophobically modified poly-C 2 -C 4 -alkyleneimine, 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-C2-C4-alkylenimine.

The hydrophobically modified P0IV-C ₂ -C ₄ -alkyleneimines used according to the invention are known in part from the prior art cited at the beginning or can be prepared analogously to the methods described there. As a rule, hydrophobically modified poly-C ₂ -C ₄ -alkyleneimines are prepared by polymer-analogous reaction of unmodified poly-C ₂ -C ₄ -alkyleneimines with a water repellent. Accordingly, one embodiment of the invention relates to the use of a hydrophobically modified poly-C ₂ -C ₄ -alkyleneimine obtainable by a process which does not involve the reaction of an unmodified poly-C ₂ -C ₄ -alkyleneimine, in particular one modified, branched poly-C ₂ -C ₄ -alkylenimines, and especially a non-modified, branched polyethyleneimine, with a hydrophobing agent comprises.

Examples of suitable hydrophobizing agents are: i) long-chain, linear or branched carboxylic acids having 8 to 30 C atoms, preferably 10 to 22 C atoms, in particular 10 to 18 C atoms in the alkyl or alkenyl radical, such as caprylic acid, pelargonic acid, undecanoic acid, Lauric acid, tridecanic acid, myristic acid, pentadecanoic acid, palmitic 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, palmitic acid and oleic acid, or their amide-forming derivatives as acid chlorides, esters or anhydrides of said carboxylic acids and mixtures thereof, ii) linear or branched alkyl halides having 8 to 30 C atoms, preferably 10 to 22 C atoms, in particular 10 to 18 C atoms in the linear or branched alkyl radical, such as octyl chloride, nonyl chloride, decyl chloride, dodecyl chloride, tetradecyl chloride, hexadecyl chloride, octad ecyl 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 hexadecyl oxide, dodecenyloxide 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 Laurylketen-, Palmitylketen-, Stearylketen- and Oleylketen dimers and mixtures thereof , v) cyclic dicarboxylic 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 dodecenylsuccinic anhydride, tetradecylsuccinic anhydride, hexadecenylsuccinic anhydride and their Mixtures, 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) chloroformate of linear or branched alkanols or alkenoles having 8 to 30 C atoms, preferably 10 to 22 C atoms, in particular 10 to 18 C atoms and mixtures thereof as well as 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 a total of 8 to 30 carbon atoms, preferably 10 to 22 C atoms, in particular 10 to 18 C atoms in the two alkyl groups and mixtures thereof.

Preferred hydrophobizing agents are long-chain, linear or branched carboxylic acids having 8 to 30 C atoms, preferably 10 to 22 C atoms, in particular 10 to 18 C atoms in the alkyl or alkenyl radical and their amide-forming derivatives, in particular linear saturated carboxylic acids with 10 to 22 C atoms, in particular 10 to 18 C atoms in the alkyl radical.

Preferred water repellents are also alkyl epoxides having 8 to 30 carbon atoms, preferably 10 to 22 carbon atoms, in particular 10 to 18 carbon atoms.

The unmodified poly-C 2 -C 4 -alkyleneimines which underlie the hydrophobically modified poly-C 2 -C 4 -alkyleneimines used according to the invention include homopolymers of ethyleneimine (aziridine) and its higher homologues propylenimine (methylaziridine) and butylenimines (1, 2-dimethylaziridine, 1, 1-dimethylaziridine and 1-ethylaziridine), copolymers of ethyleneimine with its higher homologs and the graft polymers of polyamidoamines or polyvinylamines with ethyleneimine and / or its higher homologues.

Also suitable are the graft polymers described in WO 02/095122 of C 2 -C 4 -alkyleneimines such as ethyleneimine on polyamidoamines or on polyvinylamines. Such graft polymers generally have a weight fraction of C 2 -C 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 the unmodified poly-C 2 -C 4 -alkyleneimine.

In particular, the unmodified poly-C 2 -C 4 -alkyleneimines are branched poly-C 2 -C 4 -alkyleneimines, preferably polyethylenimines, in particular branched polyethylenimines and especially homopolymers of ethylenimine, which are in particular branched.

The unmodified poly-C ₂ -C ₄ -alkyleneimine used for the preparation is preferably branched, with the above-mentioned degree of branching being for hydrophobically modified poly-C ₂ -C ₄ -alkyleneimines.

The unmodified poly-C ₂ -C ₄ -alkyleneimine used for the preparation preferably has a number-average molecular weight in the range from 1000 to 200 000 dalton, in particular in the range from 2000 to 100 000 dalton.

The reaction of the unmodified poly-C ₂ -C ₄ -alkylenimine with the hydrophobing agent can be carried out in analogy to known methods of the prior art. The reaction conditions naturally depend on the nature and functionality of the hydrophobing agent.

The reaction can be carried out in bulk or in solution. Preferably, the reaction is carried out in a suitable solvent for the reaction. Examples of suitable solvents are hydrocarbons, especially aromatic hydrocarbons, e.g. Alkylbenzenes such as xylene, toluene, cumene, tert-butylbenzene and the like.

Optionally, the reaction can be carried out in the presence of catalysts, which improves the reactivity of the hydrophobing agent over the poly-C ₂ - C ₄ -alkylenimin. The type of catalyst depends in a conventional manner on the nature and reactivity of the hydrophobing agent. As a rule, the catalysts are Lewis or Bronsted acids. Often, for example in the case of carboxylic acids, one can do without the use of catalysts.

In the case of the inventively preferred carboxylic acids and carboxylic acid derivatives, it has proven to be advantageous to remove the resulting low molecular weight products in the reaction (water, alcohols or hydrogen chloride) 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 entraining agent. Typical entrainers are hydrocarbons, in particular alkylaromatics such as toluene or xylene. The reaction is then preferably carried out in an organic solvent suitable as an entraining agent.

In general, one will use the hydrophobizing agent in an amount corresponding to the desired functionalization, wherein also the hydrophobing agent can use funds in excess. As far as the molar ratio of hydrophobizing agent to nitrogen atoms in the unmodified polyalkyleneimine is the same as that previously stated for the functionalization of the hydrophobicized polyalkyleneimine. In particular, the hydrophobizing agent, calculated as the parts of the hydrophobizing agent remaining in the product (that is, the amount of hydrophobing agent less any low molecular weight products such as water), in an amount of 0.35 to 20 parts by weight, in particular in an amount of 0.5 to 10 Parts by weight, per part by weight of unmodified poly-C ₂ -C ₄ -alkylenimin.

According to a preferred embodiment of the invention, the hydrophobically modified poly-C ₂ -C ₄ -alkyleneimines are quaternized. Accordingly, the preparation of the hydrophobically modified poly-C ₂ -C ₄ -alkyleneimines additionally comprises a quaternization. The quaternization can take place before or in particular after the hydrophobicization.

For quaternization 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 contain alkyl radicals having 1 to 10 carbon atoms 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. Other suitable alkylating agents are e.g. Benzyl halides, especially benzyl chloride and benzyl bromide; Chloroacetic acid; Fluorschwefelsäuremethylester; 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 sulfate and diethyl sulfate. In the quaternization, the secondary or, in particular, the tertiary nitrogen atoms of the underlying poly-C 2 -C 4 -alkyleneimine moiety are converted into quaternary nitrogen atoms, ie, ammonium groups, whereby the hydrophobically modified poly-C 2 -C 4 -alkyleneimine is given a positive overall charge.

The hydrophobically modified poly-C 2 -C 4 -alkylenimines are generally water-soluble or water-dispersible and can be used in solid and liquid detergents and in laundry after-treatment agents. They are distinguished in particular by high compatibility with conventional detergent ingredients, in particular with the constituents of liquid detergent formulations, especially those which have a low content of anionic surfactants.

The incorporation in the respective detergent or Wäschenachbehandlungsmittel- formulation is carried out in a conventional manner, the hydrophobically modified polyalkyleneimines are often used in liquid, ie dissolved or dispersed form. The hydrophobically modified polyalkyleneimines can also be used in powder or granular form. The color transfer to mitgeschaschenes tissue and the associated undesirable discoloration of these tissues is effectively inhibited. Already at concentrations of 10 to 150 ppm of the hydrophobically modified poly-C 2 -C 4 -alkyleneimine in the washing or rinsing liquor good to very good dye transfer-inhibiting effects are achieved, which are well above the reference substances such as polyvinylpyrrolidone.

The solid detergent formulations contain in particular the following components:

(a) 0.05 to 20% by weight of at least one hydrophobically modified P0IV-C 2 -C 4 -alkyleneimine,

(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) from 0% to 10% by weight of an organic cobuilder; and (e) from 0.1% to 60% by weight of other conventional ingredients such as sizing agents, enzymes, perfume, chelating agents, corrosion inhibitors, bleaches, bleach activators, bleach catalysts, other color protective additives, and Dye transfer inhibitors, grayness inhibitors, soil release polyesters, fiber protective additives, silicones, dyes, bactericides and preservatives, dissolution improvers and / or disintegrants, water, the sum of components (a) to (e) being 100% by weight ,

The solid detergent formulations may be in powder, granule, extrudate or tablet form.

The liquid detergent formulations preferably have the following composition: (a) 0.05 to 20 wt .-% of at least one hydrophobically modified P0IV-C2-C4-alkylenimine, (b) 0.5 to 70 wt .-% 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) from 0.1% to 60% by weight of other conventional ingredients, such as soda, enzymes, perfume, chelating agents, corrosion inhibitors, bleaches, bleach activators, bleach catalysts, other color protective additives and dye transfer inhibitors, grayness inhibitors, soil release polyesters, fiber protective additives, silicones, Dyes, bactericides and preservatives, organic solvents, solubilizers, hydrotropes, thickeners and / or alkanolamines and (f) 0 to 99.35 wt .-% water, wherein the sum of components (a) to (f) 100 wt. -% results. The laundry aftertreatment agents, in particular laundry detergent, preferably contain

(a) from 0.05 to 20% by weight of at least one hydrophobically modified P0IV-C 2 -C 4 -alkylenimine, (b) from 0.1 to 40% by weight of at least one cationic surfactant,

(c) 0 to 30% by weight of at least one nonionic surfactant,

(D) 0.1 to 30 wt .-% of other conventional ingredients, such as silicones, other lubricants, wetting agents, film-forming polymers, fragrances and dyes, stabilizers, fiber-protective additives, other color protective additives and Farbübertragungsinhibito- ren, complexing agents, viscosity modifiers, soil release Additives, solubilizers, hydrotropes, anticorrosion additives, bactericides and preservatives, and

(e) 0 to 99.75% by weight of water, the sum of components (a) to (e) being 100% by weight.

Suitable nonionic surfactants (B) are, in particular:

Alkoxylated C 8 -C 22 -alcohols, such as fatty alcohol alkoxylates, oxo alcohol alkoxylates and Guerbet alcohol ethoxylates: The alkoxylation can be carried out with ethylene oxide, propylene oxide and / or butylene oxide. There may be block copolymers or random copolymers. They usually contain from 2 to 50 mol, preferably from 3 to 20 mol, of at least one alkylene oxide per mole of alcohol. Preferred alkylene oxide is ethylene oxide. The alcohols preferably have 10 to 18 carbon atoms; Alkylphenol alkoxylates, especially alkylphenol ethoxylates containing Ce-Cu alkyl chains and 5 to 30 moles of alkylene oxide / mole;

Alkyl polyglucosides containing C8-C22, preferably C10-C18-alkyl chains and usually 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, e.g. Polyhydroxy fatty acid amides, gemini surfactants and block copolymers of ethylene oxide, propylene oxide and / or butylene oxide; as well as their mixtures.

Suitable anionic surfactants are, for example: sulfates of (fatty) alcohols having 8 to 22, preferably 10 to 18, carbon atoms, in particular C 3 -C 5 -alcohol sulfates, C 12 -C 14 -alcohol sulfates, C 12 -C 18 -alcoholsulfates, laurylsulfate, cetylsulfate, myristylsulfate, palmitylsulfate, Stearyl sulfate and tallow fatty alcohol sulfate; Sulfated alkoxylated Cs-C22 alcohols (alkyl ether sulfates): Compounds of this type are prepared, for example, by first alkoxylating a C8-C22 alcohol, preferably a C 10 -C 18 -alcohol, for example a fatty alcohol, and Alk oxylierungsprodukt then sulfated. For the alkoxylation is preferably used ethylene oxide;

Linear C8-C2o-alkylbenzenesulfonates (LAS), preferably linear C9-C13

Alkylbenzenesulfonates and alkyltoluenesulfonates; - alkanesulfonates, in particular C8-C24-, preferably Cio-Ci8-alkanesulfonates;

olefin;

Fatty acid and fatty acid ester sulfonates.

Soaps, such as the Na and K salts of C8-C24 carboxylic acids. as well as their mixtures

The anionic surfactants are preferably added to the detergent in the form of salts. Suitable salts are e.g. Alkali metal salts such as sodium, potassium and lithium salts, and ammonium salts such as hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.

Particularly suitable cationic surfactants are:

C7-C25-alkyl amines;

N, N-dimethyl-N- (hydroxy-C7-C25-alkyl) ammonium salts; mono- and di- (C 7 -C 25 -alkyl) dimethylammonium compounds quaternized with alkylating agents;

Esterquats, especially quaternary esterified mono-, di- and trialkanolamines esterified with Cs-C22 carboxylic acids;

Imidazolinquats, in particular 1-Alkylimidazoliniumsalze of the formulas II or III

in which the variables have the following meaning: R ^{9 is} Ci-C ₂₅ -alkyl or C ₂ -C ₂ 5-alkenyl; R ^{10 is} C 1 -C ₄ -alkyl or hydroxy-C 1 -C ₄ -alkyl; R ^{11 is} C 1 -C ₄ -alkyl, hydroxy-C ¹ -C ₄ -alkyl or a radical R ¹ - (CO) -X- (CH ₂ ) _m - (X: -O- or -NH-; m: 2 or 3), wherein at least one R ^{9 is} C 7 -C ²² alkyl.

Suitable amphoteric surfactants are, for example, alkylbetaines, alkylamidbetaines, aminopropionates, aminoglycinates and amphoteric imidazolium compounds. The advantages of the hydrophobically modified polyalkyleneimines according to the invention are particularly evident in those detergent formulations which contain only a small proportion of anionic surfactants. The proportion of anionic surfactants, based on the total amount of surfactant in the detergent or laundry aftertreatment agent formulation, is preferably not more than 50% by weight, in particular not more than 30% by weight, and especially not more than 10% by weight. Preferably, the anionic surfactant does not constitute more than 8% by weight, in particular not more than 5% by weight, based on the total weight of the formulation.

Suitable inorganic builders are, in particular:

Crystalline and amorphous aluminosilicates with ion-exchanging properties, 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 partially opposes other cations such as Li, K, Ca, Mg or ammonium is exchanged;

Crystalline silicates, in particular disilicates and phyllosilicates, e.g. δ- and ß-Na2Si2θ5 The silicates can be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preference is given to the Na, Li and Mg silicates; Amorphous silicates such as sodium metasilicate and amorphous disilicate; Carbonates and bicarbonates: 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 bicarbonate; and polyphosphates, such as pentasodium triphosphate.

As organic cobuilders are particularly suitable:

Low molecular weight carboxylic acids such as citric acid, hydrophobically modified citric acid, e.g. As agaric, malic, tartaric, gluconic, glutaric, succinic, imidodisuccinic, oxydisuccinic, propanetricarboxylic, butanetetracarboxylic, cyclopentanetetracarboxylic, alkyl and

Alkenyl succinic acids and aminopolycarboxylic acids, e.g. Nitrilotriacetic acid, β-alanine diacetic acid, ethylenediaminetetraacetic acid, serinediacetic acid, isoserine diacetic acid, N- (2-hydroxyethyl) iminoacetic acid, ethylenediamine disuccinic acid, and methyl and ethyl glycine diacetic acid or their alkali metal salts; 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 C 2 -C 22 olefins, e.g. Isobutene or long-chain α-olefins, vinyl-C 1 -C 8 -alkyl ethers, vinyl acetate, vinyl propionate, (meth) acrylic esters of C 1 -C 8 -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 the sodium salt; Phosphonic acids such as 1-hydroxyethylene (1, 1-diphosphonic acid), aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid) and diethylenetriaminepenta (methylenephosphonic acid) and their alkali metal salts.

Suitable grayness inhibitors are, for example, carboxymethylcellulose and graft polymers of vinyl acetate on polyethylene glycol.

Suitable bleaching agents are, for example, adducts of hydrogen peroxide with inorganic salts, such as sodium perborate monohydrate, sodium perborate tetrahydrate and sodium carbonate perhydrate, and percarboxylic acids, such as phthalimidopercaproic acid.

Suitable bleach activators are e.g. 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 color transfer inhibitors are, for example, homopolymers, copolymers and graft polymers of 1-vinylpyrrolidone, 1-vinylimidazole or 4-vinylpyridine N-oxide. Homo- and copolymers of 4-vinylpyridine reacted with chloroacetic acid are also suitable as color transfer inhibitors.

Detergent ingredients are otherwise well known. Detailed descriptions are z. In WO-A-99/06524 and 99/04313; in Liquid Detergents, Editor: Kuo- Yann Lai, Surfactant Sei. Ser., Vol. 67, Marcel Decker, New York, 1997, p. 272-304, to find.

Application of hydrophobically modified P0IV-C 2 -C 4 -alkyleneimines according to the invention

Selected colored fabric (EMPA 130 EMPA 132 EMPA 133 or EMPA 134) was washed in the presence of white test of cotton and ballast fabric of cotton / polyester and polyester with a detergent at 6O ⁰ C with the addition of the LCST polymers. After the wash, the fabrics were rinsed, spun and dried. To determine the Farbübertragunsinhibierende effect, the staining of the white test tissue was determined photometrically (photometer: Elrepho ^® 2000 Fa. Datacolor). The color strength of the staining was determined from the remission values measured on the test fabric according to the method described in A. Kud, Seifen, Ole, Fette, Wachse, Volume 1 19, pages 590-594 (1993). From the tinting strength for the test with the respective test substance, the tinting strength for the test without test substance and the tinting strength of the test fabric before washing was the color transfer inhibiting effect of the test substance according to determined by the following formula in%.

Color strength (without polymer) - Color intensity (with polymer)

FÜI effect [%] = x 100 Color intensity (without polymer) - Color intensity (before washing)

The washing conditions are given in Table 1. The composition of the detergent A used is shown in Table 2. The color transfer inhibition test results are shown in Table 3.

Table 1

Table 2

Adjust to pH 9 with sodium hydroxide solution.

Preparation of hydrophobically modified polyethylenimine derivatives:

Starting materials:

Polyethyleneimine A: Mw 25,000 g / mol; Amine number: 20.14 mmol / g Ratio of primary π-secondary tertiary nitrogen atoms: 1, 0: 1, 1: 0.7, determined by means of ¹³ C-NMR. Polyethyleneimine B: Mw 5000 g / mol; Amine number: 9.22 mmol / g ratio of primary secondary secondary nitrogen atoms: 1, 0: 1, 0: 0.7, determined by means of ¹³ C-NMR.

Polymer 1

350 g of polyethyleneimine A were initially charged in toluene (300 ml). The mixture was heated to 100 ⁰ C. After addition of palmitic acid (179 g), the reaction mixture was brought to 120 ⁰ C and distilled off with stirring, the resulting water through a Wasserkreiskreiser (7h). Subsequently, toluene was removed under reduced pressure. The product was obtained as an orange, very viscous oil (503 g).

Polymer 2

210 g of polyethyleneimine A were initially charged in toluene (300 ml). It was heated to 100 ° C. After addition of palmitic acid (322 g), the reaction mixture was brought to 120 ⁰ C and distilled off with stirring, the resulting water over a Wasserkreis- (50h). Subsequently, the toluene was removed under reduced pressure. The product was obtained as an orange wax (501 g).

Polymer 3

200 g of polyethyleneimine A were initially charged in toluene (700 ml). The mixture was heated to 100 ⁰ C. After addition of palmitic acid (502 g), the reaction mixture was brought to 120 ⁰ C and distilled off with stirring, the resulting water through a Wasserkreis- (30h). 400 ml of toluene were removed from the reaction mixture and then distilled off a further 12 h of water. Subsequently, the toluene was removed under reduced pressure. The product was obtained as a brown wax (670 g).

Polymer 4 231 g of polyethyleneimine A were initially charged and heated to 100.degree. The C12 epoxide (Vikolox 12, 425 g) was added dropwise. It was then stirred at 100 ° C for 9 h. A yellow, highly viscous oil was obtained (656 g).

Polymer 5 199 g of polyethyleneimine A are initially charged in toluene (400 ml). It was heated to 100 ⁰ C. After addition of dodecylic acid (396 g), the reaction mixture was brought to 120 ⁰ C and stirring the resulting water over a water distiller distilled off (30h). Subsequently, the toluene was removed under reduced pressure. A tough reddish brown product was obtained (558 g).

Polymer 6

A 149 g polyethyleneimine were placed in toluene (400 ml) and heated to 100 ⁰ C. After addition of stearic acid (424 g), the reaction mixture was brought to 120 ⁰ C and distilled off with stirring the resulting water through a Wasserauskreiser (30h). Subsequently, the toluene was removed under reduced pressure. The product was obtained as a yellow-tan wax (451 g).

Polymer 7

550 g of polyethyleneimine B were initially charged in toluene (500 ml). It was heated to 100 ⁰ C. After addition of palmitic acid (258 g), the reaction mixture was brought to 120 ⁰ C and distilled off with stirring the resulting water through a Wasserauskreiser (3d). Subsequently, the toluene was removed under reduced pressure. The product was obtained as an orange wax (510 g).

Polymer 8

434 g of polyethyleneimine B were initially charged in toluene (400 ml). It was heated to 100 ° C. After addition of palmitic acid (497 g), the reaction mixture was brought to 120 ° C and distilled off with stirring the resulting water through a Wasserauskreiser (3d). Subsequently, the toluene was 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 sulfate was then added (71.8 g, Dosimat 2.5 ml / min). Subsequently, the excess dimethyl sulfate was removed under reduced pressure. The product was obtained as a brown amorphous substance (407.5 g).

Table 3: Application of liquid detergent A

PVP = Polyvinylpyrrolidone with K value 30 PEI 25000 = Polyethyleneimine A PEI 5000 = Polyethyleneimine B Negative effect: Polymer shows no inhibition of the dye transfer but favors it. * Polyvinylpyrrolidone: reference substance

Claims

claims

1. Use of hydrophobically modified poly-C 2 -C 4 -alkyleneimines as color transfer inhibitors in detergent compositions for textiles.

2. Use according to claim 1, wherein on average at least 10 mol .-% of the nitrogen atoms of the poly-C2-C4-alkylenimine carry an aliphatic, saturated or unsaturated hydrocarbon radical which has at least 8 carbon atoms.

3. Use according to claim 2, wherein the proportion of hydrocarbon radicals, based on the total weight of the poly-C2-C4-alkyleneimine, 25 to 95 wt .-% constitutes.

4. Use according to claim 2 or 3, wherein the hydrocarbon radicals in the form of Cs-Cso-alkyl, Cs-Cso-alkylcarbonyl, Cs-Cso-alkenyl, Cs-Cso-alkenylcarbonyl, Cs-Cso-alkadienyl, Cs -Cso-alkadienylcarbonyl and / or hydroxy-Cs-Cso- alkyl groups present.

5. Use according to one of the preceding claims, wherein the hydrophobically modified poly-C 2 -C 4 -alkyleneimine has a number average molecular weight in the range of 3000 to 300,000 daltons.

6. Use according to one of the preceding claims, wherein the hydrophobically modified poly-C 2 -C 4 -alkyleneimine is branched in the poly-C 2 -C 4 -alkyleneimine moiety.

7. Use according to one of the preceding claims, wherein the hydrophobically modified poly-C 2 -C 4 -alkyleneimine has quaternized nitrogen atoms.

Use according to any one of the preceding claims, wherein the hydrophobically modified poly-C 2 -C 4 -alkylenimine is obtainable by a process comprising reacting a non-modified poly-C 2 -C 4 -alkylenimine with a hydrophobing agent.

9. Use according to claim 8, wherein the hydrophobizing agent is selected from saturated, mono- or polyunsaturated aliphatic C9-C31 carboxylic acids, their amide-forming derivatives and Cs-Cso-alkylene oxides.

10. Use according to claim 8 or 9, wherein the hydrophobing agent, calculated as remaining in the product parts of the hydrophobing agent, in an amount of 0.35 to 20 parts by weight per part by weight of unmodified poly-C 2 -C 4 -alkyleneimine is used.

1 1. Use according to any one of claims 8 to 10, wherein the preparation of the hydrophobically modified poly-C2-C4-alkylenimine additionally comprises a quaternization.

12. Use according to any one of claims 8 to 1 1, wherein the unmodified poly-C2-C4-alkylenimine used for the preparation is branched.

13. Use according to any one of claims 8 to 12, wherein the unmodified poly-C 2 -C 4 -alkyleneimine used for the preparation has a number-average molecular weight in the range from 1000 to 200 000 daltons.

14. Use according to one of the preceding claims, wherein the proportion of nonionic surfactants in detergent composition, based on the total amount of surfactant in the detergent composition is at least 50 wt .-%.

15. Use according to one of the preceding claims, wherein the hydrophobically modified poly-C 2 -C 4 -alkyleneimine is used in a concentration of 5 to 150 ppm in the wash liquor.