EP2126020B1 - Hydrophobically modified polyalkylenimines for use as dye transfer inhibitors - Google Patents

Abstract

The invention relates to the use of hydrophobically modified polyalkylenimines as dye 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 undesirable 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. B. the 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 used for this purpose in the DE 19621509 and the WO 98/30664 described.

The copolymers described in these documents are characterized in part by a good inhibition of color transfer in washing processes. However, they generally have 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.

The DE 2025829 describes reaction products of fatty acid glycidyl esters with polyethyleneimines and their use as fabric softeners.

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

The DE 2165900 describes reaction products of alkylglycidyl ethers with polyethylenimines and their use as grayness inhibitors.

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

The 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 having a good ink 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 poly-C ₂ -C ₄ -alkyleneimines, in particular hydrophobically modified polyethyleneimines, as color transfer inhibitors in detergent compositions for textiles.

By hydrophobically modified poly-C ₂ -C ₄ -alkyleneimines is meant here and below poly-C ₂ -C ₄ -alkyleneimines 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. Radicals such as alkyl, alkenyl, alkadienyl or hydroxyalkyl radicals are replaced. The hydrocarbon radicals generally have at least 8, eg 8 to 30 C atoms, preferably 10 to 22 C atoms, in particular 10 to 18 C atoms.

The hydrocarbon radicals, depending on the hydrophobizing agent used in each case, directly or via a functional group, for example via a carbonyl group (* -C (= O) - ^# ), via an oxycarbonyl group (* -OC (= O) - ^# ), over an aminocarbonyl 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) - ^# with the nitrogen atom of the poly-C ₂ - C ₄ -alkylenimines (* represents in the above formulas the linkage with the hydrocarbon radical and # the linkage with the nitrogen atom of the poly-C ₂ -C ₄ -alkylenimine). The hydrocarbon radical may also form an aldimine or ketimine group with the nitrogen of the poly-C ₂ -C ₄ -alkyleneimine or be linked to 2-nitrogen atoms of the poly-C ₂ -C ₄ -alkyleneimine 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 ₈ -C ₃₀ -alkyl, C ₈ -C ₃₀ -alkylcarbonyl, C ₈ -C ₃₀ -alkenyl, C ₈ - C ₃₀ -alkenylcarbonyl, C ₈ -C ₃₀ -alkadienyl, C ₈ -C ₃₀ -alkadienyl-carbonyl and / or hydroxy-C ₈ -C ₃₀ -alkyl groups, in particular in the form of C ₁₀ -C ₂₂ -alkyl- C ₁₀ -C ₂₂ -alkylcarbonyl, C ₁₀ -C ₂₂ -alkenyl, C ₁₀ -C ₂₂ -alkenylcarbonyl, C ₁₀ -C ₂₂ -alkadienyl, C ₁₀ -C ₂₂ -alkadienylcarbonyl- and / or hydroxy-C C ₁₀ -C ₂₂ -alkyl groups, particularly preferably in the form C ₁₀ -C ₁₈ -alkyl, C ₁₀ -C ₁₈ -alkylcarbonyl, C ₁₀ -C ₁₈ -alkenyl, C ₁₀ -C ₁₈ -alkenylcarbonyl, C ₁₀ -C _18- alkadienyl, C ₁₀ -C ₁₈ -Alkadienylcarbonyl- and / or hydroxy-C ₁₀ -C ₁₈ 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 ₈ -C ₃₀ -alkylcarbonyl or C ₈ -C ₃₀ -alkenyl-carbonyl 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 C ₁₀ -C ₁₈ -alkylcarbonyl or C ₁₀ -C ₁₈ -alkenylcarbonyl groups, the alkyl and alkenyl radicals of the abovementioned groups preferably being 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%, for example 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 25 to 95 wt .-%, in particular 30 to 90 wt .-% and especially 40 to 80 wt .-%, based on the total weight of the hydrophobically modified poly-C ₂ -C ₄ -alkyleneimine from ,

The weight-average molecular weight Mw of hydrophobically modified poly-C ₂ -C ₄ -alkyleneimines 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-C ₂ -C ₄ -alkylenimin 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 refer to those indicated by dynamic light scattering, to dilute ones 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; C ₂ -C ₄ -alkylenimin part are branched. While 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 poly-C ₂ -C ₄ -alkyleneimines in addition to the linear repeating units according to tertiary nitrogen atoms the structural unit B on:

Preference is given to such branched, hydrophobically modified poly-C ₂ -C ₄ -alkyleneimines, in particular branched, hydrophobically modified polyethyleneimines, based on the underlying poly-C ₂ -C ₄ -alkylenimin, on average per Polyalkyleniminmolekül at least one, preferably at least 5 or at least 10 branch points according to formula B. In particular, at least 5%, especially at least 10, and more preferably at least 15%, eg 5 to 40% and especially 15 to 35% of the nitrogen atoms of the underlying poly-C ₂ -C ₄ -alkyleneimine are tertiary nitrogen atoms.

In particular at higher degrees of branching, ie when at least 10%, in particular at least 15%, for example 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 polyols have C ₂ -C ₄ -alkyleneimines have a core-shell-like structure wherein the poly-C ₂ -C ₄ -alkyleneimine moieties form the core and the hydrophobic moieties form the shell.

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

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, ie the number of quaternized nitrogen atoms bzeogen on the total amount of the 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%, for example 1 to 80 mol%, in particular 5 to 50 mol%, based on the nitrogen atoms of the poly-C ₂ -C ₄ -alkyleneimine.

The hydrophobically modified poly-C ₂ -C ₄ -alkyleneimines used according to the invention are in part known from the cited prior art or can be prepared analogously to the methods described therein. 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 hydrophobicizing agent. Accordingly, one embodiment of the invention relates to the use of a hydrophobically modified poly-C ₂ -C ₄ -alkylenimine obtainable by a process which comprises reacting a non-modified poly-C ₂ -C ₄ -alkylenimine, in particular an unmodified one , branched poly-C ₂ -C ₄ -alkyleneimine, and especially an unmodified, branched polyethyleneimine, with a hydrophobing agent.

• i) langkettige, lineare oder verzweigte Carbonsäuren mit 8 bis 30 C-Atomen, vorzugsweise 10 bis 22 C-Atomen, insbesondere 10 bis 18 C-Atomen im Alkyl- oder Alkenylrest, wie Caprylsäure, Pelargonsäure, Undecansäure, Laurinsäure, Tridecansäure, Myristinsäure, Pentadecansäure, Palmitinsäure, Margarinsäure, Stearinsäure, Nonadecansäure, Arachinsäure, Behensäure, Palmitoleinsäure, Ölsäure, Linolsäure, Linolensäure, Arachidonsäure und deren Gemischen, bevorzugt Laurinsäure, Stearinsäure, Palmitinsäure und Ölsäure, oder deren Amid-bildenden Derivate wie Säurechloride, Ester oder Anhydride der genannten Carbonsäuren und deren Gemische,
• ii) lineare oder verzweigte Alkylhalogenide mit 8 bis 30 C-Atomen, vorzugsweise 10 bis 22 C-Atomen, insbesondere 10 bis 18 C-Atomen im linearen oder verzweigten Alkylrest, wie Octylchlorid, Nonylchlorid, Decylchlorid, Dodecylchlorid, Tetradecylchlorid, Hexadecylchlorid, Octadecylchlorid und deren Gemische,
• iii) Alkylepoxide mit 8 bis 30 C-Atomen, vorzugsweise 10 bis 22 C-Atomen, insbesondere 10 bis 18 C-Atomen im linearen oder verzweigten Alkylrest, wie Hexadecenyloxid, Dodecenyloxid und Octadecenyloxid und deren Gemische,
• iv) Alkylketen-Dimere mit 8 bis 30 C-Atomen, vorzugsweise 10 bis 22 C-Atomen, insbesondere 10 bis 18 C-Atomen im linearen oder verzweigten Alkylrest, wie Laurylketen-, Palmitylketen-, Stearylketen- und Oleylketen-Dimeren und deren Gemische,
• v) cyclische Dicarbonsäureanhydride, insbesondere alkylsubstiuierte Bernsteinsäureanhydride mit 8 bis 30 C-Atomen, vorzugsweise 10 bis 22 C-Atomen, insbesondere 10 bis 18 C-Atomen im linearen oder verzweigten Alkylrest, wie Dodecenylbernsteinsäureanhydrid, Tetradecylbernsteinsäureanhydrid, Hexadecenylbernsteinsäureanhydrid und deren Gemische,
• vi) Alkylisocyanate mit 8 bis 30 C-Atomen, vorzugsweise 10 bis 22 C-Atomen, insbesondere 10 bis 18 C-Atomen im linearen oder verzweigten Alkylrest, wie Tetradecylisocyanat, Hexadecylisocyanat, Octadecylisocyanat und deren Gemische,
• vii) Chlorameisensäureester von linearen oder verzweigten Alkanolen oder Alkenolen mit 8 bis 30 C-Atomen, vorzugsweise 10 bis 22 C-Atomen, insbesondere 10 bis 18 C-Atomen und deren Gemische sowie
• viii) lineare oder verzweigte aliphatische Aldehyde mit 8 bis 30 C-Atomen, vorzugsweise 10 bis 22 C-Atomen, insbesondere 10 bis 18 C-Atomen sowie Dialkylketone mit insgesamt mit 8 bis 30 C-Atomen, vorzugsweise 10 bis 22 C-Atomen, insbesondere 10 bis 18 C-Atomen in den beiden Alkylgruppen und deren Gemische.

Examples of suitable water repellents 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, tridecanoic 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 such as acid chlorides, esters or anhydrides of said Carboxylic acids and their mixtures,
• 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, octadecyl chloride and their mixtures,
• iii) alkyl epoxides 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 hexadecenyl 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 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 dodecenylsuccinic anhydride, tetradecylsuccinic anhydride, hexadecenylsuccinic anhydride and mixtures thereof,
• vi) alkyl isocyanates 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 tetradecyl isocyanate, hexadecyl isocyanate, octadecyl isocyanate and mixtures thereof,
• vii) chloroformates 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 C atoms, preferably 10 to 22 C atoms, in particular 10 to 18 C atoms, and dialkyl ketones having a total of 8 to 30 C atoms, preferably 10 to 22 C atoms, in particular 10 to 18 carbon atoms in the two alkyl groups and mixtures thereof.

Preferred hydrophobizing 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 their amide-forming derivatives, in particular linear saturated carboxylic acids having 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 are based on the hydrophobically modified poly-C ₂ -C ₄ -alkyleneimines used according to the invention, include homopolymers of ethyleneimine (aziridine) and its higher homologues propyleneimine (methylaziridine) and butyleneimines (1, 2-dimethylaziridine, 1,1-dimethylaziridine and 1-ethylaziridine), copolymers of ethyleneimine with its higher homologues and the graft polymers of polyamidoamines or polyvinylamines with ethyleneimine and / or its higher homologues.

Also suitable are the in WO 02/095122 described graft polymers 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 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 polyethyleneimines, in particular branched polyethyleneimines and especially homopolymers of ethyleneimine, 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 daltons, in particular in the range from 2000 to 100 000 daltons.

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 xylenes, 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 xylenes. The reaction is then preferably carried out in an organic solvent suitable as an entraining agent.

In general, you will use the hydrophobing agent in an amount that corresponds to the desired functionalization, which also includes the water repellent can use 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. Further suitable alkylating agents are, for example, benzyl halides, in particular 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 -alkylenimin part are converted into quaternary nitrogen atoms, ergo ammonium groups, whereby the hydrophobically modified poly-C ₂ -C ₄ -alkylenimin imparted a positive overall charge becomes.

The hydrophobically modified poly-C ₂ -C ₄ -alkyleneimines 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 into the respective detergent or laundry aftertreatment agent formulation is carried out in a manner known per se, the hydrophobically modified polyalkyleneimines frequently being 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.

1. (a) 0,05 bis 20 Gew.-% mindestens eines hydrophob modifizierten Poly-C₂-C₄-alkylenimins,
2. (b) 0,5 bis 40 Gew.-% mindestens eines nichtionischen, anionischen und/oder kationischen Tensids,
3. (c) 0,5 bis 50 Gew.-% eines anorganischen Builders,
4. (d) 0 bis 10 Gew.-% eines organischen Cobuilders und
5. (e) 0,1 bis 60 Gew.-% anderer üblicher Inhaltsstoffe, wie Stellmittel, Enzyme, Parfüm, Komplexbildner, Korrosionsinhibitoren, Bleichmittel, Bleichaktivatoren, Bleichkatalysatoren, weitere Farbschutzadditive und Farbübertragungsinhibitoren, Vergrauungsinhibitoren, Soil-Release-Polyester, Faserschutzadditive, Silicone, Farbstoffe, Bakterizide und Konservierungsmittel, Auflösungsverbesserer und/oder Sprengmittel, Wasser,

wobei die Summe der Komponenten (a) bis (e) 100 Gew.-% ergibt.The solid detergent formulations contain in particular the following components:

1. (a) 0.05 to 20% by weight of at least one hydrophobically modified poly-C ₂ -C ₄ -alkyleneimine,
2. (b) 0.5 to 40% by weight of at least one nonionic, anionic and / or cationic surfactant,
3. (c) 0.5 to 50% by weight of an inorganic builder,
4. (d) 0 to 10% by weight of an organic cobuilder and
5. (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, Dyestuffs, bactericides and preservatives, dissolution improvers and / or disintegrants, water,

wherein the sum of components (a) to (e) gives 100 wt .-%.

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

1. (a) 0,05 bis 20 Gew.-% mindestens eines hydrophob modifizierten Poly-C₂-C₄-alkylenimins,
2. (b) 0,5 bis 70 Gew.-% mindestens eines nichtionischen, anionischen und/oder kationischen Tensids,
3. (c) 0 bis 20 Gew.-% eines anorganischen Builders,
4. (d) 0 bis 10 Gew.-% eines organischen Cobuilders,
5. (e) 0,1 bis 60 Gew.-% anderer üblicher Inhaltsstoffe, wie Soda, Enzyme, Parfüm, Komplexbildner, Korrosionsinhibitoren, Bleichmittel, Bleichaktivatoren, Bleichkatalysatoren, weitere Farbschutzadditive und Farbübertragungsinhibitoren, Vergrauungsinhibitoren, Soil-Release-Polyester, Faserschutzadditive, Silicone, Farbstoffe, Bakterizide und Konservierungsmittel, organische Lösemittel, Löslichkeitsvermittler, Hydrotrope, Verdicker und/oder Alkanolamine und
6. (f) 0 bis 99,35 Gew.-% Wasser,

wobei die Summe der Komponenten (a) bis (f) 100 Gew.-% ergibt.The liquid detergent formulations preferably have the following composition:

1. (a) 0.05 to 20% by weight of at least one hydrophobically modified poly-C ₂ -C ₄ -alkyleneimine,
2. (b) 0.5 to 70% by weight of at least one nonionic, anionic and / or cationic surfactant,
3. (c) 0 to 20% by weight of an inorganic builder,
4. (d) 0 to 10% by weight of an organic cobuilder,
5. (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
6. (f) 0 to 99.35% by weight of water,

wherein the sum of components (a) to (f) gives 100 wt .-%.

• (a) 0,05 bis 20 Gew.-% mindestens eines hydrophob modifizierten Poly-C₂-C₄-alkylenimins,
• (b) 0,1 bis 40 Gew.-% mindestens eines kationischen Tensids,
• (c) 0 bis 30 Gew.-% mindestens eines nichtionischen Tensids,
• (d) 0,1 bis 30 Gew.-% anderer üblicher Inhaltsstoffe, wie Silicone, andere Gleitmittel, Benetzungsmittel, filmbildende Polymere, Duft- und Farbstoffe, Stabilisatoren, Faserschutzadditive, weitere Farbschutzadditive und Farbübertragungsinhibitoren, Komplexbildner, Viskositätsmodifizierer, Soil-Release-Additive, Löslichkeitsvermittler, Hydrotrope, Korrosionsschutzadditive, Bakterizide und Konservierungsmittel und
• (e) 0 bis 99,75 Gew.-% Wasser,

wobei die Summe der Komponenten (a) bis (e) 100 Gew.-% ergibt.The laundry aftertreatment agents, in particular laundry detergent, preferably contain

• (a) 0.05 to 20% by weight of at least one hydrophobically modified poly-C ₂ -C ₄ -alkyleneimine,
• (b) 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% by weight 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 color transfer inhibitors, chelating agents, viscosity modifiers, soil release additives , Solubilizers, hydrotropes, anticorrosion additives, bactericides and preservatives, and
• (e) 0 to 99.75% by weight of water,

wherein the sum of components (a) to (e) gives 100 wt .-%.

• Alkoxylierte C₈-C₂₂-Alkohole, wie Fettalkoholalkoxylate, Oxoalkoholalkoxylate und Guerbet-alkoholethoxylate: Die Alkoxylierung kann mit Ethylenoxid, Propylenoxid und/oder Butylenoxid erfolgen. Es können Blockcopolymerisate oder statistische Copolymere vorliegen. Pro mol Alkohol enthalten sie üblicherweise 2 bis 50 mol, vorzugsweise 3 bis 20 mol, mindestens eines Alkylenoxids. Bevorzugtes Alkylenoxid ist Ethylenoxid. Die Alkohole haben vorzugsweise 10 bis 18 Kohlenstoffatome;
• Alkylphenolalkoxylate, insbesondere Alkylphenolethoxylate, die C₆-C₁₄-Alkylketten und 5 bis 30 mol Alkylenoxid/mol enthalten;
• Alkylpolyglucoside, die C₈-C₂₂-, vorzugsweise C₁₀-C₁₈-Alkylketten und in der Regel 1 bis 20, vorzugsweise 1,1 bis 5, Glucosideinheiten enthalten;
• N-Alkylglucamide, Fettsäureamidalkoxylate, Fettsäurealkanolamidalkoxylate, langkettige Aminoxide, Polyhydroxy(alkoxy)fettsäurederivate wie z.B. Polyhydroxyfettsäureamide, Geminitenside sowie Blockcopolymere aus Ethylenoxid, Propylenoxid und/oder Butylenoxid;

sowie ihre Mischungen.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;
• Alkylphenolalkoxylate, in particular alkylphenol ethoxylates containing C ₆ -C ₁₄ alkyl chains and 5 to 30 moles of alkylene oxide / mol;
• Alkyl polyglucosides containing C ₈ -C ₂₂ -, preferably C ₁₀ -C ₁₈ -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 such as, for example, polyhydroxy fatty acid amides, gemini surfactants and also block copolymers of ethylene oxide, propylene oxide and / or butylene oxide;

as well as their mixtures.

• Sulfate von (Fett)alkoholen mit 8 bis 22, vorzugsweise 10 bis 18, Kohlenstoffatomen, insbesondere C₉C₁₁-Alkoholsulfate, C₁₂C₁₄-Alkoholsulfate, C₁₂-C₁₈-Alkoholsulfate, Laurylsulfat, Cetylsulfat, Myristylsulfat, Palmitylsulfat, Stearylsulfat und Talgfettalkoholsulfat;
• Sulfatierte alkoxylierte C₈-C₂₂-Alkohole (Alkylethersulfate): Verbindungen dieser Art werden beispielsweise dadurch hergestellt, dass man zunächst einen C₈-C₂₂-, vorzugsweise einen C₁₀-C₁₈-Alkohol, z.B. einen Fettalkohol, alkoxyliert und das Alk-oxylierungsprodukt anschließend sulfatiert. Für die Alkoxylierung verwendet man vorzugsweise Ethylenoxid;
• Lineare C₈-C₂₀-Alkylbenzolsulfonate (LAS), vorzugsweise lineare C₉-C₁₃-Alkylbenzolsulfonate und Alkyltoluolsulfonate;
• Alkansulfonate, insbesondere C₈-C₂₄-, vorzugsweise C₁₀-C₁₈-Alkansulfonate;
• Olefinsulfonate;
• Fettsäure und Fettsäureestersulfonate.
• Seifen, wie die Na- und K-Salze von C₈-C₂₄-Carbonsäuren.

sowie ihre MischungenSuitable anionic surfactants are, for example:

• Sulfates of (fatty) alcohols having 8 to 22, preferably 10 to 18, carbon atoms, in particular C ₉ C ₁₁ -alcohol sulfates, C ₁₂ C ₁₄ -alcohol sulfates, C ₁₂ -C ₁₈ -alcohol sulfates, lauryl sulfate, cetyl sulfate, myristyl sulfate, palmitylsulfate, stearyl sulfate and tallow fatty alcohol sulfate;
• Sulfated alkoxylated C ₈ -C ₂₂ alcohols (alkyl ether): Compounds of this type are prepared for example by firstly treating a C ₈ -C ₂₂ -, preferably a C ₁₀ -C ₁₈ alcohol, for example a fatty alcohol alkoxylated and Alk oxylierungsprodukt then sulfated. For the alkoxylation is preferably used ethylene oxide;
• C ₈ -C ₂₀ linear alkyl benzene sulfonates (LAS), preferably linear C ₉ -C ₁₃ alkyl benzene sulfonates and alkyl toluenesulfonates;
• Alkanesulfonates, in particular C ₈ -C ₂₄ -, preferably C ₁₀ -C ₁₈ -alkanesulfonates;
• olefin;
• Fatty acid and fatty acid ester sulfonates.
• Soaps, such as the Na and K salts of C ₈ -C ₂₄ 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.

• C₇-C₂₅-Alkylamine;
• N,N-Dimethyl-N-(hydroxy-C₇-C₂₅-alkyl)ammoniumsalze;
• mit Alkylierungsmitteln quaternisierte Mono- und Di-(C₇-C₂₅-alkyl)dimethylammoniumverbindungen;
• Esterquats, insbesondere quaternäre veresterte Mono-, Di- und Trialkanolamine, die mit C₈-C₂₂-Carbonsäuren verestert sind;
• Imidazolinquats, insbesondere 1-Alkylimidazoliniumsalze der Formeln II oder III
  
  in denen die Variablen folgende Bedeutung haben:
  • R⁹ C₁-C₂₅-Alkyl oder C₂-C₂₅-Alkenyl;
  • R¹⁰ C₁-C₄-Alkyl oder Hydroxy-C₁-C₄-alkyl;
  • R¹¹ C₁-C₄-Alkyl, Hydroxy-C₁-C₄-alkyl oder ein Rest R¹-(CO)-X-(CH₂)_m- (X:-O-oder -NH-; m: 2 oder 3),

wobei mindestens ein Rest R⁹ C₇-C₂₂-Alkyl ist.Particularly suitable cationic surfactants are:

• C ₇ -C ₂₅ -alkylamines;
• N, N-dimethyl-N- (hydroxy-C ₇ -C ₂₅ -alkyl) ammonium salts;
• mono- and di (C ₇ -C ₂₅ -alkyl) dimethylammonium compounds quaternized with alkylating agents;
• Esterquats, in particular quaternary esterified mono-, di- and trialkanolamines esterified with C ₈ -C ₂₂ -carboxylic acids;
• Imidazolinquats, in particular 1-Alkylimidazoliniumsalze of the formulas II or III
  
  in which the variables have the following meaning:
  • R ^{9 is} C ₁ -C ₂₅ alkyl or C ₂ -C ₂₅ 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.

• Kristalline und amorphe Alumosilikate mit ionenaustauschenden Eigenschaften, wie vor allem Zeolithe: Verschiedene Typen von Zeolithen sind geeignet, insbesondere die Zeolithe A, X, B, P, MAP und HS in ihrer Na-Form oder in Formen, in denen Na teilweise gegen andere Kationen wie Li, K, Ca, Mg oder Ammonium ausgetauscht ist;
• Kristalline Silikate, wie insbesondere Disilikate und Schichtsilikate, z.B. δ- und β-Na₂Si₂O₅. Die Silikate können in Form ihrer Alkalimetall-, Erdalkalimetall- oder Ammoniumsalze eingesetzt werden, bevorzugt sind die Na-, Li- und Mg-Silikate;
• Amorphe Silikate, wie Natriummetasilikat und amorphes Disilikat;
• Carbonate und Hydrogencarbonate: Diese können in Form ihrer Alkalimetall-, Erd-alkalimetall- oder Ammoniumsalze eingesetzt werden. Bevorzugt sind Na-, Li- und Mg-Carbonate und -Hydrogencarbonate, insbesondere Natriumcarbonat und/oder Natriumhydrogencarbonat; sowie
• Polyphosphate, wie Pentanatriumtriphosphat.

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 sheet silicates, for example δ- and β-Na ₂ Si ₂ O ₅ . The silicates may be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preferred are 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; such as
• Polyphosphates, such as pentasodium triphosphate.

• Niedermolekulare Carbonsäuren, wie Citronensäure, hydrophob modifizierte Citronensäure, z. B. Ägaricinsäure, Äpfelsäure, Weinsäure, Gluconsäure, Glutarsäure, Bernsteinsäure, Imidodibernsteinsäure, Oxydibernsteinsäure, Propantricarbonsäure, Butantetracarbonsäure, Cyclopentantetracarbonsäure, Alkyl- und Alkenylbemsteinsäuren und Aminopolycarbonsäuren, z.B. Nitrilotriessigsäure, β-Alanin-diessigsäure, Ethylendiamintetraessigsäure, Serindiessigsäure, Isoserindiessigsäure, N-(2-Hydroxyethyl)-iminoessigsäure, Ethylendiamindibernsteinsäure und Methyl- und Ethyl-glycindiessigsäure oder deren Alkalimetallsalze;
• Oligomere und polymere Carbonsäuren, wie Homopolymere von Acrylsäure und Asparaginsäure, Oligomaleinsäuren, Copolymere der Maleinsäure mit Acrylsäure, Methacrylsäure oder C₂-C₂₂-Olefinen, z.B. Isobuten oder langkettigen α-Olefinen, Vinyl-C₁-C₈-alkylether, Vinylacetat, Vinylpropionat, (Meth)Acrylsäureester von C₁-C₈-Alkoholen und Styrol. Bevorzugt sind die Homopolymere der Acrylsäure und Copolymere von Acrylsäure mit Maleinsäure. Die oligomeren und polymeren Carbonsäuren werden in Säureform oder als Natriumsalz eingesetzt;
• Phosphonsäuren wie z.B. 1-Hydroxyethylen(1,1-diphosphonsäure), Ami-notri(methylenphosphonsäure), Ethylendiamintetra(methylenphosphonsäure) und Diethylentriaminpenta(methylenphosphonsäure) und deren Alkalimetallsalze.

As organic cobuilders are particularly suitable:

• Low molecular weight carboxylic acids such as citric acid, hydrophobically modified citric acid, e.g. B. Ägaricinsäure, malic acid, tartaric acid, gluconic acid, glutaric acid, succinic acid, Imidodibernsteinsäure, Oxydibernsteinsäure, propanetricarboxylic acid, butanetetracarboxylic, cyclopentanetetracarboxylic, alkyl and alkenylsuccinic and aminopolycarboxylic acids, eg nitrilotriacetic acid, β-alanine-diacetic acid, ethylenediaminetetraacetic acid, Serindiessigsäure, Isoserindiessigsäure, 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, for example isobutene or long-chain α-olefins, vinyl-C ₁ -C ₈ -alkyl ethers, vinyl acetate, Vinyl propionate, (meth) acrylic acid esters of C ₁ -C ₈ -alcohols and styrene. Preferred are 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), Ami-notri (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. Tie 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 , to find.

Application of hydrophobically modified poly-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 cotton and polyester / polyester and polyester / cotton ballast fabrics and polyester with a detergent at 60 ° 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). From the remission values measured on the test fabric, after the in A. Kud, soaps, oils, fats, waxes, volume 119, pages 590-594 (1993 ) determines the color strength of the staining. 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%. $$\mathrm{F}\ddot{\mathrm{U}}\mathrm{l}\mathrm{-}\mathrm{effect}\left[\mathrm{\%}\right]\mathrm{=}\frac{\mathrm{Dyer}\ddot{\mathrm{a}}\mathrm{strength}\left(\mathrm{without\; polymer}\right)\mathrm{-}\mathrm{Dyer}\ddot{\mathrm{a}}\mathrm{strength}\left(\mathrm{with\; polymer}\right)}{\mathrm{Dyer}\ddot{\mathrm{a}}\mathrm{strength}\left(\mathrm{without\; polymer}\right)\mathrm{-}\mathrm{Dyer}\ddot{\mathrm{a}}\mathrm{strength}\left(\mathrm{in\; front\; of\; the\; W}\ddot{\mathrm{a}}\mathrm{cal}\right)}\mathrm{x}\mathrm{100}$$

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 washing conditions Washing conditions main wash device Launder-o-meter of the company Atlas, Chicago, USA Dosage detergent 5.0 g / l liquor detergent A water hardness 3 mmol / l Ca: Mg 4: 1 liquor ratio 1:16 wash temperature 60 ° C washing time 30 min Dosage of polymer 0.05 g / l liquor colored fabric 1 g of EMPA 130 (CI Direct Red 83: 1) 1 g of EMPA 132 (CI Direct Black 22) 1 g of EMPA 133 (CI Direct Blue 71) 0.5 g EMPA 134 (CI Direct Orange 39) (all Federal Material Testing Institute, St. Gallen, Switzerland) Test fabric 5 g cotton fabric 221 (bleached) ballast fabric 5 g blended fabric 768 (65:35 PES: BW) + 5 g polyester fabric 854 Composition detergent A (liquid detergent) ingredients [Wt .-%] C ₁₃ C ₁₅ oxo alcohol x 7 EO 12 C ₆ -alcohol x 5 EO 5 citric acid 3 propylene glycol 10 ethanol 2 Diethylenetriamine-penta (methylenephosphonic acid) 1.0 water on 100 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: 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: tertiary 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). It was heated to 100 ° C. After addition of palmitic acid (179 g), the reaction mixture was brought to 120 ° C and distilled off with stirring the resulting water through a Wasserauskreiser (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 ° C and distilled off with stirring the resulting water through a Wasserauskreiser (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). It was heated to 100 ° C. After addition of palmitic acid (502 g), the reaction mixture was brought to 120 ° C and distilled off with stirring the resulting water through a Wasserauskreiser (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 ° C. After addition of dodecylic acid (396 g), the reaction mixture was brought to 120 ° C and the resulting water with stirring over a Wasserauskreiser distilled off (30h). Subsequently, the toluene was removed under reduced pressure. A tough reddish brown product was obtained (558 g).

Polymer 6

149 g of polyethyleneimine A were initially charged in toluene (400 ml) and heated to 100.degree. After addition of stearic acid (424 g), the reaction mixture was brought to 120 ° C and distilled off the resulting water over a Wasserauskreiser with stirring (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 ° C. After addition of palmitic acid (258 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 (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 FÜI 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 25000 neg. effect 46.1 40.2 41.7 PEI 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 25000 = polyethyleneimine A
PEI 5000 = polyethyleneimine B
Negative effect: Polymer shows no inhibition of the dye transfer but favors it.
* Polyvinylpyrrolidone: reference substance

Claims (15)

1. The use of hydrophobically modified poly-C₂-C₄-alkylenimines as dye transfer inhibitors in detergent compositions for textiles.
2. The use according to claim 1, where, 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. The use according to claim 2, where the fraction of the hydrocarbon radicals, based on the total weight of the poly-C₂-C₄-alkylenimine, constitutes 25 to 95% by weight.
4. The use according to claim 2 or 3, where the hydrocarbon radicals are present in the form of C₈-C₃₀-alkyl-, C₈-C₃₀-alkylcarbonyl, C₈-C₃₀-alkenyl-, C₈-C₃₀-alkenylcarbonyl-, C₈-C₃₀-alkadienyl-, C₈-C₃₀-alkadienylcarbonyl-and/or hydroxy-C₈-C₃₀-alkyl groups.
5. The use according to any one of the preceding claims, where the hydrophobically modified poly-C₂-C₄-alkylenimine has a number-average molecular weight in the range from 3000 to 300 000 Daltons.
6. The use according to any one of the preceding claims, where the hydrophobically modified poly-C₂-C₄-alkylenimine in the poly-C₂-C₄-alkylenimine moiety is branched.
7. The use according to any one of the preceding claims, where the hydrophobically modified poly-C₂-C₄-alkylenimine has quaternized nitrogen atoms.
8. The use according to any one of the preceding claims, where the hydrophobically modified poly-C₂-C₄-alkylenimine is obtainable by a process which comprises the reaction of a nonmodified poly-C₂-C₄-alkylenimine with a hydrophobicizing agent.
9. The use according to claim 8, where the hydrophobicizing agent is selected from saturated, mono- or polyunsaturated aliphatic C₉-C₃₁-carboxylic acids, their amide-forming derivatives and C₈-C₃₀-alkylene oxides.
10. The use according to claim 8 or 9, where the hydrophobicizing 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 per part by weight of unmodified poly-C₂-C₄-alkylenimine.
11. The use according to any one of claims 8 to 10, where the preparation of the hydrophobically modified poly-C₂-C₄-alkylenimine additionally comprises a quaternization.
12. The use according to any one of claims 8 to 11, where the unmodified poly-C₂-C₄-alkylenimine used for the preparation is branched.
13. The use according to any one of claims 8 to 12, where the unmodified poly-C₂-C₄-alkylenimine used for the preparation has a number-average molecular weight in the range from 1000 to 200 000 Daltons.
14. The use according to any one of the preceding claims, where the fraction of nonionic surfactants in the detergent composition, based on the total amount of surfactants in the detergent composition, is at least 50% by weight.
15. The use according to any one of the preceding claims, where the hydrophobically modified poly-C₂-C₄-alkylenimine is used in a concentration of from 5 to 150 ppm in the wash liquor.