EP1972683A1 - Amphoterous polymers as soil release additive in washing agents - Google Patents

Abstract

Use of polymers, which soluble in water at 20[deg] C comprising at least a polymerized monomer of: alkene amide monomer (a); alkene amide monomer (b); acryl- or methacryl acid; and/or other monomer groups of 3-6 carbon ethylenically unsaturated carboxylic acid such as crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid and their salts, or amide monomer (c) and its salt, preferably alkali metal and ammonium salts, as soil-release additive in detergents, is claimed, where the acryl- or methacryic acid monomer is present at greater than 25 wt.%. Use of polymers, which soluble in water at 20[deg] C comprising at least a polymerized monomer of: alkene amide monomer of formula (H 2C=CR 1>-CO-NH-R 2>-N +>R 3>R 4>R 5>X ->) (a); alkene amide monomer of formula (H 2C=CR 6>-CO-NR 7>R 8>) (b); acryl- or methacryl acid; and/or other monomer groups of 3-6 carbon ethylenically unsaturated carboxylic acid such as crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid and their salts, or amide monomer of formula (H 2C=CR-CO-NH-CR1aR2aR3a-SO 3H) (c) and its salt, preferably alkali metal and ammonium salts, as soil-release additive in detergents, is claimed, where the acryl- or methacryic acid monomer is present at greater than 25 wt.%. R 1>H or 1-4C alkyl; R 2>1-12C alkylene; R 3>-R 5>H, 1-18C alkyl or phenyl; X ->anion of halo, sulfates and/or alkylsulfate, OH, phosphate, acetate, formiate or ammonium; R 6>H, 1-6C alkyl; R 7>, R 8>H, 1-4C alkyl or 3-6C cycloalkyl; and R1a, R2a, R3a : H or 1-4C alkyl(ene). Provided that R 7> and R 8> not simultaneously H. Independent claims are included for: (1) process of incorporating a soil-release polymer with the textiles comprising: contacting the textile in an alkaline solution with an agent containing (I) and, optionally surfactant and further additives; heating the obtained textile by at least 30[deg] C; and subsequently drying, where optionally the textile is contacted with clean water before drying; (2) liquid detergent, comprising: (I) (0.05-10 (preferably 0.05-5) wt.%); surfactant (5-45 wt.%); water (at least 16 wt.%); and optionally further auxiliary material and additives; and (3) solid detergent comprising: (I) (0.05-10 (preferably 0.05-5) wt.%); surfactant (2-20 wt.%); water (0.05-10 wt.%); and optionally further auxiliary material and additives.

Description

The present application relates to additives for laundry detergents, which additives improve soil release from the fibers or surfaces and / or prevent or reduce redeposition, as well as laundry detergents containing such polymers.

Detergents contain in addition to the indispensable for the washing process ingredients such as surfactants and builders usually other ingredients that can be summarized under the term washing aids and include such different active ingredients such as foam regulators, grayness inhibitors, bleach, bleach activators and dye transfer inhibitors. Such excipients also includes substances which impart soil repellency properties to the laundry fiber and which, if present during the wash, aid the soil release properties of the remaining detergent ingredients. These polymers are applied to the fiber by a first washing process and then facilitate the washing process in the following washing process by a reduced adhesion of the dirt. If then always washed with the polymer, the effect is retained. The same applies mutatis mutandis to cleaners for hard surfaces. Such soil release agents are often referred to as "soil release" agents or because of their ability to impart soil repellency to the treated surface, such as the fiber, as "soil repellents".
The prior art already shows a large number of chemical compounds which are suitable as soil-release additives. For example, describes the EP 253 567 Soil-release polymers having a molecular weight of 900 to 9000 of ethylene terephthalate and polyethylene oxide terephthalate, wherein the polyethylene glycol units have molecular weights of 300 to 3000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 0.6 to 0.95. From the DE 101 52 308 A1 For example, polymers of polyisocyanates with polymeric polyols are known as soil-release additives for cotton fibers.

All polymers of the prior art have a rather specific and very narrow spectrum of activity, ie they either act only on certain tissues or only against certain soiling. There is therefore a continuous need for new soil-release additives, with the broadest possible spectrum of action. A particular need is seen in oil and / or greasy stains, such as engine oil, and in particular stains on blended fabrics (cotton / synthetic) or on pure cotton, since such soiling is difficult to remove by detergents.

It has been found that certain amphoteric, water-soluble terpolymers can achieve the object.

• a) H₂C=CR¹-CO-NH-R²-N⁺R³R⁴R⁵ X^-
  wobei R¹ für ein Wasserstoffatom oder einen Alkylrest mit 1 bis 4 C-Atomen steht, R² für einen linearen oder verzweigten Alkylenrest mit 1 bis 12 C-Atomen und R³, R⁴, R⁵ unabhängig voneinander ein Wasserstoffatom, einen Alkylrest mit 1 bis 18 C-Atomen oder einen Phenlyrest bedeuten, und X- für ein Anion aus der Gruppe der Halogene, Sulfate bzw. Alkylsulfate oder Hydroxid, Phosphat, Acetat, Formiat oder Ammonium steht, und
• b) H₂C=CR⁶-CO-NR⁷R⁸
  wobei R⁶ für ein Wasserstoffatom oder einen Alkylrest mit 1 bis 4 C-Atomen steht und R⁷ und R⁸, jeweils unabhängig voneinander für ein Wasserstoffatom, einen Alkylrest mit 1 bis 4 C-Atomen oder einen C3-C6 Cycloalkylrest steht, mit der Maßgabe, dass R⁷ und R⁸ nicht gleichzeitig für eine Wasserstoffatom stehen, und
• c) Acryl- und/oder Methacrylsäure und / oder
• d) weitere Monomere aus der Gruppe der C3-C6 einfach ethylenisch ungesättigten Carbonsäuren wie Crotonsäure, Maleinsäure, Maleinsäureanhydrid, Fumarsäure, Itaconsäure, sowie deren Halbester, und Salze, oder H₂C=CR-CO-NH-CR'R"R"'-SO₃H und deren Salze, insbesondere die Alkalimetall- und Ammoniumsalze, wobei R, R', R" und R'" unabhängig voneinander für ein Wasserstoffatom oder einen Alkyl(en)rest mit 1 bis 4 C-Atomen steht,

mit der Maßgabe, dass in dem Polymer das Monomere c) in Mengen von höchstens 25 Gew.-% bezogen auf das Polymer enthalten sind, als Soil-release Additive für Waschmittel.A first subject of the present application therefore relates to the use of water-soluble at 20 ° C polymers containing at least one polymerized monomer

• a) H ₂ C = CR ¹ -CO-NH-R ² -N ⁺ R ³ R ⁴ R ⁵ X ^-
  where R ^{1 is} a hydrogen atom or an alkyl radical having 1 to 4 C atoms, R ^{2 is} a linear or branched alkylene radical having 1 to 12 C atoms and R ³ , R ⁴ , R ⁵ are each independently a hydrogen atom, an alkyl radical 1 to 18 C atoms or a phenyl radical, and X- represents an anion from the group of halogens, sulfates or alkyl sulfates or hydroxide, phosphate, acetate, formate or ammonium, and
• b) H ₂ C = CR ⁶ -CO-NR ⁷ R ⁸
  where R ^{6 is} a hydrogen atom or an alkyl radical having 1 to 4 C atoms and R ⁷ and R ⁸ , each independently of one another represent a hydrogen atom, an alkyl radical having 1 to 4 C atoms or a C 3 -C 6 cycloalkyl radical, with Provided that R ⁷ and R ^{8 are} not simultaneously a hydrogen atom, and
• c) acrylic and / or methacrylic acid and / or
• d) other monomers from the group of C3-C6 monoethylenically unsaturated carboxylic acids such as crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, and their half-esters, and salts, or H ₂ C = CR-CO-NH-CR'R "R"'-SO ₃ H and salts thereof, in particular the alkali metal and ammonium salts, where R, R', R "and R '" independently of one another represent a hydrogen atom or an alkyl (ene) radical having 1 to 4 C atoms,

with the proviso that in the polymer, the monomer c) are contained in amounts of at most 25 wt .-% based on the polymer, as soil-release additives for detergents.

The polymers according to the above description are the subject of the earlier European application no. 06019028.7 the applicant. Although this application also describes a use of the polymers for preventing re-soiling, but only with regard to hard surfaces, ie, for example, in dishwashing detergents. However, this does not anticipate the specific use now claimed for detergents.
For the use according to the invention, preference is given to polymers according to the above description whose weight fraction of monomers c) is less than 15% by weight and in particular equal to or less than 10% by weight. A preferred weight range for the monomer c) is 5 to 25, preferably 5 to 15 and in particular from 5 to 10 wt .-%, each based on the total weight of the polymer. The polymers to be used according to the invention contain as polymerized monomers at least three different monomers a) to d). In this case, all polymers are included which contain either the monomer units a), b) and c), or a), b) and d) or a), b), c) and d) side by side. It is also within the meaning of the present invention possible to use mixtures of the listed polymers.

Monomer component a)

The monomers of this type follow the general formula

H ₂ C = CR ¹ -CO-NH-R ² -N ⁺ R ³ R ⁴ R ⁵ X ^-

where R ^{1 is} a hydrogen atom or an alkyl radical having 1 to 4 C atoms, R ^{2 is} a linear or branched alkylene radical having 1 to 12 C atoms and R ³ , R ⁴ , R ⁵ are each independently a hydrogen atom, an alkyl radical 1 to 18 carbon atoms or a phenyl radical, and X is an anion from the group of halogens, sulfates or alkyl sulfates, for hydroxide, phosphate, acetate, formate or ammonium. Particular preference is given to those monomers of type a) in which R ^{1 is} a methyl radical, R ^{2 is} a CH ₂ -CH ₂ -CH _{2 group} , and R ³ , R ⁴ and R ^{5 are} each methyl. X - represents a suitable counterion such as halide, hydroxide, sulfate, hydrogen sulfate, phosphate, formate or acetate, preferably chloride. These are known to those skilled in the art under the name 3-trimethylammoniumpropylmethacrylamidchlorid (MAPTAC).

Monomer component b)

The second, necessarily in the polymers of the invention contained monomer is a nitrogen-containing ethylenically unsaturated compound of the following general formula:

H ₂ C = CR ⁶ -CO-NR ⁷ R ⁸

where R ^{6 is} a hydrogen atom or an alkyl radical having 1 to 4 C atoms and R ⁷ and R ⁸ , each independently of one another represent a hydrogen atom, an alkyl radical having 1 to 4 C atoms or a C 3 -C 6 cycloalkyl radical, with Provided that R ⁷ and R ^{8 are} not simultaneously a hydrogen atom. These are therefore alkylacrylamides. Particular preference is given to N-isopropylacrylamide, also known by the abbreviation NIPAM.

Monomer component c)

As a third component c) ethylenically unsaturated acids and their salts, such as acrylic or methacrylic acid are suitable. Acrylic acid (AA) is the most preferred monomer here. Particularly suitable salts are their alkali metal and ammonium salts.

Monomer component d)

Further monomers may additionally or instead of component c) be contained in the polymers according to the invention as building blocks. They are selected from the group of C3-C6 monoethylenically unsaturated carboxylic acids such as crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid and their half-esters, and salts or H ₂ C =CR-CO-NH-CR'R "R"'- SO ₃ H and their salts, in particular the alkali metal and ammonium salts, where R, R ', R "and R"' independently of one another represent a hydrogen atom or an alkyl (ene) radical having 1 to 4 C atoms. Particularly preferred is the monomer of the type d), the molecule having the general formula H ₂ C = CR-CO-NH-CR'R "R '" - SO ₃ H, in particular a derivative, the 2-acrylamido-2 methylpropanesulfonic acid (AMPS) is emphasized.

There may be further monomer units in addition to the above-mentioned a) to d) in the polymers of the invention, in which case nitrogen-containing monomers are particularly preferred. Examples are dimethyldiallylammonium chloride (DADMAC), 2-dimethylaminoethyl (meth) acrylate (DMAE (M) A), 2-diethylaminoethyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylamide (DMAP (M) A), 3-dimethylamino-2, 2-dimethylpropyl acrylamide (DMADMPA), as well as the optionally resulting therefrom by protonation or quaternization derivatives, in particular 2-trimethylammoniumethyl (meth) acrylate chloride and 3-Diethylmethylammoniumpropylacrylamidchlorid. The polymers according to the invention are water-soluble, ie that at least 0.1 g of the polymer in 100 ml of water at 20 ° C are soluble. The polymers are ampholytic, ie the polymers have both acidic and basic hydrophilic groups and behave acidic or basic depending on the condition. The polymers of the invention preferably have a mean molecular weight (weight average molecular weight, M _w), measured by gel permeation chromatography aqueous (GPC) with light scattering detection (SEC-MALLS), in the range of 10,000 to 500,000 Da. Preferably, the molecular weight of the polymers is between 50,000 and 350,000 Da and in particular between 100,000 and 250,000 Da. A particularly preferred range may be between 110,000 and 140,000 Da. The various monomer building blocks a) to d) preferably coexist in certain selected proportions. Preference is given in each case to those polymers which contain component (b) in excess (based on both moles and weight of the components) to components a) and c). Preferred here are polymers in which the molar ratio between the monomers a), b) and c) in the range of 1: 10: 1 to 5: 10: 5 and preferably in the range of 4: 10: 1 to 4: 10: 3 and especially in the range of 3: 8: 2 to 3: 8: 1. Particular preference is given in particular to those polymers in which the molar ratio between components a) and b) is from 1:10 to 1: 1 and in particular from 1: 5 to 1: 1. Based on mol% of the respective monomers, preferably 20 to 30% of monomer a), 50 to 70% of monomer b) and 10 to 20% of monomer c) are contained. If, instead of component c), the monomer component of type d) is present, the same conditions apply analogously. However, particularly preferred polymers may be those which contain both monomers of type c) and of type d) side by side. Preferably, the monomer units c) and d) are then present in a molar ratio of 2: 1 to 1: 2, more preferably in a ratio of 1: 1, side by side. Particularly preferred polymers with four different monomer building blocks have molar ratios a): b): c): d) of 2: 4: 1: 1 to 1: 10: 1: 1. A particularly preferred ratio is 3: 8: 1: 1. Preferred polymers are, in particular, those in which the monomer a) is selected from those compounds of the general formula in which R ^{1 is} a methyl group, R ^{2 is} an alkylene radical having 3 C Atoms, R ³ , R ⁴ and R ^{5 are} each methyl radicals and X is chloride, the monomer b) is selected from those compounds of the general formula in the R ⁶ and R ^{7 is} a hydrogen atom and R ^{8 is} an isopropyl radical and monomer c) is acrylic acid. Also preferred are polymers in which the monomer a) is selected from those compounds of the general formula in which R ^{1 is} a methyl group, R ^{2 is} an alkylene radical having 3 C atoms, R ³ , R ⁴ and R ^{5 are} each methyl and X is are chloride, the monomer b) is selected from those compounds of the general formula in which R ⁶ and R ^{7 are} a hydrogen atom and R ^{8 is} an isopropyl radical and monomer c) for H ₂ C = CR-CO-NH-CR ' R "R"'- SO ₃ H and salts thereof, in particular the alkali metal and ammonium salts, where R, R', R "and R"'independently of one another represent a hydrogen atom or an alkyl radical having 1 to 4 C -Atoms stands, is.

Such polymers to be used according to the invention can be prepared by polymerization processes which are known to the person skilled in the art. They can be prepared, for example, by solution polymerization or bulk polymerization. Preferably, they are prepared by solution polymerization, ie, a polymerization of monomers in solvents and / or water, in which both the monomers and the polymers resulting from them are soluble. Furthermore, the polymerization can be carried out with presentation of the total amount of monomer or with monomer feed, batchwise, semicontinuously or continuously. Preferably, the polymerization is carried out as a batch polymerization with or without monomer feed.

A particularly preferred subject matter of the present invention is the use of a polymer which is water-soluble at 20 ° C. and contains at least three different monomers a), b), c) and / or d), it being true that the monomers a) and b) are mandatory in the molar ratio of 1: 1 to 1: 10 must be included and in addition the monomers c) and / or d) are contained, wherein as monomer a) the 3-trimethylammoniumpropylmethacrylamidchlorid (MAPTAC), as monomer b) the N-isopropylacrylamide (NIPAM ), as monomer c) acrylic acid (AA) and / or methacrylic acid (MA), as monomer d) 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) are selected, with the proviso that in the water-soluble polymer, the monomer c) is contained in amounts of at most 25 wt .-% based on the total weight of the water-soluble polymer. Preferred are those polymers according to the above description whose weight fraction of monomers c) is less than 15% by weight and in particular equal to or less than 10% by weight. A preferred weight range for the monomer c) is at 5 to 25, preferably 5 to 15 and in particular from 5 to 10 wt .-%, each based on the total weight of the polymer as a soil-release additive in detergents.

These polymers can also be described by the following formula scheme:

The indices m, n, p and q represent the number of monomer building blocks NIPAM, MAPTAC, AA and AMPS in the polymer molecule. However, the sequence of the building blocks in the polymers according to the invention is generally not necessarily predetermined; rather, all sequences of the individual building blocks, whether blocks of the individual monomers or their purely statistical sequence in the molecule, are encompassed. In this pre-defined type of polymer, particular preference is given to those derivatives which contain the monomers MAPTAC, NIPAM and AMPS polymerized in weight ratios of 25 to 50% MAPTAC, 40 to 75% NIPAM and 1 to 15% AMPS, with the proviso that the Summer of percentages 100 gives. An independently preferred polymer is one which contains the monomers MAPTAC, NIPAM, and AA polymerized in weight ratios of 25 to 50% MAPTAC, 40 to 75% NIPAM, and 1 to 15% AA, with the proviso that the percentages of the percents 100 results. Finally, independently of this, a water-soluble polymer at 20 ° C. is also preferred in that it contains the monomers MAPTAC, NIPAM, AA and AMPAS in a weight ratio of 25 to 45% MAPTAC, 40 to 70% NIPAM, 1 to 15% AA and 1 to 15% AMPS contains, provided that the sum of the percentage shares 100. Also for these polymers, the preferred molar ratios described above as well as the preferred face ratios of the monomers within the polymers, ie, that the molar ratio between the monomers a), b) and c) or d) in the range of 1: 10: 1 to 5: 10: 5, and preferably in the range of 4: 10: 1 to 4: 10: 3 and in particular in the range of 3: 8: 2 to 3: 8: 1. A particularly preferred polymer comprises the monomers a), b), c) and d) in a molar ratio of 3: 8: 1: 1. The weight ratio based on the polymer is 20 to 30 wt .-% of monomer a), 50 to 70 wt .-% of monomer b) and 10 to 20% by weight of monomers c) and / or d) with the proviso that the sum of the proportions is 100. The monomers c) and d), if they are present side by side in the polymer, are preferably in a weight ratio of 1: 1. The average molecular weight of the polymers selected, as described in detail above, is preferably in the range of 10,000 to 500,000.

The polymers described above are added as additives to known detergents - which may be solid or liquid. In this case, amounts between 0.01 to 10 wt .-% and in particular 0.05 to 10 wt .-% are particularly preferred. Very particular preference is given to the range from 0.05 to 5% by weight, in particular from 0.1 to 1.5% by weight.

The detergents may contain, in addition to the polymers, further adjuvants and additives customary for detergents, for example surfactants (anionic, nonionic, cationic and / or amphoteric surfactants), builders, other complexing agents, enzymes, bleaches and bleach activators or bleach boosters, builders, Perfumes and dyes, foam activators or foam inhibitors, non-aqueous solvents, disinfectants, optical brighteners, color transfer inhibitors, etc ..

As surfactants in particular anionic and nonionic surfactants are of importance. Typical examples of anionic surfactants are alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, alpha-ethyl ester sulfonates, sulfo fatty acids, alkyl sulfates, glycerol ether sulfates, fatty acid ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acyl amino acids such as acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially wheat based vegetable products) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution.

In this case, alkyl and / or alkenyl ether sulfates are preferably selected. Alkyl and / or alkenyl ether sulfates, which are suitable as component (b), are known and industrially available sulfation products of linear fatty alcohols or partially branched oxo alcohols. They preferably follow the formula (Ia),

RO (CH ₂ CH ₂ O) _n SO ₃ X (Ia)

in which R is a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms, n is a number from 1 to 10 and X is alkali and / or alkaline earth, ammonium, alkylammonium, alkanolammonium or glucammonium. Ether sulfates of the type mentioned are industrially produced by sulfation and subsequent neutralization of the corresponding alcohol polyglycol ether. Typical examples are the sulfates based on addition products of 1 to 10 and in particular 2 to 5 moles of ethylene oxide to caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol , Linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol, and technical mixtures thereof in the form of the sodium, potassium or magnesium salts.

Another class of preferred anionic surfactants are the alkylbenzenesulfonates (ABS). These preferably follow the formula (Ib)

R'-Ph-SO ₃ X (Ib)

in which R 'is a branched, but preferably linear, alkyl radical having 10 to 18 carbon atoms, Ph is a phenyl radical and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Preferably, dodecylbenzenesulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures are used in the form of the sodium salts.

In addition to the preferred alkyl and / or alkenyl ether sulfates or ABS, soaps, preferably sodium and potassium soaps, may additionally or instead be present as anionic surfactants in the compositions according to the invention. They are also the ones Ethanolamine salts suitable. In this case, amounts between 1 to 45 wt .-%, preferably 1 to 40 wt .-% and in particular of 30 wt .-%, preferably up to 15 wt .-% (each based on the total amount of detergent) are preferred. Preferably, the potassium or more preferably the sodium soaps of C 12 - C 18 fatty acids are used.

Furthermore, the concomitant use of nonionic surfactants is possible and preferred. A particularly preferred type of nonionic surfactants are those from the class of alkyl (oligo) glycosides, fatty alcohols and / or alkoxylated, preferably ethoxylated fatty alcohols.
Alkyl and alkenyl oligoglycosides are known nonionic surfactants which follow formula (II),

R ¹ O- [G] _p (II)

in which R ^{1 is} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry. The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (II) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound must always be an integer, and here especially If p = 1 to 6 can be assumed, the value p for a given alkyloligoglycoside is an analytically determined arithmetic quantity, which usually represents a fractional number. Preference is given to using alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization p of from 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4 are preferred. The alkyl or alkenyl radical R ¹ can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and technical mixtures thereof, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxo synthesis. Preference is given to alkyl (oligo) glucosides of chain length C ₈ -C ₁₀ (DP = 1 to 3), which are used as a feedstock in the distillative separation of technical C ₈ -C ₁₈ coconut fatty alcohol incurred and may be contaminated with a proportion of less than 6 wt .-% C ₁₂ alcohol and alkyl oligoglucosides based on technical C _9/11 -oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ¹ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14 carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and technical mixtures thereof which can be obtained as described above. Preference is given to alkyl oligoglucosides based on hydrogenated C _12/14 coconut alcohol having a DP of 1 to 3.

Alcohol ethoxylates are referred to as fatty alcohol or oxo alcohol ethoxylates and preferably follow the formula (III),

R ² O (CH ₂ CH ₂ O) _n H (III)

in which R ^{2 is} a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms and n is a number from 1 to 50, the range from 3 to 30 and in particular from 3 to 12 being particularly preferred. Typical examples are the adducts of an average of 1 to 50, preferably 5 to 40 and especially 10 to 25 moles of, for example, caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol , Petroselinylalkohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures, for example, in the high pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxo synthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols incurred. Also preferred are adducts of 10 to 40 moles of ethylene oxide with technical fatty alcohols having 12 to 18 carbon atoms, such as coconut, palm, palm kernel or tallow fatty alcohol.

As surfactants, in addition to the substances described above, it is also possible for all other nonionic, anionic, cationic and / or amphoteric agents known to the person skilled in the art to be present. Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, Fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or optionally mixed partially oxidized alk (en) yloligoglycosides or glucuronic acid derivatives, fatty acid N-alkylglucamides, protein hydrolysates (especially wheat-based vegetable products), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution.

Typical examples of cationic surfactants are quaternary ammonium compounds and ester quats, especially quaternized fatty acid trialkanolamine ester salts. Typical examples of amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. The surfactants mentioned are exclusively known compounds.

Preferably, those agents are used which contain nonionic surfactants in amounts of 1 to 35 wt .-%, preferably 5 to 25 wt .-% and in particular from 5 to 20 wt .-%. A further additional component may advantageously be soap, which then advantageously in amounts of 1 to 40 wt .-%, preferably from 10 to 38 wt .-% and in particular from 12 to 38 wt .-% based on the total weight of the liquid agent may be included. It may also be advantageous that the means gem. the above description are free of cationic surfactants and in particular free of cationic fabric softeners.
With particular advantage, agents are selected which contain a surfactant mixture consisting of anionic surfactants (other than soaps), alkyl (oligo) glycosides and fatty alcohol alkoxylates in the preferred weight ratio of 1: 1: 4 to 1: 1: 2. If soap is included, then in a ratio of preferably 4: 1 with respect to the other anionic surfactants also present. Furthermore, surfactant mixtures which contain anionic and / or nonionic surfactants in amounts of from 50 to 90% by weight are preferred.

Without being bound by any particular theory, the Applicant assumes with respect to the active principle of Soil-release additives that the polymers to be used according to the invention initially pass from the detergents into the aqueous wash liquor during the washing of the textiles and are then transferred from there to the fibers be and on the surface of the fibers, a thin polymer film is formed, which then, after drying of the laundry remains there and prevents or reduces further contamination, especially if in each further washing process again a polymer-containing detergent is used.

Another object of the invention is therefore directed to a process for the temporary (ie not to a permanent equipment, as used in textile production and finishing) equipment of textiles with a soil-release additives, wherein in a first step, the textile in one aqueous liquor with an agent containing polymers as described above, and optionally surfactants and other ingredients is brought into contact, wherein secondly, the aqueous liquor is heated together with the textile to a temperature of at least 30 ° C, and then dried the fabric optionally, the textile can be brought into contact with clear water before drying. The method is preferably carried out in washing machines, preferably those for private use, ie household washing machines. In this case, all conventional fiber materials, such as those used for laundry can be treated with the polymers of the invention. Preference is given to textiles made of cotton, in particular of pure cotton, cotton / synthetic blend fabrics or pure synthetic fabrics, wherein textiles of cotton and / or cotton / synthetic blend fabrics are particularly preferred. As synthetic fibers, in particular those of polyester are preferred.
A particularly advantageous effect to be used according to the invention polymers in the prevention of re-soiling with oil and / or greasy soil, such as engine oils or similar stains.

Particularly preferred is the use of the polymers of the invention in detergents, which may be liquid as well as solid. In this case, detergents are, in particular, understood as meaning those agents which are used for washing textiles and preferably items of laundry, preferably household laundry.

Another object of the invention therefore relates to a liquid detergent containing a) 0.05 to 10 wt .-%, and preferably 0.05 to 5 wt .-% of a polymer according to the above description and b) 5 to 45 wt. % of surfactants and c) at least 16 wt .-% water, and optionally d) other auxiliaries and additives. Such agents are, but with the addition of a specific color transfer inhibitor in the EP 1 645 619 A1 described. The Co-use of specific soil-release polymers within the meaning of the present technical teaching is not apparent from the document. However, the concomitant use of Polydiallyldimethylammoniumchloriden or their derivative may be excluded for the means (solid as liquid) of the present invention.

The surfactant component b) is preferably composed of the types described above. In addition to the surfactants mentioned, the liquid detergents may contain further typical ingredients such as, for example, solvents, hydrotropes, bleaches, builders, viscosity regulators, enzymes, enzyme stabilizers, optical brighteners, other soil repellents than the polymers according to the invention (however, it is preferred that only the polymers according to the invention for this purpose are included), foam inhibitors, inorganic salts and fragrances and dyes, provided that they are sufficiently stable in the aqueous environment. Suitable organic solvents are, for example, monofunctional and / or polyfunctional alcohols having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Preferred alcohols are ethanol, 1,2-propanediol, glycerol and mixtures thereof. The compositions preferably contain from 2 to 20% by weight and in particular from 5 to 15% by weight of ethanol or any mixture of ethanol and 1,2-propanediol or, in particular, of ethanol and glycerol. It is also possible that the preparations contain either in addition to the mono- and / or polyfunctional alcohols having 1 to 6 carbon atoms or polyethylene glycol alone with a molecular weight of between 200 and 2000, preferably to 600 in amounts of 2 to 17 wt .-% , As hydrotrope, for example, toluene sulfonate, xylene sulfonate, cumene sulfonate or mixtures thereof can be used.
Among the compounds serving as bleaches, which yield hydrogen peroxide in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents are, for example, peroxycarbonate, citrate perhydrates and salts of peracids, such as perbenzoates, peroxyphthalates or diperoxydodecanedioic acid. They are usually used in amounts of 8 to 25 wt .-%. Preference is given to the use of sodium perborate monohydrate in amounts of from 10 to 20% by weight and in particular from 10 to 15% by weight. Its ability to bind free water to form tetrahydrate contributes to increasing the stability of the agent. Preferably, however, the preparations are free of such bleaching agents.
Suitable builders are ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid and inorganic phosphonic acids, such as the neutral reacting sodium salts of 1-hydroxyethane-1,1-diphosphonate, which may be present in amounts of 0.5 to 5, preferably 1 to 2 wt .-%. As viscosity regulators, for example, hardened castor oil, salts of long-chain fatty acids, preferably in amounts of 0 to 5 wt .-% and in particular in amounts of 0.5 to 2 wt .-%, for example, sodium, potassium, aluminum, magnesium - And titanium stearates or the sodium and / or potassium salts of behenic acid, and other polymeric compounds are used. The latter preferably include polyvinylpyrrolidone, urethanes and the salts of polymeric polycarboxylates, for example homopolymeric or copolymeric polyacrylates, polymethacrylates and especially copolymers of acrylic acid with maleic acid, preferably those of 50% to 10% maleic acid. The molecular weight of the homopolymers is generally between 1,000 and 100,000, that of the copolymers between 2,000 and 200,000, preferably between 50,000 and 120,000, based on the free acid. In particular, water-soluble polyacrylates which are crosslinked, for example, with about 1% of a polyallyl ether of sucrose and which have a molecular weight of more than one million are also suitable. Examples of these are the thickening polymers available under the name Carbopol 940 and 941. The crosslinked polyacrylates are preferably used in amounts of not more than 1% by weight, preferably in amounts of from 0.2 to 0.7% by weight. The agents may additionally contain about 5 to 20% by weight of a partially esterified copolymer. These partially esterified polymers are prepared by copolymerization of (a) at least one C4-C28 olefin or mixtures of at least one C4-C28 olefin with up to 20 mol% of C1-C28 alkyl vinyl ethers and (b) ethylenically unsaturated dicarboxylic anhydrides of 4 to 8 carbon atoms in a molar ratio of 1: 1 to copolymers with K values of 6 to 100 and subsequent partial esterification of the copolymers with reaction products such as C 1 -C 13 alcohols, C 8 -C 22 fatty acids, C 1 -C 12 alkylphenols, secondary C 2 -C 30 amines or mixtures thereof with at least one C 2 -C 4 -alkylene oxide or tetrahydrofuran and hydrolysis of the anhydride groups of the copolymers to give carboxyl groups, wherein the partial esterification of the copolymers is carried out so far that 5 to 50% of the carboxyl groups of the copolymers are esterified. Preferred copolymers contain ethylenically unsaturated dicarboxylic anhydride maleic anhydride. The partially esterified copolymers can be present either in the form of the free acid or preferably in partially or completely neutralized form. Advantageously, the copolymers are used in the form of an aqueous solution, in particular in the form of a 40 to 50 wt .-% solution. The copolymers not only contribute to the primary and Secondary washing performance of the liquid detergent and cleaning agent, but also cause a desired viscosity reduction of the concentrated liquid detergent. By using these partially esterified copolymers concentrated aqueous liquid detergents are obtained, which are flowable under the sole influence of gravity and without the action of other shear forces. The concentrated aqueous liquid detergents preferably contain partially esterified copolymers in amounts of from 5 to 15% by weight and in particular in amounts of from 8 to 12% by weight. Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. The preparation of such liquid detergents takes place in the methods known to those skilled in the art, preferably by stirring the ingredients, if appropriate at elevated temperatures. The pH of such agents is generally 7 to 10.5, preferably 7 to 9.5 and especially 7 to 8.5. The setting of higher pH values, for example above 9, can be achieved by using small amounts of caustic soda or alkaline salts such as sodium carbonate or sodium silicate. The liquid detergents according to the invention generally have viscosities between 150 and 10,000 mPas (Brookfield viscometer, spindle 1, 20 revolutions per minute, 20 ° C.). In the process, viscosities of between 150 and 5000 mPas are preferred. The viscosity of the aqueous agents is preferably below 2000 mPas and is in particular between 150 and 1000 mPas.

Also a solid detergent comprising a) from 0.05 to 10% by weight, and preferably from 0.05 to 5% by weight of a polymer as described above, b) from 2 to 20% by weight of surfactants c) 0, 05 to 10 wt .-% water, and optionally d) other auxiliaries and additives is an object of the present technical teaching. In the case of solid detergents which can generally be formulated as powders, granules, extrudates or as shaped articles, for example tablets, adjuvants are, in particular, builders, bleaches and bleach activators.
As a solid builder in particular fine-crystalline, synthetic and bound water-containing zeolite such as zeolite NaA is used in detergent quality. Also suitable, however, are zeolite NaX and mixtures of NaA and NaX. The zeolite can be used as a spray-dried powder or else as undried, still moist, stabilized suspension of its preparation. Among the compounds serving as bleaches, which yield hydrogen peroxide in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents are, for example, peroxycarbonate, citrate perhydrates and salts of peracids, such as perbenzoates, peroxyphthalates or diperoxydodecanedioic acid. They are usually in quantities of 8 used to 25 wt .-%. Preference is given to the use of sodium perborate monohydrate in amounts of from 10 to 20% by weight and in particular from 10 to 15% by weight. Its ability to bind free water to form tetrahydrate contributes to increasing the stability of the agent. In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below, bleach activators can be incorporated into the preparations. Examples thereof are N-acyl or O-acyl compounds which form organic peracids with hydrogen peroxide, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols, such as glucose pentaacetate. The content of the bleach-containing agents in bleach activators is in the usual range, preferably between 1 and 10 wt .-% and in particular between 3 and 8 wt .-%. Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.

The preparation of the solid detergents can be carried out by any of the known methods such as mixing, spray-drying, granulation and extrusion. Particularly suitable are those processes in which several subcomponents, for example spray-dried components and granulated and / or extruded components, are mixed together. It is also possible that spray-dried or granulated components are subsequently applied in the preparation, for example, with nonionic surfactants, in particular ethoxylated fatty alcohols, according to the usual methods.

Examples

Three liquid detergents were prepared in which one (M1) without, one with (M2) a soil release additive (Repellotex: Fa. Rhodia) of the prior art and an inventive agent (E1) were compared.
The polymer used in the invention was prepared as follows: 12.4 g of MAPTAC, 1.4 g of acrylic acid and 50 g of water were mixed. The pH of the aqueous mixture was adjusted in the range of 6.5 to 7.5. Then, 8.5 g of NIPAM and 23 g of isopropanol were added, and this mixture was heated to 65 ° C. Then, as a starter, 0.15 g of 2,2'-azobis (2-amidinopropane) dihydrochloride was added and the reaction started. The mixture is heated to about 80 ° C. After the reaction had elapsed, the azeotrope water / isopropanol was distilled off at 80-100 ° C. The concentration of the resulting polymer solution was about 22 wt .-%. The pH of the solution was 5 to 7.5. The polymer had a molecular weight of 130,000 Da (measured by SEC-MALLS).

The composition of the liquid detergents can be found in the following table: Wt .-% active ingredient M1 E1 M2 water 53.8 52.8 52.8 NaOH 3.4 3.4 3.4 Soap 8.9 8.9 8.9 propylene glycol 5.0 5.0 5.0 Lauryl ether sulfate sodium salt 3.4 3.4 3.4 C12-18 fatty alcohol + 7 EO 13.5 13.5 13.5 C12-16-alkyl-1,4-glucoside 3.4 3.4 3.4 Inventive polymer - 1.0 - Repellotex SRP-4 - - 1.0 ethanol 3.0 3.0 3.0 borax 0.2 0.2 0.2 defoamers 0.4 0.4 0.4 NaCl 1.0 1.0 1.0 citric acid 3.0 3.0 3.0 biocide 0.1 0.1 0.1 amylase 0.5 0.5 0.5 protease 0.5 0.5 0.5 PH value 9.5 9.5 9.5

To test the performance of the test, test textiles were washed in a household washing machine at 40 ° C., the textiles being provided with various test stains were, or after passing through the washing process were provided. The following table shows the results for the detergents described above:

• Miele W 985
• 40°C Buntwaschprogramm
• Wasserhärte = 14°dH
• Balastwäsche = 4 kg bestehend aus sauberer Baumwolle IEC 456 und
• 4x Schmutzbalast wfk SBL 2004
• Dosierung WM = 75g/ Zyklus

Die gewaschenen Prüfmonitore wurden getrocknet und gebügelt. Anschließend wurde der Y Wert für jede Verfleckung mit Hilfe eines Spectralphotometers (Spectraflash 600 der Fa. Datacolor) unter Einsatz des UV Sperrfilters FL 42 bei Tageslicht D 65 ermittelt. Die angegebenen Werte sind Mittelwerte aus 5 Waschwiederholungen. Je höher der gemessene Wert, desto besser. Waschleistung 40°C nach dem 2. Waschzyklus : Anschmutzung Fasermaterial* M1 E1 M2 Staub Hautfett PES 78,7 82,7 79,9 Frittierfett PES 86,4 87,4 86,7 Motoröl PES/ Co 35 41,2 35,5 Motoröl PES 81,5 84 81,1 * PES= Polyester; PES/Co = Mischgewebe Polyester/ Baumwolle The tissues (= test monitors) were each prewashed 3 times with the recipe to be tested. On the fabric thus treated, the specified soiling were then abandoned, so that for each soiling an approximately 2 cm circular staining was generated. The stained tissues were aged for 1 week at room temperature. It was then washed again with the associated detergent.
Conditions for this wash cycle:

• Miele W 985
• 40 ° C Buntwaschprogramm
• Water hardness = 14 ° dH
• Balast laundry = 4 kg consisting of clean cotton IEC 456 and
• 4x dirt balancer wfk SBL 2004
• Dosage WM = 75g / cycle

The washed test monitors were dried and ironed. Subsequently, the Y value for each stain was determined by means of a spectrophotometer (Spectraflash 600 from Datacolor) using the UV blocking filter FL 42 in daylight D 65. The values given are average values of 5 washing repetitions. The higher the measured value, the better. <b> Washing performance 40 ° C after the 2nd washing cycle: </ b> soiling Fiber material * M1 E1 M2 Dust skin fat PES 78.7 82.7 79.9 frying oil PES 86.4 87.4 86.7 Engine oil PES / Co 35 41.2 35.5 Engine oil PES 81.5 84 81.1 * PES = polyester; PES / Co = blended fabric polyester / cotton

The results prove the particular effectiveness of the polymers according to the invention over oily or greasy stains.

Claims (10)

Use of water-soluble polymers at 20 ° C, containing at least one polymerized monomer e) H ₂ C = CR ¹ -CO-NH-R ² -N ⁺ R ³ R ⁴ R ⁵ X ^-
where R ^{1 is} a hydrogen atom or an alkyl radical having 1 to 4 C atoms, R ^{2 is} a linear or branched alkylene radical having 1 to 12 C atoms and R ³ , R ⁴ , R ⁵ are each independently a hydrogen atom, an alkyl radical 1 to 18 C atoms or a phenyl radical, and X ^{- represents} an anion from the group of the halogens, sulfates or alkyl sulfates or hydroxide, phosphate, acetate, formate or ammonium, and f) H ₂ C = CR ⁶ -CO-NR ⁷ R ⁸
where R ^{6 is} a hydrogen atom or an alkyl radical having 1 to 4 C atoms and R ⁷ and R ⁸ , each independently of one another represent a hydrogen atom, an alkyl radical having 1 to 4 C atoms or a C 3 -C 6 cycloalkyl radical, with Provided that R ⁷ and R ^{8 are} not simultaneously a hydrogen atom, and g) acrylic and / or methacrylic acid and / or h) other monomers from the group of C3-C6 monoethylenically unsaturated carboxylic acids such as crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, and their half-esters, and salts, or H ₂ C = CR-CO-NH-CR'R "R"'-SO ₃ H and salts thereof, in particular the alkali metal and ammonium salts, where R, R', R "and R '" independently of one another represent a hydrogen atom or an alkyl (ene) radical having 1 to 4 C atoms, with the proviso that in the polymer, the monomer c) is contained in amounts of at most 25 wt .-% based on the polymer,
as a soil-release additive in detergents. Process for finishing textiles with a soil-release polymer, characterized in that a) the textile is brought into contact in an aqueous liquor with an agent containing polymers as described in claim 1, and optionally surfactants and other ingredients, and then b) the aqueous liquor is heated together with the textile to a temperature of at least 30 ° C, and then c) the textile is dried, wherein d) optionally, the textile can be brought into contact with clear water before drying. A method according to claim 2, characterized in that it is carried out in a washing machine, preferably a household washing machine. A method according to any one of claims 1 to 3, characterized in that the textiles are made of cotton or synthetic fabric, but preferably of cotton and / or / cotton / synthetic .Mischgewebe. Liquid detergent containing a) 0.05 to 10 wt .-%, and preferably 0.05 to 5 wt .-% of a polymer as described in claim 1 b) 5 to 45 wt .-% of surfactants and c) at least 16 wt .-% water, and optionally d) other auxiliaries and additives. Composition according to claim 5, characterized in that it contains as component b) a surfactant mixture containing nonionic surfactants, anionic surfactants and optionally soap side by side. Composition according to claim 6, characterized in that anionic surfactants in amounts of 0.5 to 70 wt .-%, preferably 0.5 to 50 wt .-% and in particular in amounts of 1 to 25 wt .-%, based on the agent , are included. Composition according to at least one of claims 5 to 7, characterized in that water is contained in amounts of 20 to 90 wt .-%, preferably 25 to 80 wt .-% and in particular from 45 to 75 wt .-%. Solid detergent containing a) 0.05 to 10 wt .-%, and preferably 0.05 to 5 wt .-% of a polymer as described in claim 1 b) 2 to 20 wt .-% of surfactants c) 0.05 to 10 wt .-% water, and optional d) other auxiliaries and additives. Use of polymers as described in claim 1 as soil-release additives for use on pure cotton and / or on cotton / synthetic blend fabrics.