EP1743018B1 - Copolymers comprising n-heterocyclic groups, and use thereof as an additive in detergents - Google Patents

Abstract

The present invention relates to the use of a copolymer comprising, in polymerized form, (a) from 80 to 99.9 mol %, based on the total amount of the monomers polymerized to prepare the copolymer, of at least one monomer A which in each case comprises a heterocycle having at least 1 nitrogen atom and composed of from 3 to 10 ring members and a C2-C6-alkenyl group bonded to a carbon or nitrogen ring atom of the heterocycle; and (b) from 0.1 to 20 mol %, based on the total amount of the monomers polymerized to prepare the copolymer, of at least one monomer B copolymerizable with monomer A, said monomer B having a monoethylenically unsaturated double bond and also a linear or branched poly-C2-C4-alkylene oxide group having on average from 4 to 500 C2-C4-alkylene oxide units, in liquid and in solid detergent formulations. In addition, the invention relates to a process for preparing such a copolymer, and also to a liquid or solid detergent formulation comprising at least one such copolymer.

Description

The present invention relates to novel copolymers having N-heterocyclic groups and their use in liquid and solid detergent formulations. These copolymers show in the washing process a color transfer inhibiting effect.

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 with nitrogen-heterocyclic radicals (= N-heterocyclic groups or N-heterocycles) in copolymerized form.

So describes z. B. the DE 4235798 Copolymers of a) 1-vinylpyrrolidone, 1-vinylimidazole, 1-vinylimidazolium compounds or mixtures thereof; b) further nitrogen-containing, basic ethylenically unsaturated monomers; and optionally c) other monoethylenically unsaturated monomers and their use to inhibit dye transfer during the washing process.

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.

To solve the compatibility problem in the DE 10156134 proposed as color transfer inhibitors graft polymers, the A) a polymeric graft base without monoethylenically unsaturated units and B) formed by polymerization of a cyclic, 3- to 7-membered N-vinylamide polymeric side chains contain, wherein the proportion of the side chains (B) in the total polymer ≥ 60 wt .-% is. Similar graft polymers are disclosed in U.S. Pat DE 10156135 and the DE 10156133 described for this purpose.

Although such graft polymers are distinguished by improved compatibility with detergent constituents, in particular liquid detergents, the disadvantage of a poorer ink transfer inhibition is at the same time accepted for this advantage. In addition, the achieved compatibility is not completely satisfactory.

From the older German patent application 10256162.2 copolymers of vinyllactams with (meth) acrylic acid esters of alkylpolyalkylene glycols are known which have an aliphatic hydrocarbon radical having 3 to 40 C atoms at the end groups of the polyether chain.

It was therefore an object of the present invention to provide polymers having a good ink transfer during the washing process inhibiting effect, which have a good compatibility with conventional detergent ingredients, especially in liquid detergent formulations.

It has surprisingly been found that this object is achieved by copolymers based on monomers with N-heterocycles (monomers A) which contain copolymerized ethylenically unsaturated monomers B with polyalkylene oxide groups in an amount of 0.1 to 20 mol%.

Accordingly, the present invention relates to the use of such copolymers in liquid or solid detergent formulations comprising in polymerized form: (a) 80 to 99.9 mol% at least one monomer A, each comprising a heterocycle having at least 1 N atom (N-heterocycle) of 3 to 10 ring members and a C ₂ -C ₆ alkenyl group bonded to a C or N ring atom of the heterocycle; and (b) 0.1 to 20 mol% at least one monomer B which is copolymerizable with the monomer A and has a monoethylenically unsaturated double bond and a linear or branched poly-C ₂ -C ₄ -alkylene oxide group having on average 4 to 500 C ₂ -C ₄ -alkylene oxide units and 1 or 2, independently of one another comprises radicals selected from C ₁ -C ₂ -alkyl, wherein here and in the following all quantities of monomers in mol% are based on the total amount of monomers used to prepare the copolymers.

The invention also relates to such copolymers, with the proviso that the end group of the poly-C ₂ -C ₄ alkylene oxide group in the monomers B is selected from C ₁ -C ₂ -alkyl, when the monomer B is an ester of a ethylenically unsaturated carboxylic acid with a linear poly-C ₂ -C ₄ alkylene oxide. The invention further relates to a process for preparing such copolymers comprising the radical polymerization of at least one monomer A with the at least one monomer B.

Here and below, N-heterocycle is an aromatic or non-aromatic, heterocyclic radical having usually 3 to 10, in particular 4 to 8 and especially 5 to 7 ring atoms, where 1, 2 or 3 of the ring atoms are heteroatoms, preferably under nitrogen and oxygen are selected, wherein at least one ring member is a nitrogen atom. The N-heterocycle may be aromatic (heteroaryl) or partially or fully saturated. Furthermore, the N-heterocycle may optionally have one or more, for example, 1, 2, 3 or 4 substituents selected from C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl and phenyl. Furthermore, the N-heterocycle may have a carbonyl group and / or an N-oxide group as a ring member. Incidentally, the N-heterocycle in quaternized form, for. B. by alkylation of at least one N-ring atom, are present. In addition, the 3) N-heterocycle may also be present as a betainic structure in which at least one N atom of the heterocycle has a C ₁ -C ₂₀ -alkanediyl group with a lower -SO ₃ ^- , -OSO ₃ ^- , -COO ^- , -OPO (OH) O ^- , -OPO (OR ^f ) O ^- or -PO (OH) O ^- selected anionic group, wherein R ^{f is} C ₁ -C ₆ alkyl. C ₁ -C ₂₀ -alkanediyl here means a linear or branched aliphatic, two-membered, ie bonded via two carbon atoms, Hydrocarbon radical with usually 1 to 20 and in particular 1 to 10 C-atoms.

Here and below is alkyl for a linear or branched aliphatic hydrocarbon radical having usually 1 to 10, in particular 1 to 6 and especially 1 to 4 carbon atoms, such as. Methyl, ethyl, n -propyl, 1-methylethyl, n -butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n -pentyl, 1-methylbutyl, 2-ethylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2- Dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-3-methylpropyl, n-heptyl, n-octyl, n-nonyl, n-decyl, 1-methylhexyl, 1-ethylhexyl, 2-ethylhexyl, 1-methylheptyl, 1-methyloctyl or 1-methylnonyl:

Here and below is cycloalkyl for a cycloaliphatic hydrocarbon radical having usually 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

Here and below is alkenyl for a monoethylenically unsaturated hydrocarbon radical having generally 2 to 6 and in particular 2 to 3 carbon atoms, for. Vinyl, propen-1-yl, propen-2-yl, allyl, 1-buten-1-yl, 1-buten-2-yl, 2-methyl-propen-3-yl (methallyl), 1-pentene 2-yl and 1-hexen-2-yl. In particular, alkenyl is vinyl and allyl, particularly preferably allyl.

C ₂ -C ₄ -alkylene oxide represents a linear or branched alkanedyloxy group having generally 2 to 4 and in particular 2 C atoms, such as CH ₂ CH ₂ O, (CH ₂ ) ₃ O, (CH ₂ ) ₄ O. , CH (CH ₃ ) -CH ₂ O, CH ₂ -CH (CH ₃ ) O, CH ₂ -C (CH ₃ ) ₂ O, CH (CH ₃ ) -CH (CH ₃ ) -O, C (CH ₃ ) ₂ -CH ₂ O, CH ₂ CH (CH ₃ ) -CH ₂ O, CH (CH ₃ ) - (CH ₂ ) ₂ O and (CH ₂ ) ₂ -CH (CH ₃ ) O, in particular for one of the abovementioned Alkane-1,2-diyloxy groups and especially for CH ₂ CH ₂ O.

worin

x

für eine ganze Zahl im Bereich von 1 bis 6 steht; und

R^a

für H oder C₁-C₄-Alkyl steht;

und worin eine oder mehrere der den Lactamring bildenden CH₂-Gruppen gegebenenfalls 1 oder 2 unter C₁-C₄-Alkyl ausgewählte Substituenten aufweist, beschrieben werden. Die unter den Lactamen III bevorzugten N-Vinyllactame weisen insbesondere 5 bis 7 Ringatome auf. Beispiele für derartige N-Vinyllactame sind N-Vinylpyrrolidone, z.B. N-Vinyl-3-methylpyrrolidon und N-Vinylpyrrolidon; N-Vinylcapro- und -valerolactame, z.B. N-Vinyl-3-methyl-ε-caprolactam, N-Vinyl-ε-caprolactam und N-Vinyl-δ-valerolactam; N-Vinylpiperidon und N-Vinyloxazolidone, z.B. N-Vinyl-5-methyloxazolidon und N-Vinyloxazolidon. Bevorzugte N-Vinyllactame sind N-Vinylpyrrolidon, N-Vinyl-ε-caprolactam und N-Vinyl-δ-valerolactam, besonders bevorzugt N-Vinylpyrrolidon. Die Lactame III werden im Folgenden auch als Monomere A1 bezeichnet.The monomers A include cyclic lactams which carry on their nitrogen atom a C ₂ -C ₆ -alkenyl radical, in particular a vinyl radical. Such lactams can be represented by the general formula (III)

wherein

x

is an integer in the range of 1 to 6; and

R ^a

is H or C ₁ -C ₄ alkyl;

and wherein one or more of the lactam ring forming CH ₂ groups optionally has 1 or 2 substituents selected from C ₁ -C ₄ alkyl. The preferred among the lactams III N-vinyl lactams have in particular 5 to 7 ring atoms. Examples of such N-vinyllactams are N-vinylpyrrolidones, for example N-vinyl-3-methylpyrrolidone and N-vinylpyrrolidone; N-vinylcapro- and -valerolactams, eg N-vinyl-3-methyl-ε-caprolactam, N-vinyl-ε-caprolactam and N-vinyl-δ-valerolactam; N-vinylpiperidone and N-vinyl oxazolidones, eg, N-vinyl-5-methyloxazolidone and N-vinyl oxazolidone. Preferred N-vinyllactams are N-vinylpyrrolidone, N-vinyl-ε-caprolactam and N-vinyl-δ-valerolactam, more preferably N-vinylpyrrolidone. The lactams III are also referred to below as monomers A1.

The monomers A furthermore include N-vinylheterocyclic monomers having one of imidazoles, imidazolines and imidazolidines, pyridines, pyrroles, pyrrolidines, quinolines, isoquinolines, purines, pyrazoles, triazoles, tetrazoles, indolizines, pyridazines, pyrimidines, pyrazines, indoles, isoindoles, oxazoles , Oxazolidines, morpholines, piperazines, piperidines, isoxazoles, thiazoles, isothiazoles, indoxylene, isatins, dioxindoles and hydanthoines and derivatives thereof, eg barbituric acid, uracil and derivatives thereof, selected N-heterocycle. The monomers A different from the lactams III are also referred to below as monomers A2.

The stated monomers A2 can also be used as betaine derivatives or quaternized products.

N-heterocycles used in the monomers A2 are selected in particular from imidazoles, pyridines, pyridine-N-oxides and also betaine derivatives and quaternization products thereof, especially from imidazoles.

worin

R^b, R^c, R^d, R^e

jeweils unabhängig voneinander für H, C₁-C₄-Alkyl oder Phenyl, bevorzugt H oder C₁-C₄-Alkyl, besonders bevorzugt H stehen;

W¹

für C₁-C₂₀-Alkylen, beispielsweise -CH₂-, -CH(CH₃)-, -(CH₂)₂-, -CH₂- CH(CH₃)-, -(CH₂)₃-, -(CH₂)₄-, -(CH₂)₅-, -(CH₃)₆-, vorzugsweise C₁-C₃- Alkylen; insbesondere -CH₂-, -(CH₂)₂- oder -(CH₂)₃- steht;

Q^-

für -SO₃ ^-, -OSO₃ ^- , -COO^-, -OPO(OH)O^-, -OPO(OR^f)O^- oder -PO(OH)O^- steht; und

R^f

für C₁-C₂₄-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso- Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo- Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n- Heptyl, n-Octyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl steht.

In a preferred embodiment, the monomers A2 are N-vinylimidazoles of the general formula IVa, betainic N-vinylimidazoles of the general formula IVb, 2- and 4-vinylpyridines of the general formulas IVc and IVd, and betainic 2- and 4-vinylpyridines of general formulas IV e and IV f:

wherein

R ^b, R ^c, R ^d, R ^e

each independently of one another are H, C ₁ -C ₄ -alkyl or phenyl, preferably H or C ₁ -C ₄ -alkyl, particularly preferably H;

W ¹

for C ₁ -C ₂₀ -alkylene, for example -CH ₂ -, -CH (CH ₃ ) -, - (CH ₂ ) ₂ -, -CH ₂ -CH (CH ₃ ) -, - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₃ ) ₆ -, preferably C ₁ -C ₃ - alkylene; in particular -CH ₂ -, - (CH ₂ ) ₂ - or - (CH ₂ ) ₃ -;

Q ^-

is -SO ₃ ^- , -OSO ₃ ^- , -COO ^- , -OPO (OH) O ^- , -OPO (OR ^f ) O ^- or -PO (OH) O ^- ; and

R ^f

for C ₁ -C ₂₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec. -Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso -hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; C ₁ -C ₄ -alkyl is particularly preferred.

Particularly preferred monomers A2 are N-vinylimidazole and C ₁ -C ₄ -alkylvinylimidazoles, for example N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, N-vinyl-5-methylimidazole, N-vinyl-2-ethylimidazole, in particular N-vinylimidazole and methylvinylimidazoles, especially N-vinylimidazole and N-vinyl-2-methylimidazole; 3-vinylimidazole-N-oxide; 2- and 4-vinylpyridines, eg 2-vinyl-4-methylpyridine, 2-vinyl-6-methylpyridine and 2- and 4-vinylpyridine; Vinylpyridine N-oxides, such as 2- and 4-vinylpyridine N-oxides, for example 2-vinyl-4-methylpyridine-N-oxide, 4-vinyl-2-methylpyridine-N-oxide and 2- and 4-vinylpyridine N-oxide; and betaine derivatives and quaternization products thereof.

Especially preferred betaine monomers A2 are monomers of the formula IV b, IV and IV e f, in which the group W ¹ -X ^- is -CH ₂ -COO ^-, - (CH _{2) 2} -SO ₃ ^- or - (CH ₂ ) ₃ -SO ₃ ^- and R ^b , R ^c , R ^d , R ^{e are} each H.

The quaternized monomers A2 used are preferably vinylimidazoles and vinylpyridines, these having been quaternized before or after the polymerization. Particular preference is given to using 1-methyl-3-vinylimidazolium methosulfate and methachloride.

The quaternization can be carried out in particular with alkylating agents such as alkyl halides, which generally have 1 to 24 C atoms in the alkyl radical, or dialkyl sulfates, which generally contain alkyl radicals having 1 to 10 C atoms. Examples for 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.

Suitable monomers A are furthermore mixtures of the abovementioned monomers A1 and A2.

In a preferred embodiment, the monomers A are selected to be at least 85 mol% and especially 90 mol% among the monomers A1 (N-vinyllactams), and more preferably among N-vinylpyrrolidones. Very particularly preferred N-vinyllactam is N-vinylpyrrolidone. Particular preference is given to the N-vinyllactams and in particular N-vinylpyrrolidone as the sole monomer A.

In a further preferred embodiment, the monomers A comprise at least one N-vinyllactam as monomer A1 and at least one monomer A2 different therefrom, in particular an N-vinylimidazole. The molar ratio A1: A2 is then preferably in the range from 9: 1 to 1: 9, in particular 4: 1 to 1: 4.

In a particularly preferred embodiment, the monomers A are selected from N-vinylpyrrolidone and mixtures of N-vinylpyrrolidone with N-vinylimidazole.

For the dye transfer-inhibiting effect of the copolymers of the invention, it has proved to be advantageous if the proportion of the monomers A at least 85 mol% and in particular at least 90 mol% of the total amount of the monomers used for the preparation of the copolymers. In particular, the proportion of the monomers A, based on the total amount of monomers, is from 85 mol% to 99.5 mol% and particularly preferably from 90 to 99 mol%.

It has furthermore proved to be advantageous for the purposes according to the invention if the proportion of ethylene oxide units in the poly-C ₂ -C ₄ -alkylene oxide group of the monomers B is chosen such that it contains at least 50 mol%, in particular 75 mol% and specifically about 100 mol% with respect to the C ₂ -C ₄ -alkylene oxide units contained in the monomer B.

The poly-C ₂ -C ₄ alkylene oxide group of the monomers B naturally has 2 end groups in the case of a linear structure and 3 or more end groups in the case of a branched structure, one of which carries one ethylenically unsaturated group. The remaining terminal radicals (end groups) may be hydrogen or OH or an organic radical. Preferred organic end groups have 1 to 10 C atoms, in particular 1 to 4 C atoms, and are usually selected from H, C ₁ -C ₁₀ -alkyl and benzyl (or OH, C ₁ -C ₁₀ -alkyloxy and benzyloxy), in particular H and C ₁ -C ₄ -alkyl and especially C ₁ -C ₂ -alkyl. The monomers B preferably have 1 or 2 of such end groups and in particular 1 end group.

X

für H oder COOH steht;

R¹

für C₁-C₄-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec- Butyl und tert-Butyl, insbesondere H oder Methyl steht;

Y

für O, CH₂-O, C(O)O, C(O)NH, NHC(O) oder CH₂-NHC(O) steht; und

Z

für eine lineare oder verzweigte Poly-C₂-C₄-Alkylenoxidgruppe steht, umfassend im Mittel 4 bis 500 C₂-C₄-Alkylenoxideinheiten und 1 oder 2 endständige, unab- hängig voneinander unter H, C₁-C₁₀-Alkyl und Benzyl, vorzugsweise unter H und C₁-C₄-Alkyl und speziell unter C₁-C₂-Alkyl ausgewählte Reste.

Monomers B which are suitable according to the invention preferably have the general formula (1):

X-CH = CR ¹ -YZ (I),

wherein

X

is H or COOH;

R ¹

C ₁ -C ₄ alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl, in particular H or methyl;

Y

O, CH ₂ -O, C (O) O, C (O) NH, NHC (O) or CH ₂ -NHC (O); and

Z

represents a linear or branched poly-C ₂ -C ₄ -alkylene oxide group comprising on average 4 to 500 C ₂ -C ₄ -alkylene oxide units and 1 or 2 terminal, independently of one another by H, C ₁ -C ₁₀ -alkyl and Benzyl, preferably selected from H and C ₁ -C ₄ alkyl and especially C ₁ -C ₂ alkyl radicals.

If the orientation of the radicals Y during incorporation into the formula (I) can be realized in different ways, then the installation is carried out in the manner indicated above from left to right.

When referring to the number of C ₂ -C ₄ -alkylene oxide units in the linear or branched poly-C ₂ -C ₄ -alkylene oxide group Z, the term "on average" here and below refers to the number average of the alkylene oxide units per monomer B The term "degree of alkoxylation" is also used synonymously.

The linear or branched poly-C ₂ -C ₄ -alkylene oxide groups Z generally have a degree of alkoxylation in the range from 4 to 500, in particular from 6 to 200 and especially from 6 to 100.

worin

Z¹, Z² und Z³

jeweils unabhängig voneinander für C₂-C₄-Alkandiyl stehen;

Z⁴

für C₂-C₄-Alkantriyl steht;

n+1 bzw. m+k+1

für eine ganze Zahl steht, wobei das Zahlenmittel von n+1 bzw. m+k+1 im Bereich von 4 bis 500, insbesondere von 6 bis 200 und speziell von 6 bis 100 liegt; und

R² und R³

jeweils unabhängig voneinander für H, C₁-C₁₀-Alkyl oder Benzyl, vorzugsweise H oder C₁-C₄-Alkyl und speziell für C₁-C₂Alkyl stehen.

The poly-C ₂ -C ₄ -alkylene oxide groups Z of the monomers B preferably have a linear or branched structure of the formulas (II.1) or (II.2):

-Z ¹ -O- [Z ² -O] _n -R ² (II.1)

or

wherein

Z ¹ , Z ² and Z ³

each independently represent C ₂ -C ₄ alkanediyl;

Z ⁴

is C ₂ -C ₄ alkanetriyl;

n + 1 and m + k + 1, respectively

is an integer, wherein the number average of n + 1 and m + k + 1 is in the range of 4 to 500, especially 6 to 200 and especially 6 to 100; and

R ² and R ³

each independently of one another are H, C ₁ -C ₁₀ -alkyl or benzyl, preferably H or C ₁ -C ₄ -alkyl and especially C ₁ -C ₂ -alkyl.

Here and below alkanetriyl means a linear or branched aliphatic, trivalent, preferably bonded via three different carbon atoms hydrocarbon radical having generally 2 to 4, in particular 3 C-atoms.

In the formulas (II.1) and (II.2), the radicals Z ² or Z ² and Z ^{3 are} preferably each at least 50%, more preferably at least 75% and most preferably about 100% ethylene oxide units.

In a preferred embodiment, the radicals R ² and R ³ in the formulas (II.1) and (II.2) are each independently of one another methyl.

Particular preference is given to monomers B of the formula (I) in which Z is a radical of the formula (II.1).

In a further preferred embodiment, in formula (I) the variable X is H and Y is C (O) O or C (O) NH. In this embodiment, the variable Z in formula (I) is in particular the structures of the formula (II.1) or (II.2) mentioned above as being preferred. R ¹ is in particular H or methyl. Particular preference is given to the methylpoly-C ₂ -C ₃ -alkylene glycol esters of acrylic acid or of methacrylic acid and, among these, especially those having a proportion of at least 50 mol%, in particular at least 80 mol% of ethylene oxide groups, in each case based on the total amount of C ₂ C ₃ alkylene oxide groups, and especially methyl polyethylene glycol esters of (meth) acrylic acid.

In a further preferred embodiment, in formula (I) the variable X is H and Y is CH ₂ -O. In this embodiment, the variable Z in formula (I) is in particular the structures of the formula (II.1) or (II.2) mentioned above as being preferred. R ¹ is in particular H or methyl. Particularly preferred are the allyl ether C ₂ -C ₃ alkoxylates (R ¹ = H) and 2-methylallyl-C ₂ -C ₃ alkoxylates (R ¹ = methyl), in particular those having a terminal methyl group, and especially those having a Proportion of at least 50 mol%, in particular at least 80 mol% of ethylene oxide groups, in each case based on the total amount of C ₂ -C ₃ alkylene oxide groups, and especially allyl ether ethoxylates (R ¹ = H).

The monomers B can be prepared by standard methods of organic chemistry known to the person skilled in the art (see, for example, US Pat. Houben-Weyl, Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart, 1954 ) are prepared, for. Example, by esterification, amidation, transamidation, transesterification or alkoxylation of suitable (meth) acrylic acids, (meth) acrylic esters, (meth) acrylamides and maleic acid, maleic acid (half) esters, maleic acid (half) amides; by alkoxylation of allyl alcohol; by etherification of allyl halides with poly-C ₂ -C ₄ -alkylene oxides and vinylation of polyalkylene oxides with OH or NH terminus with acetylene. Accordingly, in particular z. For example, methyl polyethylene glycol (meth) acrylic acid can be obtained by esterification of (meth) acrylic acid with polyethylene glycol monomethyl ethers.

Allyl alcohol polyalkoxylates suitable as monomers B are also commercially available, e.g. under the names Pluriol® A 010 R and Pluriol® A 11 RE from BASF Aktiengesellschaft.

With regard to the dye transfer-inhibiting performance of the copolymers of the invention in detergents commonly used, it has proved to be advantageous if the proportion of the monomers B at most 15 mol.% And especially at most 10 mol .-% of the total amount of the monomers used to prepare the copolymers. In particular, the proportion of the monomers B is 0.5 to 15 mol .-% and particularly preferably 1 to 10 mol .-%.

In addition to the monomers A and B copolymers of the invention, one or more further with the A and B monomers copolymerizable monomers C include: Examples of monomers C are monoethylenically unsaturated C ₃ -C ₁₀ monocarboxylic and C ₄ -C ₁₀ dicarboxylic acids, e.g. , (Meth) acrylic acid, crotonic acid, fumaric acid and maleic acid; ethylenically unsaturated sulfonic acids and their salts, such as vinylsulfonic acid, 2-acryloxyethanesulfonic acid, 2- and 3-acryloxypropanesulfonic acid, 2-methyl-2-acrylamidopropanesulfonic acid and styrenesulfonic acid and their sodium salts; Vinyl esters of saturated C ₁ -C ₁₀ carboxylic acids, e.g. Vinyl acetate and vinyl propionate; Vinyl and allyl ethers of linear or branched C ₁ -C ₁₀ -alcohols, e.g. Vinyl ethyl ether, vinyl propyl ether, allyl methyl ether, allyl ethyl ether and allyl propyl ether; Vinylformamide, e.g. N-vinyl-N-methylformamide and N-vinylformamide itself; the quaternary products of N-vinyl and N-allylamines, such as alkylated N-vinyl and N-allylamines, e.g. N-vinylmethylamine, N-vinylethylamine, N-allylmethylamine, N-allylethylamine and N-allylpropylamine; the esters of monoethylenically unsaturated C ₃ -C ₆ -monocarboxylic acids or C ₄ -C ₆ -dicarboxylic acids with linear or branched aliphatic C ₁ -C ₁₀ -alcohols, for. Methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, dimethyl maleate, diethyl maleate, 2-ethylhexyl acrylate and 2-ethylhexyl methacrylate; the half-esters of monoethylenically unsaturated C ₄ -C ₆ -dicarboxylic acids with linear or branched C ₁ -C ₁₀ -alcohols, eg. B. maleic acid monomethyl ester and maleic acid monoethyl ester; the anhydrides of monoethylenically unsaturated C ₄ -C ₆ dicarboxylic acids, eg. For example, maleic anhydride; Amides of monoethylenically unsaturated C ₃ -C ₆ carboxylic acids with primary and secondary C ₁ -C ₁₂ amines, eg. B. (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide or N-butyl (meth) acrylamide; unsaturated nitriles, e.g. For example, acrylonitrile and methacrylonitrile; and the salts of said acids, the derivatives thereof and mixtures thereof.

The requirements of certain applications may influence the choice of the type and amount of monomers C. Thus, it may be desirable to further react the polymers of the invention in a selective manner prior to use, e.g. As by targeted alcoholysis, aminolysis or hydrolysis. Thus, in particular vinyl alcohol units, corresponding units of vinyl ester units and units corresponding to vinylamine units can be formed from vinylformamide units.

In a preferred embodiment, the monomer C is selected from monoethylenically unsaturated C ₃ -C ₁₀ -mono- and C ₄ -C ₁₀ -dicarboxylic acids, in particular acrylic acid, methacrylic acid and maleic acid.

In a preferred embodiment, the proportion of monomers C is less than 20 mol .-%, in particular less than 15 mol .-% and especially less than 10 mol .-%, based on the total weight of the copolymer.

In a further embodiment, the proportion of the monomers C is 1 to 20 mol .-%, in particular 1 to 15 mol .-%, based on the total weight of the copolymer.

The K values of the copolymers used according to the invention are usually from 10 to 150, preferably from 10 to 80 and more preferably from 15 to 60 (determined by H. Fikentscher, Cellulosic Chemistry, Vol. 13, pp. 58-64 and 71-74 (1932 ) in water or aqueous sodium chloride solutions at 25 ° C (concentration NaCl 0.1 to 7.0 wt .-%) and polymer concentrations, depending on the K value range at 0.1 wt .-% to 5 wt .-%. % lie). The respective desired K value can be adjusted by the composition of the starting materials.

The present invention furthermore relates to a process for the preparation of the copolymers according to the invention in which the at least one monomer A is radically polymerized with the at least one monomer B and optionally with the monomers C.

The free-radical polymerization of the monomers can be carried out by any known method, such as solution polymerization, emulsion polymerization, suspension polymerization or bulk polymerization, preferably the methods of solution polymerization and bulk polymerization, very particularly preferably solution polymerization.

It is advantageous to carry out a solution polymerization in water or in mixtures of water with organic solvents as the reaction medium. However, organic solvents (mixtures) may also be used alone as the reaction medium.

Examples of suitable organic solvents are aliphatic and cycloaliphatic monohydric C ₁ -C ₄ -alcohols, e.g. For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and tert-butanol; polyhydric alcohols, such as C ₁ -C ₄ -glycols, for. Ethylene glycol, propylene glycol and butylene glycol and glycerin; Mono- and dialkyl ethers of polyhydric alcohols, such as C ₁ -C ₄ -alkyl ethers of said polyhydric alcohols, eg. Monomethylethyleneglycol, monoethylethyleneglycol, dimethylethyleneglycol and dimethylpropyleneglycol; Ether alcohols, eg. For example, diethylene glycol and triethylene glycol; and cyclic ethers, e.g. Eg dioxane. Preferred organic solvents are alcohols.

The polymerization is preferably carried out in an aqueous polymerization medium which contains at least 50% by volume, in particular at least 80% by volume and particularly preferably at least 95% by volume of water, based on the total amount of solvent. Particularly preferably, the polymerization is carried out in water.

If the solution polymerization is carried out in an aqueous polymerization medium, a pH in the range from 2 to 10, in particular from 3 to 8, is preferably maintained during the polymerization.

Suitable radical initiators are, in particular, peroxo compounds, azo compounds, redox initiator systems and reducing compounds. Of course you can also use mixtures of radical starters.

Among the thermally activatable polymerization initiators, preference is given to initiators having a decomposition temperature ("10 h half-life decomposition temperature") in the range from 20 to 180 ° C., in particular from 50 to 120 ° C. Examples of preferred thermal initiators are inorganic peroxo compounds, such as peroxodisulfates (ammonium and alkali metal sulfates, preferably sodium peroxodisulfate), peroxosulfates, percarbonates and hydrogen peroxide; organic peroxy compounds, such as diacetyl peroxide, di-tert-butyl peroxide, diamyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, bis (o-toluyl) peroxide, succinyl peroxide, tert-butyl peracetate, tert-butyl permalate, tert-butyl perisobutyrate, tert. Butyl perpivalate, tert-butyl peroctoate, tert-butyl perodecanoate, tert-butyl perbenzoate, tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxy-2-ethylhexanoate and diisopropyl peroxydicarbamate; Azo compounds such as 2,2'-azobis-isobutyronitrile, 2,2'-azobis (2-methylbutyronitrile) and azobis (2-amidinopropane) dihydrochloride.

These initiators can be used in combination with reducing compounds as starter / regulator systems. Examples of such reducing compounds include phosphorus-containing compounds such as phosphorous acid, hypophosphites and phosphinates, sulfur-containing compounds such as sodium hydrogen sulfite, sodium sulfite and sodium formaldehyde sulfoxilate, and hydrazine. Suitable examples are the combinations tert-butyl hydroperoxide / sodium disulfite and tert-butyl hydroperoxide / sodium hydroxymethanesulfinate; furthermore systems with addition small amounts of redox metal salts such as iron salts, eg ascorbic acid / iron (II) sulfate / sodium peroxodisulfate.

Preferred initiators are soluble in the amount used in the polymerization medium. Therefore, particularly water-soluble initiators are preferred. Particularly preferred initiators are the aforementioned diazo compounds, in particular water-soluble diazo compounds such as azobis (2-amidinopropane) dihydrochloride.

Also suitable are photoinitiators; e.g. Benzophenone, acetophenone, benzoin ethers, Benzyldialkylketone and their derivatives.

Depending on the requirements of the material to be polymerized, the polymerization initiators are usually used in amounts of from 0.01 to 15% by weight, preferably from 0.25 to 5% by weight, based in each case on the monomers to be polymerized, and may be used singly or as Exploitation of beneficial synergistic effects in combination with each other.

To limit the molecular weights of the copolymers according to the invention, it is possible to use regulators conventional in the polymerization, e.g. Mercapto compounds such as mercaptoethanol, thioglycolic acid, 1,4-bismercaptobutane-2,3-diol; Alkali metal sulfites and hydrogen sulfites such as sodium sulfite; Alkali metal phosphites and hypophosphites such as sodium hypophosphite, etc. are added. Suitable amounts of regulator are generally in the range of 0.01 to 5 wt .-%, based on the monomers to be polymerized.

The polymerization temperature is generally in the range from 10 to 200.degree. C., preferably from 40 to 140.degree. C., more preferably from 50 to 120.degree.

The polymerization may be carried out under atmospheric pressure, optionally it may also be carried out in a closed system under the evolving autogenous pressure.

Frequently, the production of the copolymers is followed by a chemical and / or physical deodorization, ie removal of unreacted monomers. In physical deodorization, the monomers are mixed with water vapor, e.g. B. by distilling off part of the aqueous polymerization medium and / or by passing superheated steam out of the polymerization mixture. In chemical deodorization, unreacted monomers in the reaction mixture are removed by use of more severe polymerization conditions, e.g. B. by the addition of further polymerization, often by addition of the above-mentioned redox initiators and especially by the addition of hydroperoxides, such as hydrogen peroxide and alkyl hydroperoxides, z. For example, tert-butyl hydroperoxide, in combination with reducing agents, in particular sulfur-containing reducing agents such as hydrogen sulfite, dithionite, adducts of bisulfite to ketones, such as the acetone-bisulfite adduct, hydroxymethanesulfinate and the like, optionally in the presence of traces of transition metals, eg Fe ^{2 +} or Fe ³⁺ .

As an alternative to the process described, the copolymers according to the invention can also be obtained by reacting the poly-C ₂ -C ₄ -alkylene oxide groups Z of the monomer units B by polymer-analogous reaction of suitable functional groups contained in a precursor copolymer to the monomer units X-CH = CR ¹ -the monomers B are attached, linked to the precursor polymer. As polymer-analogous reaction z. As the amination, transamidation, transesterification or alkoxylation in the polymer molecule contained (meth) acrylic acid units, (meth) acrylic acid ester units, (meth) acrylamide units and maleic acid units, maleic acid (half) ester units, maleic acid (half ) amide units, vinyl alcohol units, allyl alcohol units, vinylamine units and allylamine units, in particular the polymer-analogous esterification and amidation of (meth) acrylic acid units containing precursor polymers into consideration.

Accordingly, should the copolymers of the invention based on (meth) acrylic acid esters or amides as components of the monomer units B, z. Example, proceed by copolymerizing (meth) acrylic acid in an amount equivalent to the molar amount of the monomer B with the monomer A and optionally the monomer C and then the copolymer formed with polyalkylene glycols which are not end-capped, unilaterally by alkyl , Phenyl or alkylphenyl radicals end-capped or aminated on one side or end-capped on one side by alkyl, phenyl or alkylphenyl radicals and aminated on one side, esterified or aminated.

If a vinylpyridine N-oxide is used as monomer A, it has proven advantageous to first copolymerize the desired amount of the corresponding vinylpyridine compound with the other monomers and then to add the copolymerized vinylpyridine to vinylpyridine N-oxide units oxidize.

The copolymers according to the invention are outstandingly suitable as dye transfer inhibitors in the washing of colored textiles. They effectively reduce or prevent dye transfer between the textiles. In addition, they can be used universally in a wide variety of detergents, such as liquid and solid detergents or detergent formulations. In particular, they have a good compatibility with the usual detergent components, especially with regard to liquid detergents and detergent formulations.

Good compatibility means, for the purposes of the present invention, that the copolymers according to the invention can easily be incorporated or formulated into detergent component formulations containing conventional components without segregation processes occurring, and that the resulting detergent formulations have good stability, in particular against segregation, within the usual life. In the case of liquid detergent formulations, this means, in particular, that no significant precipitation of the copolymers according to the invention takes place before or during use or turbidity does not occur.

It is believed that the color transfer inhibiting effect of the copolymers of the invention is due to the N-heterocyclic groups of the monomers A. In contrast, it is assumed in view of the good compatibility of the copolymers according to the invention with customary detergent constituents that this is due to the alkylene oxide units present in the monomers B. This effect is surprising in particular because the graft polymers known from the prior art (see, for example, US Pat. DE 10156134 ), the z. T. include similar structural features, have a not completely satisfactory compatibility.

The copolymers of the invention are generally used in amounts ranging from 0.05 to 5 wt .-%, preferably 0.1 to 2 wt .-%, each based on the total weight of the detergent (formulations). They are suitable for both heavy-duty detergents and special detergents, such as color detergents. In color-preserving color detergents, they are usually used in amounts ranging from 0.1 to 1.5% by weight, preferably 0.1 to 1% by weight, based in each case on the total weight of the detergents (formulations).

The detergents can be in solid form, for. B. in powder, granule, extrudate or tablet form, as a so-called compact detergent with a bulk density in the range of 500 to 950 g / l, or in liquid setting. They contain the anionic, nonionic and / or cationic surfactants commonly used in amounts of 2 to 50 wt .-%, preferably 8 to 30 wt .-%, each based on the total weight of the detergent (formulations). Particular preference is given to producing phosphate-free or reduced-phosphate detergents which have a phosphate content of at most 25% by weight, based in each case on the total weight of the detergent formulations (formulations), calculated as pentasodium tripolyphosphate.

Suitable anionic surfactants are, for example, C ₈ -C ₂₂ , preferably C ₁₀ -C _18, fatty alcohol sulfates, for example C ₉ / C ₁₁ -alcohol sulfate, C ₁₂ / C ₁₄ -alcohol sulfates, lauryl sulfate, cetyl sulfate, myristyl sulfate, palmitylsulfate, stearyl sulfate and tallow fatty alcohol sulfate.

Other suitable anionic surfactants are sulfated alkoxylated C ₈ -C ₂₂ -, preferably C ₁₀ -C ₁₈ -alcohols or their soluble salts. Compounds of this type are prepared, for example, by first alkoxylating the alcohol and then sulfating the alkoxylation product. Ethylene oxide is preferably used for the alkoxylation, with 2 to 50 mol, in particular 3 to 20 mol, of ethylene oxide being used per mole of fatty alcohol. However, the alkoxylation can also be carried out with propylene oxide or with butylene oxide. Of course, the alkylene oxides can also be used in combination. The alkoxylated alcohols may then contain the ethylene oxide, propylene oxide and / or butylene oxide units in the form of blocks or in random distribution.

Also suitable as anionic surfactants are alkyl sulfonates, in particular C ₈ -C ₂₄ - and especially C ₁₀ -C ₁₈ -alkyl sulfonates, and soaps, for example the salts of aliphatic C ₈ -C ₂₄ -carboxylic acids.

Further suitable anionic surfactants are linear C ₉ -C ₂₀ -alkylbenzenesulfonates (LAS).

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

Examples of suitable nonionic surfactants are alkoxylated C ₈ -C ₂₂ -alcohols, in particular C ₁₀ -C ₁₈ -alcohols, such as fatty alcohol alkoxylates, oxo alcohol alkoxylates and guerbet alcohol alkoxylates. The alkoxylation can be carried out with ethylene oxide, propylene oxide and / or butylene oxide. The alkoxylated alcohols may then contain the alkylene oxide units in the form of blocks or in random distribution. From 2 to 50, preferably from 3 to 20, moles of at least one of these alkylene oxides are used per mole of alcohol. The alkylene oxide used is preferably ethylene oxide.

Further suitable nonionic surfactants are alkylphenol alkoxylates, in particular C ₆ -C ₁₄ -alkylphenol ethoxylates containing on average 5 to 30 alkylene oxide units.

Further suitable nonionic surfactants are C ₈ -C ₂₂ -, in particular C ₁₀ -C ₁₈ -alkylpolyglucosides. These compounds contain 1 to 20, preferably 1.1 to 5 glucoside units.

bei denen D für C₆-C₂₂-Alkyl, bevorzugt C₁₀-C₁₈-Alkyl, E für Wasserstoff oder C₁-C₄-Alkyl, bevorzugt Methyl, und G für Polyhydroxy-C₅-C₁₂-alkyl mit mindestens 3 Hydroxylgruppen, bevorzugt Polyhydroxy-C₅-C₆-alkyl, stehen. Beispielsweise erhält man derartige Verbindungen durch Acylierung von reduzierend aminierten Zuckern mit Säurechloriden von C₁₀-C₁₈-Carbonsäuren.Another class of suitable nonionic surfactants are N-alkylglucamides of structures (NT1) and (NT2):

in which D is C ₆ -C ₂₂ -alkyl, preferably C ₁₀ -C ₁₈ -alkyl, E is hydrogen or C ₁ -C ₄ -alkyl, preferably methyl, and G is polyhydroxy-C ₅ -C ₁₂ -alkyl with at least 3 hydroxyl groups, preferably polyhydroxy-C ₅ -C ₆ alkyl. For example, such compounds are obtained by acylation of reducing aminated sugars with acid chlorides of C ₁₀ -C ₁₈ carboxylic acids.

Preferably, the detergent formulations containing 3 to 12 moles of ethylene oxide ethoxylated C ₁₀ -C ₁₈ alcohols as nonionic surfactants.

worin R^aa für C₁-C₂₅-Alkyl oder C₂-C₂₅-Alkenyl, R^bb für C₁-C₄-Alkyl oder -Hydroxyalkyl und R^cc für C₁-C₄-Alkyl, -Hydroxyalkyl oder einen Rest R^aa-(CO)-W²-(CH₂)_n- mit W² = O oder NH und n = 2 oder 3 steht, wobei mindestens ein Rest R^aa für C₇-C₂₂-Alkyl steht.Particularly suitable cationic surfactants are, for example, C ₇ -C ₂₅ -alkylamines; C ₇ -C ₂₅ N, N-dimethyl-N- (hydroxyalkyl) ammonium salts; quaternized mono- and di- (C ₇ -C ₂₅ ) -alkyldimethylammonium compounds; Esterquats, such as quaternary esterified mono-, di- or trialkanolamines esterified with C ₈ -C ₂₂ carboxylic acids; and imidazoline quats such as 1-alkyl-imidazolinium salts of the general formulas KT1 or KT2:

wherein R ^{aa is} C ₁ -C ₂₅ alkyl or C ₂ -C ₂₅ alkenyl, R ^{bb is} C ₁ -C ₄ alkyl or hydroxyalkyl and R ^{cc is} C ₁ -C ₄ alkyl, hydroxyalkyl or a radical R ^{aa is} - (CO) -W ² - (CH ₂ ) _n - with W ² = O or NH and n = 2 or 3, where at least one radical R ^{aa is} C ₇ -C ₂₂ -alkyl.

The powdery and granular detergents and optionally also structured (multiphase) liquid detergents also contain one or more inorganic builders. Suitable inorganic builders are all commonly used compounds, such as aluminosilicates, silicates, carbonates and polyphosphates.

Specific examples are crystalline and amorphous aluminosilicates with ion-exchanging properties, such as zeolites, for example zeolite A, X, B, P, MAP and HS in their Na-form and in forms in which Na is partially exchanged for other cations, such as Li, K, Ca, Mg or ammonium.

For the silicates, e.g. amorphous and crystalline silicates such as amorphous disilicates, sodium metasilicate, crystalline disilicates and layered silicates, e.g. the layered silicate SKS-6 (Clariant AG). The silicates can be used in the form of their alkali, alkaline earth or ammonium salts. Preferably, Na, Li and Mg silicates are used.

Carbonates and bicarbonates suitable as inorganic builders may also be used in the form of their alkali metal, alkaline earth metal and ammonium salts. Preference is given to sodium, lithium and magnesium carbonates and hydrogencarbonates, particular preference being given to sodium carbonate and / or sodium bicarbonate. As a suitable phosphate in particular pentasodium triphosphate called.

The inorganic builders may be included in the detergents in amounts of from 5 to 60% by weight. They can be incorporated alone or in any combination with each other in the detergent. In powder and granular detergents, they are added in amounts of from 10 to 60% by weight, preferably from 20 to 50% by weight. In structured Flüssigwaschmittein inorganic builders in amounts up to 40 wt .-%, preferably up to 20 wt .-%, are used. They are suspended in the liquid formulation ingredients.

The detergents contain one or more organic co-builders in addition to the inorganic builders.

• Niedermolekulare Carbonsäuren, wie Citronensäure, hydrophob modifizierte Citronensäure, z. B. Agaricinsäure, Äpfelsäure, Weinsäure, Gluconsäure, Glutarsäure, Bernsteinsäure, Imidodibernsteinsäure, Oxyddibernsteinsäure, Propantricarbonsäure, Butantetracarbonsäure, Cyclopentantetracarbonsäure, Alkyl- und Alkenylbernsteinsäuren und Aminopolycarbonsäuren, z.B. Nitrilotriessigsäure, β-Alanindiessigsäure, Ethylendiamintetraessigsäure, Serindiessigsäure, Isoserindiessigsäure, N-(2-Hydroxyethyl)iminodiessigsäure, Ethylendiamindibernsteinsäure und Methyl- und Ethylglycindiessigsäure.
• 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-C₃-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.

As organic cobuilders are particularly suitable:

• Low molecular weight carboxylic acids such as citric acid, hydrophobically modified citric acid, e.g. B. agaricic, malic, tartaric, gluconic, glutaric, succinic, imidodisuccinic, oxydisuccinic, propanetricarboxylic, butanetetracarboxylic, cyclopentanetetracarboxylic, alkyl- and alkenylsuccinic and aminopolycarboxylic, eg nitrilotriacetic acid, β-Alanindiessigsäure, ethylenediaminetetraacetic, Serindiessigsäure, Isoserindiessigsäure, N- (2-hydroxyethyl ) iminodiacetic acid, ethylenediamine disuccinic acid and methyl and ethylglycinediacetic acid.
• 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 ₃ -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.

The organic co-builders are present in the powdered and granular as well as in the structured liquid detergent formulations in amounts of from 0.1 to 15% by weight, preferably from 0.25 to 8% by weight. In liquid detergent formulations, they are present in amounts of from 0.1 to 20% by weight and preferably from 0.25 to 10% by weight.

The powdered and granular heavy-duty detergents may also contain a bleach system consisting of at least one bleach, optionally in combination with a bleach activator and / or a bleach catalyst.

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, as well as inorganic and organic peracids in the form of their alkali metal or magnesium salts or partly also in the form of the free acids. Examples of suitable organic percarboxylic acids and their salts are Mg monoperphthalate, phthalimidopercaproic acid and dodecane-1,10-diacetic acid. An example of an inorganic peracid salt is K-peroxomonosulfate (oxone).

If bleaching agents are used, they are present in amounts of 5 to 30% by weight, preferably 10 to 25% by weight, in the formulations.

Suitable bleach activators are, for example: acylamines, such as N, N, N ', N'-tetraacetylethylenediamine (TAED), tetraacetylglycoluril, N, N'-diacetyl-N, N'-dimethylurea and 1,5-diacetyl-2,4- dioxohexahydro-1,3,5-triazine; acylated lactams, such as acetylcaprolactam, octanoylcaprolactam and benzoylcaprolactam; substituted phenol esters of carboxylic acids such as Na-acetoxybenzenesulfonate, Na-octanoyloxybenzenesulfonate and sodium p-nonanoyloxybenzenesulfonate; N-Methylmorpholiniumacetonitrilmethylsulfat and hydrogen sulfate; acylated sugars, such as pentaacetylglucose; Anthranil derivatives such as 2-methylanthranil and 2-phenylanthranil; Enol esters, such as isopropenyl acetate; Oxime esters such as o-acetylacetone oxime; carboxylic acid anhydrides, such as phthalic anhydride and acetic anhydride.

Preference is given to using tetraacetylethylenediamine, sodium nonanoyloxybenzenesulphonates and N-methylmorpholinium acetonitrile methylsulfate and hydrogensulfate as bleach activators.

If the bleach activators are used in detergents, they are present in amounts of from 0.1 to 15% by weight, preferably in amounts of from 1 to 8% by weight, more preferably in amounts of from 1.5 to 6% by weight ,

Suitable bleach catalysts are quaternized imines and sulfonimines and Mn or Co complexes. If bleach catalysts are used in the detergent formulations, they are in amounts of up to 1.5% by weight, preferably up to 0.5% by weight, in the case of the very active Mn complexes in amounts up to 0.1% by weight .-% contain.

The detergents preferably contain an enzyme system. These are usually proteases, lipases, amylases or cellulases. The enzyme system may be limited to a single enzyme or may include a combination of different enzymes. Of the commercial enzymes, the detergents are generally added amounts of 0.1 to 1.5 wt .-%, preferably 0.2 to 1 wt .-%, of the ready-made enzyme. Suitable proteases are e.g. Savinase and Esperase (manufactured by Novo Nordisk), a suitable lipase is e.g. Lipolase (manufactured by Novo Nordisk), a suitable cellulase is e.g. Celluzym (manufacturer also Novo Nordisk).

The detergents also preferably contain soil release polymers and / or grayness inhibitors. These are, for example, polyesters made from on one side with dihydric and / or polyhydric alcohols, in particular ethylene glycol and / or propylene glycol, closed polyethylene oxides (alcohol component) and aromatic dicarboxylic acids or aromatic and aliphatic dicarboxylic acids (acid component). Further suitable soil-release polymers are amphiphilic graft copolymers and copolymers of vinyl and / or acrylic esters with or on polyalkylene oxides and modified celluloses, for example methylcellulose, hydroxypropylcellulose and carboxymethylcellulose.

Preferably used soil release polymers are graft polymers of vinyl acetate on polyethylene oxide of average molecular weight M _w 2500 to 8 000 in a weight ratio of 1.2: 1 to 3: 1, and commercially available polyethylene terephthalate / polyoxyethylene terephthalates of average molecular weight M _w 3000 to 25000 from polyethylene oxides of average molecular weight M _w 750 to 5000 with terephthalic acid and ethylene oxide and a molar ratio of polyethylene terephthalate to polyoxyethylene terephthalate of 8: 1 to 1: 1 and block polycondensates containing blocks of (a) ester units of polyalkylene glycols of average molecular weight M _w from 500 to 7500 and aliphatic dicarboxylic acids and / or monohydroxymonocarboxylic acids and (b) ester units of aromatic dicarboxylic acids and polyhydric alcohols. These amphiphilic block polymers have average molecular weights M _w of 1500 to 25000.

Grayness inhibitors and soil release polymers are in the detergent formulations in amounts of 0 to 2.5 wt .-%, preferably 0.2 to 1.5 wt .-%, particularly preferably 0.3 to 1.2 wt .-% , contain.

1. a) 0,05 bis 5 Gew.-%, vorzugsweise 0,1 bis 2 Gew.-%, des erfindungsgemäßen farbübertragungsinhibierenden Copolymers;
2. b) 0,5 bis 40 Gew.-% mindestens eines nichtionischen, anionischen und/oder kationischen Tensids;
3. c) 0,5 bis 50 Gew.-% mindestens eines anorganischen Builders;
4. d) 0 bis 10 Gew.-% mindestens eines organischen Cobuilders; und
5. e) 0 bis 60 Gew.-% anderer üblicher Inhaltsstoffe wie Stellmittel, Enzyme, Parfüm, Komplexbildner, Korrosionsinhibitoren, Bleichmittel, Bleichaktivatoren, Bleichkatalysatoren, weitere Farbübertragungsinhibitoren, Vergrauungsinhibitoren, Soil-Release-Polyester, Faser- und Farbschutzadditive, Silicone, Farbstoffe, Bakterizide, Auflösungsverbesserer und/oder Sprengmittel;

wobei die Summe der Komponenten a) bis e) 100 Gew.-% ergibt.Another object of the invention is a solid detergent formulation containing

1. a) 0.05 to 5 wt .-%, preferably 0.1 to 2 wt .-%, of the inventive color transfer inhibiting copolymer;
2. b) from 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 at least one inorganic builder;
4. d) 0 to 10% by weight of at least one organic cobuilder; and
5. e) 0 to 60% by weight of other conventional ingredients such as setting agents, enzymes, perfume, complexing agents, corrosion inhibitors, bleaching agents, bleach activators, bleach catalysts, other color transfer inhibitors, grayness inhibitors, soil release polyesters, Fiber and color protective additives, silicones, dyes, bactericides, dissolution enhancers and / or disintegrants;

the sum of components a) to e) being 100% by weight.

1. a) 0,05 bis 5 Gew.-%, vorzugsweise 0,1 bis 2 Gew.-%, des erfindungsgemäßen farbübertragungsinhibierenden Copolymers;
2. b) 0,5 bis 40 Gew.-% mindestens eines nichtionischen, anionischen und/oder kationischen Tensids;
3. c) 0 bis 20 Gew.-% mindestens eines anionischen Builders;
4. d) 0 bis 10 Gew.-% mindestens eines organischen Cobuilders;
5. e) 0 bis 60 Gew.-% anderer üblicher Inhaltsstoffe wie Soda, Enzyme, Parfum, Komplexbildner, Korrosionsinhibitoren, Bleichmittel, Bleichaktivatoren, Bleichkatalysatoren, weitere Farbübertragungsinhibitoren, Vergrauungsinhibitoren, Soil-Release-Polyester, Faser- und Farbschutzadditive, Silicone, Farbstoffe, Bakterizide, Löslichkeitsvermittler, Hydrotrope, Verdicker und/oder Alkanolamine; und
6. f) 0 bis 99,45 Gew.-% Wasser, und/oder mehrwertige mit Wasser mischbare Alkohole, wie Monopropylenglycol, Dipropylenglycol und Glycerin, sowie Mischungen davon.

The invention further relates to a liquid detergent formulation containing

1. a) 0.05 to 5 wt .-%, preferably 0.1 to 2 wt .-%, of the inventive color transfer inhibiting copolymer;
2. b) from 0.5 to 40% by weight of at least one nonionic, anionic and / or cationic surfactant;
3. c) 0 to 20% by weight of at least one anionic builder;
4. d) 0 to 10% by weight of at least one organic cobuilder;
5. e) 0 to 60 wt .-% of other conventional ingredients such as soda, enzymes, perfume, complexing agents, corrosion inhibitors, bleaching agents, bleach activators, bleach catalysts, other color transfer inhibitors, grayness inhibitors, soil release polyester, fiber and color protective additives, silicones, dyes, bactericides , Solubilizers, hydrotropes, thickeners and / or alkanolamines; and
6. f) 0 to 99.45% by weight of water, and / or polyhydric water-miscible alcohols, such as monopropylene glycol, dipropylene glycol and glycerol, and mixtures thereof.

A detailed description of the detergent ingredients can be found, for. B. in the WO 99/06524 or WO 99/04313 and in Liquid Detergents, Editor: Kuo-Yann Lai, Surfactant Sci. Ser .; Vol. 67, Marcel Decker, New York, 1997, pp. 272-304 ,

Furthermore, the copolymers according to the invention are suitable for the following applications: as brighteners in detergents, auxiliaries in textile production, adjuvants in cosmetic formulations, adjuvants in agrofuels, additives in water treatment, auxiliaries in metalworking agents and coolants and as gas hydrate inhibitors and in other fields of application oilfield.

The following examples serve to illustrate the invention.

Examples of polymerization Example 1:

In a reactor 800 g of distilled water were heated under nitrogen supply to about 82 ° C (T) internal temperature. Then, 360 g of vinylpyrrolidone (VP) and, in parallel, a mixture of 20.8 g of methacrylic acid (MAS), 19.2 g of α-methoxy-.omega.-methacryloylpolyethylene glycol (having a number-average molecular weight of polyethylene glycol (PEG) of about 1000) (MPEGMA). and 60 g of water (W1) within 3 h continuously (ie at a constant rate) added. At the same time, 8 g of 2,2'-azobis (2-methylpropionamidine) -dihydrochloride (V-50, Wako Chemicals) (V50) in 80 g of water (W2) were added continuously within 4 h. Then, stirring was continued for a further hour at 82 ° C under a nitrogen atmosphere. Within 30 minutes, 2 g of 2,2'-azobis (2-methylpropionamidine) dihydrochloride in 20 g of water were added. After a further 2 h stirring at 82 ° C, the solution was adjusted to a pH of 7.2 with 50% aqueous sodium hydroxide solution. A slightly yellowish, clear solution having a solids content (F.G.) of 28% and a K value (1% by weight in aqueous solution) of 28.0 was obtained.

Examples 2 to 10 were carried out analogously to Example 1, wherein in each case indicated in Table 1 below amounts of vinylpyrrolidone (VP), optionally as a mixture with the particular amount of vinylimidazole (VI), as well as methacrylic acid (MAS), α-Metoxy -ω-methacryloylpolyethylene glycol (MPEGMA), water (W1 and W2) and 2,2'-azobis (2-methylpropionamidine) dihydrochloride (V50) were used.

Examples 11 to 20: Example 11:

In a reactor, 385 g of distilled water and 80 g of allyl ether ethoxylate (allyl alcohol with 10 ethylene oxide (EO) units) were heated to 87 ° C (T) internal temperature while supplying nitrogen. Then, 320 g of vinylpyrrolidone (VP) were added continuously within 3 h. Time shifted by about 5 minutes, a solution of 6.4 g of 2,2'-azobis (2-methylpropionamidine) dihydrochloride (V50) in 58 g of water was added continuously within 3 h. Then, stirring was continued for a further hour at 87 ° C under a nitrogen atmosphere. It was then cooled to an internal temperature of 60 ° C, then 2.3 g of tert-butyl hydroperoxide (70%), dissolved in 14 g of water (W3), added all at once. Then, within 30 minutes, 1.6 g of sodium bisulfite dissolved in 50 g of demineralized water were added. The mixture was stirred for a further hour at 60.degree. A slightly yellowish, clear solution having a solids content of 46.2% and a K value (1% by weight in 3% strength by weight aqueous NaCl solution) of 33.7 was obtained.

Examples 13, 15 and 16 were carried out analogously to Example 11.

Example 12:

In a reactor 385 g were dist. Water and 80 g of allyl ether ethoxylate (allyl alcohol with 10 EO units) under nitrogen supply to 87 ° C internal temperature. Then, 320 g of vinylpyrrolidone (VP) were added continuously within 2 h. Time shifted by about 5 minutes, a solution of 6.4 g of 2,2'-azobis (2-methylpropionamidine) dihydrochloride (V50) in 58 g of water within 2 h continuously metered. Then, stirring was continued for a further hour at 87 ° C under a nitrogen atmosphere. It was then cooled to an internal temperature of 60 ° C; then 2.3 g of tert-butyl hydroperoxide (70%), dissolved in 14 g of water, were added all at once. Then, within 30 minutes, 1.6 g of sodium bisulfite dissolved in 50 g of demineralized water were added. The mixture was stirred for a further hour at 60.degree. A slightly yellowish, clear solution having a solids content of 46.7% and a K value (1% by weight in 3% strength by weight NaCl solution) of 36.7 was obtained.

Examples 14 and 17 were carried out analogously to Example 12.

Example 18:

In a reactor, 385 g of distilled water and 80 g of allyl ether ethoxylate (16.6 EO allyl alcohol) were heated to 87 ° C (T) internal temperature with nitrogen. At the same time, 220 g of vinylpyrrolidone (VP) and 100 g of vinylimidazole (VI) were continuously metered in within 3 hours. Time shifted by about 5 minutes, a solution of 6.4 g of 2,2'-azobis (2-methylpropionamidine) dihydrochloride (V50) in 58 g of water was added continuously within 3 h. Then, stirring was continued for a further hour at 87 ° C under a nitrogen atmosphere. A slightly yellowish, clear solution having a solids content of 48.7% and a K value (1% by weight in 3% strength by weight aqueous NaCl solution) of 41.5 was obtained.

Example 19 was carried out analogously to Example 18.

Example 20:

In a reactor 385 g were dist. Water and 80 g of allyl ether ethoxylate (allyl alcohol 16.6 EO units) under nitrogen to 87 ° C (T) internal temperature heated. At the same time, 220 g of vinylpyrrolidone (VP) and 100 g of vinylimidazole (VI) were continuously metered in within 3 hours. Time shifted by about 5 minutes, a solution of 6.4 g of 2,2'-azobis (2-methylpropionamidine) dihydrochloride (V50) in 58 g of water and a further solution of 1.2 g mercaptoethanol (ME), dissolved in 11 g of water, continuously added within 3 h. Then, stirring was continued for a further hour at 87 ° C under a nitrogen atmosphere. It was then cooled to an internal temperature of 60 ° C, then 2.3 g of tert-butyl hydroperoxide (70%) dissolved in 14 g of water were added all at once. Then, within 30 minutes, 1.6 g of sodium bisulfite dissolved in 50 g of demineralized water were added. The mixture was stirred for a further hour at 60.degree. There was obtained a slightly yellowish, clear solution having a solids content of 45.8% and a K value (1 wt .-% in 3 wt .-% aqueous NaCl solution) of 34.4.

Example 21 was carried out analogously to Example 20.

Example 23:

In a reactor, 385 g of distilled water and 80 g of allyl ether ethoxylate (16.6 EO allyl alcohol) were heated to 87 ° C internal temperature with nitrogen. Then, 320 g of vinylpyrrolidone (VP) were added continuously within 3 h. Time shifted by about 5 minutes, a solution of 6.4 g of 2,2'-azobis (2-methylpropionamidine) dihydrochloride (V50) in 58 g of water and a further solution of 1.6 g of mercaptoethanol (ME), dissolved in 14.4 g of water, metered in continuously over 3 h. Then, stirring was continued for a further hour at 87 ° C under a nitrogen atmosphere. It was then cooled to an internal temperature of 60 ° C; then 2.3 g of tert-butyl hydroperoxide (70%), dissolved in 14 g of water, were added all at once. Then, within 30 minutes, 1.6 g of sodium bisulfite dissolved in 50 g of demineralized water were added. The mixture was stirred for a further hour at 60.degree. A slightly yellowish, clear solution having a solids content of 32% and a K value (1% by weight in 3% strength by weight NaCl solution) of 31 was obtained.

Example 22 was carried out analogously to Example 23, but no mercaptoethanol (ME) was added.

Example 24:

In a reactor, 385 g of distilled water and 80 g of allyl ether alkoxylate (allyl alcohol with 1 EO and 42 propylene oxide (PO) units) were heated to 87 ° C internal temperature with nitrogen. Then, at the same time, 160 g of vinylpyrrolidone (VP) and 160 g of vinylimidazole (VI) were metered in continuously over the course of 3 hours. Time shifted by about 5 minutes, a solution of 6.4 g of 2,2'-azobis (2-methylpropionamidine) dihydrochloride (V50) in 50 g of water was added continuously within 3 h. Then, stirring was continued for a further hour at 87 ° C under a nitrogen atmosphere. It was then cooled to an internal temperature of 60 ° C; then 2.3 g of tert-butyl hydroperoxide (70%), dissolved in 14 g of water, were added all at once. Subsequently, within 30 minutes, 9.6 g of sodium disulfite dissolved in 50 g of demineralized water was added. The mixture was stirred for a further hour at 60.degree. A slightly yellowish, clear solution having a solids content of 39.8% and a K value (1% by weight in 3% strength by weight NaCl solution) of 40.5 was obtained.

Example 25:

In a reactor, 385 g of distilled water and 80 g of allyl ether alkoxylate (allyl alcohol with 1 EO and 42 propylene oxide (PO) units) were heated to 87 ° C (T) internal temperature with nitrogen. Then, 160 g of vinylpyrrolidone (VP) and parallei 160 g of vinylimidazole (VI) were added continuously within 3 h. Time shifted by about 5 minutes were each a solution of 6.4 g of 2,2'-azobis (2-methylpropionamidine) dihydrochloride (V50) in 50 g of water and 1.2 g of mercaptoethanol (ME) distilled in 11 g Water continuously added within 3 h. Then, stirring was continued for a further hour at 87 ° C under a nitrogen atmosphere. A slightly yellowish, clear solution having a solids content of 38.4% and a K value (1% by weight in 3% strength by weight aqueous NaCl solution) of 31.8 was obtained.

In the following Tables 2a and 2b, the parameters of the experimental procedures of Examples 11 to 25 are summarized. <b> Table 2a: </ b> In game VP [g] VP [mol%] VI [g] VI [mol%] Allyl alcohol ethoxylate [g] / [number of EO units] / [mol%] V50 [g] K value FG [%] 11 320 94.7 - - 80/10 / 5.3 6.4 33.7 46.2 12 320 94.7 - - 80/10 / 5.3 4.0 36.7 46.7 13 320 94.7 - - 80/10 / 5.3 4.0 32.8 46.9 14 320 94.7 - - 80/10 / 5.3 4.0 31.5 45.9 15 340 96.3 - - 60/10 / 3.8 6.4 32.6 52.3 16 340 96.3 - - 60/10 / 3.8 4.0 35 53.2 17 340 96.3 - - 60/10 / 3.8 4.0 39.6 52.3 18 220 63.0 100 33.8 80 / 16.6 / 3.2 6.4 41.5 48.7 19 160 44.4 160 52.5 80 / 16.6 3.1 6.4 43.3 48.9 In game VP [g] VP [mol%] VI [g] VI [mol%] Allyl alcohol ethoxylate [g] / EO content ^# / PO content ^# / [mol%] V50 [g] ME [g] K value FG [%] 20 220 63.0 100 33.8 80 / 16.6 / - / 3.2 6.4 1.2 34.4 45.8 21 160 44.4 160 52.5 80 / 16.6 / - / 3.1 6.4 1.6 32.7 45.1 22 320 94.7 - - 80/10 / - / 5.3 6.4 - 35.4 28 23 320 96.6 - - 80 / 16.6 / - / 3.4 6.4 1.6 31 32 24 160 45.4 160 53.6 80/1/42 / 1.0 6.4 - 40.5 39.8 25 160 45.4 160 53.6 80/1/42 / 1.0 6.4 1.2 31.8 38.4 # Number of EO or PO units (number average)

Application examples Testing of copolymers according to the invention as dye transfer inhibitors in detergents

The copolymers of the invention were tested as color transfer inhibitors in detergents. For this purpose, two granular detergents (WM 1, WM 2) and two liquid detergents (WM 3, WM 4) of the compositions listed in Table 3 were prepared by way of example, wherein WM 1 and WM 2 or WM 3 and WM 4 are in each case determined by the content of copolymer according to the invention (WM 1 = 0 , 15 wt%, WM2 = 0.25 wt%, WM3 = 0.15 wt%, WM4 = 1 wt%). Then it became white cotton test fabric under the washing conditions mentioned in Table 4 in the presence of dye which was added to the wash liquor as 0.03 or 0.06 wt.% Aqueous solution, washed.

The staining of the test fabric was measured photometrically using the Elrepho 2000 photometer (Datacolor). The remission (in%) was measured at the wavelength of the respective maximum absorption of the different dyes. The whiteness of the test fabric after the wash was used to evaluate staining. The measured values given in Table 5 a - c were confirmed by multiple repetition and averaging.

Table 5 a - c shows the results of the wash tests with copolymers according to the invention in comparison with washing tests without dye transfer inhibitor. <b> Table 3: </ b> Compositions of detergents WM1 to WM4 (in% by weight) WM 1 [%] WM 2 [%] WM 3 [%] WM 4 [%] C ₁₂ / C ₁₄ fatty alcohol sulfate 24 24 C ₁₂ / C ₁₄ fatty alcohol ethoxylate 2 2 C ₁₂ / C ₁₄ alkyl benzene sulfonate 9 9 C ₁₃ / C ₁₅ - tallow fatty alcohol reacted with 7 EO units 6.6 6.6 6 6 coconut fatty acid 5 5 Soap 1.8 1.8 0.7 0.7 borax 2.2 2.2 Zeolite A 45 45 Polycarboxylate (acrylic acid / maleic acid copolymer; w / w 70:30, M _w 70000) 5 5 sodium 7 7 Trisodium citrate x 2 H ₂ O 12 12 2.1 2.1 magnesium silicate 0.8 0.8 carboxymethylcellulose 0.8 0.8 propylene glycol monomethyl ether 10 10 Copolymer (above 100%) 0.15 0.25 0.15 1 water ad 100 ad 100 ad 100 ad 100 WM1 WM2 device Lauder-o-meter Lauder-o-meter cycles 1 1 duration 30 min 30 min water hardness 3.0 mmol Ca ²⁺ / l, molar ratio Ca: Mg: HCO ₃ : 4: 1: 8 3.0 mmol Ca ²⁺ / l, molar ratio Ca: Mg: HCO ₃ : 4: 1: 8 temperature 60 ° C 60 ° C dye entry dye solution dye solution Test fabric cotton swab cotton swab amount of liquor 250 ml 250 ml liquor ratio 1: 12.5 1: 12.5 detergent concentration 4.5 g / l 6 g / l Copolymer of Ex. % Remission Direct Blue 71 % Remission Direct Red 212 % Remision Direct Black 22 1 69.5 56.1 64.6 2 70.2 57.3 62.6 3 68.9 55.7 64.8 4 69.2 56.1 64.4 5 70.1 56.6 65.5 6 68.5 56.0 66.5 7 70.0 57.4 67.3 8th 68.8 56.6 68.1 9 72.5 60.4 67.0 10 74.7 64.6 70.3 without 63.4 54.3 59.7 Whiteness before washing 79.8 78.8 80 Copolymer of Ex. % Remission Direct Blue 71 % Remission Direct Red 212 % Remision Direct Black 22 11 71.48 58.14 67.71 12 73.07 58.34 69.11 13 72.89 58.83 68.31 18 76.27 65.46 74.69 19 76.58 68.31 76.44 20 76.50 65.57 75.00 21 76.70 68.26 76.94 22 73.07 58.34 69.11 23 72.89 58.83 68.31 24 76.83 69.27 76.83 25 76.68 68.98 77.23 without 63.6 53.98 65.54 Whiteness before washing 79.8 78.8 80 Copolymer of Ex. % Remission Direct Blue 71 % Remission Direct Red 212 % Remision Direct Black 22 1 69.8 57.0 70.5 2 69.8 56.9 70.1 3 69.0 57.0 70.0 4 68.2 56.4 69.8 5 69.4 55.7 69.1 6 67.6 55.8 69.9 7 69.1 56.3 69.7 8th 68.1 55.9 70.5 without 64.5 53.7 69.8 Whiteness before washing 79.8 78.8 80

The washing results obtained show the very good effectiveness of the copolymers according to the invention as color transfer inhibitors, which is independent of the type of dye.

Check for compatibility in liquid detergents

In order to evaluate the stability of the copolymers in different liquid detergent formulations, 1% by weight of copolymer was in each case formulated in the liquid detergent and a visual assessment was carried out with regard to phase separation, turbidity, incompatibilities, etc.

The stability tests were carried out with the liquid detergent formulation WM4.

Table 6 summarizes the visual ratings after 4 weeks storage at 40 ° C. <b> Table 6: </ b> Copolymer Example No. WM 4 without clear Copolymer 1 clear Copolymer 3 clear Copolymer 9 clear Copolymer 10 clear Copolymer 11 clear Copolymer 22 clear Copolymer 23 clear

Claims (18)

1. The use of a copolymer comprising, in polymerized form, (a) from 80 to 99.9 mol%, based on the total amount of the monomers polymerized to prepare the copolymer, of at least one monomer A which in each case comprises a heterocycle having at least 1 nitrogen atom and composed of from 3 to 10 ring members and a C₂-C₆-alkenyl group bonded to a carbon or nitrogen ring atom of the heterocycle; and (b)from 0.1 to 20 mol%, based on the total amount of the monomers polymerized to prepare the copolymer, of at least one monomer B copolymerizable with monomer A, said monomer B having a monoethylenically unsaturated double bond and also a linear or branched poly-C₂-C₄-alkylene oxide group having on average from 4 to 500 C₂-C₄-alkylene oxide units, in liquid and in solid detergent formulations.
2. The use according to claim 1, wherein monomer A comprises at least one N-vinyllactam and, if appropriate, at least one N-vinylimidazole, and both the former and the latter may each have 1, 2, 3 or 4 substituents each independently selected from C₁-C₄-alkyl, C₃-C₆-cycloalkyl and phenyl.
3. The use according to claim 2, wherein monomer A is selected from N-vinylpyrrolidone and mixtures of N-vinylpyrrolidone with N-vinylimidazole.
4. The use according to any of the preceding claims, wherein the proportion of ethylene oxide units in monomer B is at least 50% based on the C₂-C₄-alkylene oxide units present in monomer B.
5. The use according to any of the preceding claims, wherein the poly-C₂-C₄-alkylene oxide group in monomer B has 1 or 2 end groups which are each independently selected from H, C₁-C₁₀-alkyl and benzyl.
6. The use according to claim 5, wherein the end groups are selected from C₁-C₂-alkyl.
7. The use according to any of the preceding claims, wherein monomer B has the general formula I:
   
           X-CH=CR¹-Y-Z     (I)
   
   where

   X is H or COOH;

   R¹ is H or methyl;

   Y is O, CH₂-O, C(O)O, C(O)NH, NHC(O) or CH₂-NHC(O); and

   Z is a linear or branched poly-C₂-C₄-alkylene oxide group comprising on average from 4 to 500 C₂-C₄- alkylene oxide units and 1 or 2 terminal radicals each independently selected from H, C₁- C₁₀-alkyl and benzyl.
8. The use according to claim 7, wherein, in formula I, the variable X is H and Y is C(O)O or C(O)NH.
9. The use according to claim 8, wherein the terminal radical(s) in Z is/are C₁-C₂-alkyl.
10. The use according to any of the preceding claims, wherein monomer B is selected from the methyl polyethylene glycol esters of (meth)acrylic acid and allyl ether ethoxylates.
11. The use according to claim 7, wherein, in formula I, the variable X is H and Y is CH₂-O.
12. The use according to any of the preceding claims, wherein the copolymer additionally comprises, in polymerized form, from 0 to 20 mol% of at least one monomer C copolymerizable with monomers A and B, said monomer C being selected from monoethylenically unsaturated C₃-C₁₀-mono- and -dicarboxylic acids, vinyl esters of saturated C₁-C₁₀-carboxylic acids, vinyl and allyl ethers of C₁-C₁₀-alcohols, vinylformamides, quaternary products of N-vinyl- and N-allylamines and derivatives thereof, and also mixtures thereof.
13. The use according to any of the preceding claims, wherein the proportion of monomer C is at most 20 mol%.
14. The use according to any of the preceding claims, wherein the copolymer has a K value in the range from 10 to 150.
15. A copolymer comprising, in polymerized form, (a) from 80 to 99.9 mol%, based on the total amount of the monomers polymerized to prepare the copolymer, of at least one monomer A which in each case comprises a heterocycle having at least 1 nitrogen atom and composed of from 3 to 10 ring members and a C₂-C₆-alkenyl group bonded to a carbon or nitrogen ring atom of the heterocycle; (b) from 0.1 to 20 mol%, based on the total amount of the monomers polymerized to prepare the copolymer, of at least one monomer B copolymerizable with monomer A, said monomer B having a monoethylenically unsaturated double bond and also a linear or branched poly- C₂-C₄-alkylene oxide group having on average from 4 to 500 C₂-C₄-alkylene oxide units, with the proviso that the end group of the poly-C₂-C₄-alkylene oxide group in the monomers B is selected from C₁-C₂-alkyl when monomer B is an ester of an ethylenically unsaturated carboxylic acid with a linear poly-C₂-C₄-alkylene oxide, and, if appropriate, (c) from 0 to 20 mol%, based on the total amount of the monomers polymerized to prepare the copolymer, of at least one monomer C copolymerizable with monomers A and B, the total amount of monomers (a), (b) and (c) being 100 mol%.
16. A process for preparing the copolymer according to claim 15, which comprises free-radically polymerizing the at least one monomer A with the at least one monomer B and also, if appropriate, with the monomers C.
17. The process according to claim 16, wherein a solution polymerization is carried out in aqueous and/or alcoholic reaction medium.
18. A liquid or solid detergent formulation comprising at least one copolymer as defined in any of claims 1 to 14, and customary washing substance