EP0541588B1 - Use of polymerizates containing n-(alkyloxy-polyalkoxymethyl)carbonamide groups as additives to washing and cleaning agents - Google Patents

Abstract

The invention concerns the use of polymerizates containing, as the major monomer component, at least 5 % by wt. of N-(alkoxy-polyalkoxymethyl)carboxylic acid amides of monoethylenically unsaturated C3?-C8? carboxylic acids as additives to low-phosphate and phosphate-free washing and cleaning agents in amounts which increase the primary and secondary washing capability of the agent, plus agents containing these polymerizates.

Description

The invention relates to the use of polymers which, as an essential monomer, contain copolymerized N- (alkyloxy-polyalkoxymethyl) carboxamides of monoethylenically unsaturated C₃- to C₈-carboxylic acids, as an additive to detergents and cleaning agents and detergents and cleaning agents which contain such polymers.

For ecological reasons, there has been an increasing search for substitutes for phosphates in detergents in recent years. Polymers which are described in EP-PS 0 025 551 are of particular importance as phosphate substitutes. This involves the use of copolymers of maleic acid and acrylic acid as an incrustation inhibitor in detergents. These copolymers are used in amounts of up to 10% by weight in the detergent formulation. With the aid of these copolymers, it is possible to replace all or part of the phosphates previously used in detergents. After the washing process, the copolymers end up in the wastewater and are almost completely absorbed in sewage treatment plants. In the case of liquid detergents which contain copolymers of acrylic acid and maleic acid as a phosphate substitute, however, segregation often occurs during storage.

From US Pat. No. 4,746,456 it is known to use graft copolymers of vinyl acetate on polyalkylene glycols as graying inhibitors in detergent formulations.

EP-PS 0 116 930 describes water-soluble copolymers of 40 to 90% by weight of at least one ethylenically unsaturated monocarboxylic acid with 3 to 5 C atoms and 60 to 10% by weight of at least one ethylenically unsaturated dicarboxylic acid with 4 to 8 C Atoms and / or their corresponding dicarboxylic acid anhydrides are known, in which 2 to 60% by weight, based on the total weight of the carboxylic acids or carboxylic acid anhydrides, are esterified with alkoxylated C₁ to C₁₈ alcohols or C₁ to C₁₂ alkylphenols. The partially esterified copolymers and their water-soluble salts are used, inter alia, in amounts of 0.5 to 10% by weight in liquid detergent formulations. As is known from this reference, the compatibility of the partially esterified copolymers of at least one monoethylenically unsaturated monocarboxylic acid is and at least one monoethylenically unsaturated dicarboxylic acid is significantly cheaper than in the non-esterified products, so that there are fewer phase separations. However, the partially esterified copolymers of the type described are not stable to hydrolysis, so that they hydrolyze in liquid detergent formulations. As a result, inhomogeneities occur, which can even go so far as to result in the phase separation of the liquid detergent.

EP-A-0 237 075 discloses liquid detergents which contain at least one nonionic surface-active agent in an amount of 5 to 25% by weight, 2 to 25% by weight of a builder, about 1 to 10% by weight of C₄ - To C₃₀ α-olefin-maleic anhydride copolymers and, to make up to 100 wt .-%, water. Although these liquid detergents initially represent clear solutions, they separate relatively quickly during storage.

From US Pat. No. 3,328,309, liquid alkaline detergent formulations are known which, in addition to water and detergents as stabilizers, contain 0.1 to 5%, based on the entire formulation, of a hydrolyzed copolymer of an α, β-unsaturated carboxylic anhydride with a vinyl ester, vinyl ether or contain an α-olefin in partially esterified form. The alcohol components used for esterification include addition products of alkylene oxides, in particular ethylene oxide onto alkylphenols, also come into consideration. Only 0.01 to 5% of the carboxyl groups of the copolymer are present as ester groups. Although these liquid detergents contain components which are compatible with one another, the primary washing action of this liquid detergent formulation is still in need of improvement.

EP-A-0 215 251 describes the use of homopolymers of acrylic acid and methacrylic acid, copolymers of acrylic acid and methacrylic acid and of copolymers of ethylenically unsaturated dicarboxylic acids with 4 to 6 carbon atoms and acrylic acid or methacrylic acid in each case partially neutralized and / or with long-chain amines and / or partially amidated form as a graying-inhibiting additive to detergents and cleaning agents which promotes the primary washing action in quantities of 0.05 to 10% by weight. The partially amidated homopolymers and copolymers are prepared by reacting the polymers with long-chain amines. In many cases they still contain free amines, which are undesirable in detergent formulations because of their smell and physiological concern.

Furthermore, copolymers of acrylic acid and methacrylic acid esters of ethoxylated alcohols as addition of detergents are known from US Pat. No. 4,797,223. From EP-A-0 368 214 is the use of copolymers of monoethylenically unsaturated C₃- to C₈-carboxylic acids, esters of these carboxylic acids with alkyl vinyl ethers or mixtures of these monomers and amides of monoethylenically unsaturated C₃- to C₈-carboxylic acids in which the amide groups are one C₈- to C₂₈ alkyl radical or contain a polyalkyleneoxy radical which is bonded to the nitrogen atom via an alkylene group, known as an additive to liquid detergents in amounts of up to 20% by weight. Although such copolymers allow the production of storage-stable liquid detergents, they hydrolyze relatively quickly at the high pH values of the detergent formulations.

The object of the present invention is to provide other polymers which are easy to prepare and hydrolysis-stable at high pH values for use in detergents and cleaning agents.

        R¹-O-(CH₂-CH₂-CH₂-O)_m-



R¹ = C₁- bis C₂₈-Alkyl, C₃ bis C₂₈-Alkenyl, Phenyl und C₁- bis C₁₈-Alkylphenyl,
R², R³ = H, CH₃, C₂H₅,
n = 1 bis 200 und
m = 1 bis 100
einpolymerisiert enthalten, als Zusatz zu phosphatarmen und phosphatfreien Wasch- und Reinigungsmitteln in Mengen von 0,1 bis 20 Gew.-%, bezogen auf die Wasch- und Reinigungsmittel.The object is achieved according to the invention by using polymers which are at least 5% by weight of N- (alkyloxypolyalkoxymethyl) carbonamides of monoethylenically unsaturated C₃- to C₈-carboxylic acids with amide groups of the structure as an essential monomer



-CO-NH-CH₂-R, (I)



in the

R¹-O- (CH₂-CH₂-CH₂-O) _m -



R¹ = C₁ to C₂₈ alkyl, C₃ to C₂₈ alkenyl, phenyl and C₁ to C₁₈ alkylphenyl,
R², R³ = H, CH₃, C₂H₅,
n = 1 to 200 and
m = 1 to 100
polymerized contain, as an additive to low-phosphate and phosphate-free detergents and cleaning agents in amounts of 0.1 to 20 wt .-%, based on the detergents and cleaning agents.

   mit R¹ = C₁- bis C₂₈-Alkyl, C₃- bis C₂₈-Alkenyl, Phenyl und C₁- bis C₁₈-Alkylphenyl und
   m = 1 bis 100, vorzugsweise 3 bis 70.The polymers to be used in detergents and cleaning agents according to the invention contain as essential monomer at least 5% by weight of N- (alkyloxy-polyalkoxymethyl) carboxamides of monoethylenically unsaturated C₃- to C₈-carboxylic acids with amide groups of the structure I given above 11 of EP-B-0 063 018 obtainable by reacting N-isobutoxymethyl acrylamide in the presence of acids with alkoxylated alcohols. Instead of polyalkoxylated alcohols, the reaction products of alcohol and polytetrahydrofuran can be used as a possible reaction component. Such reaction products can be characterized using the formula II:

with R¹ = C₁- to C₂₈-alkyl, C₃- to C₂₈-alkenyl, phenyl and C₁- to C₁₈-alkylphenyl and
m = 1 to 100, preferably 3 to 70.

mit

R¹ =

C₁- bis C₂₈-Alkyl, C₃- is C₂₈-Alkenyl, Phenyl und C₁- bis C₁₈-Alkylphenyl

R², R³ =

H, CH₃, C₂H₅ und

n =

1 bis 200, vorzugsweise 3 bis 100.

Compounds with structure I are preferably obtainable by reacting N- (C₁- to C₄-alkyloxymethyl) carboxamides of ethylenically unsaturated C₃- to C₈-carboxylic acids with alkoxylated compounds of the following formulas:

With

R¹ =

C₁- to C₂₈-alkyl, C₃- is C₂₈-alkenyl, phenyl and C₁- to C₁₈-alkylphenyl

R², R³ =

H, CH₃, C₂H₅ and

n =

1 to 200, preferably 3 to 100.

Compounds of the formula III are obtained by reacting monovalent C₁ to C₂₈ alcohols, monovalent C₃ to C₂₈ alkenols, phenol and C₁- to C₁₈ alkylphenols with alkylene oxides with 2-4 carbon atoms. The compounds containing OH groups mentioned can be reacted, for example, with ethylene oxide, propylene oxide or butylene oxide. The alkylene oxides can be used either alone or as a mixture in the alkoxylation will. In the latter case, the alkoxylation produces products which contain the alkylene oxides copolymerized in a random distribution. However, the alkylene oxides can also be used in succession in the alkoxylation reaction, so that block copolymers are formed. For example, a compound of the general formula R¹-OH, in which R¹ has the meaning given in formula III, is first reacted with ethylene oxide, then with propylene oxide and then with butylene oxide. However, it is also possible to react a compound of the general formula R1-OH first with ethylene oxide, then with butylene oxide and then again with ethylene oxide. Further possible variations result from the fact that the alkoxylation is first started with propylene oxide, then ethylene oxide and then again propylene oxide. Further possible variations are conceivable for the preparation of compounds of the formula III, namely addition of alkylene oxides onto compounds of the formula R 1 -OH in the order of ethylene oxide, butylene oxide, propylene oxide or butylene oxide-ethylene oxide-propylene oxide. Preferably used as compounds of formula III for the preparation of the essential monomers, the alkoxylation products of monohydric C₁ to C₁₈ alcohols and of monohydric C₃- to C₁₈ alkenols, especially oleyl alcohol. Ethylene oxide and / or propylene oxide are preferably used as alkoxylating agents. They are preferably used in an amount of 3 to 100 mol / mol alcohol. The compounds of formula III are preferably water-soluble.

   CH₂=CH-CO-NH-CH₂-(O-CH₂-CH₂)₉-O-Oleyl
   CH₂=CH-CO-NH-CH₂-(O-CH₂-CH₂)₉₀-O-Oleyl

   CH₂=CH-CO-NH-CH₂-(O-CH₂-CH₂-CH₂-CH₂)₁₀-O-C_13/15-Alkyl
   CH₂=CH-CO-NH-CH₂-(O-CH₂-CH₂-CH₂-CH₂)₁₅-O-Oleyl
Die obengenannten Amidgruppen der Struktur I aufweisenden Monomeren werden entweder allein zu Homopolymerisaten oder untereinander zu Copolymerisaten polymerisiert. Diese Polymerisate werden erfindungsgemäß als Zusatz zu Wasch- und Reinigungsmitteln verwendet ebenso wie Copolymerisate der Carbonamidgruppen der Struktur I mit anderen ethylenisch ungesättigten Monomeren. In Betracht kommen beispielsweise Copolymerisate, die

• a) 10 bis 99 Gew.-% an N-(Alkyloxy-polyalkoxymethyl)carbonamiden monoethylenisch ungesättigter C₃- bis C₈-Carbonsäuren mit Amidgruppen der Struktur I und
• b) 90 bis 1 Gew.-% anderer monoethylenisch ungesättigter Monomere einpolymerisiert enthalten. Geeignete Monomere der Gruppe b) sind beispielsweise monoethylenisch ungesättigte C₃- bis C₈-Carbonsäuren, deren Ester mit C₁- bis C₂₈-Alkoholen, Ester von monoethylenisch ungesättigten C₃- bis C₈-Carbonsäuren mit Umsetzungsprodukten aus C₁- bis C₂₈-Alkoholen und Ethylenoxid, Propylenoxid und/oder Butylenoxid im Molverhältnis 1:1 bis 1:100, Amide, N-C₁- bis c₁₈-Alkyloxy-methylamide und Nitrile monoethylenisch ungesättigter C₃-bis C₈-Carbonsäuren, Vinylester von gesättigten Carbonsäuren mit 1 bis 20 C-Atomen, C₁- bis C₂₈-Alkylvinylether, Styrol oder deren Gemische.

The carboxylic acids on which the amides with structure I are based are, for example, acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, citraconic acid, crotonic acid, fumaric acid, itaconic acid and vinyl acetic acid. Preferred monomers for the preparation of the polymers to be used according to the invention are derived from acrylamide and methacrylamide in which the amide groups have the structure I. Some monomers with amide groups of structure I are listed below by way of example:
CH₂ = CH-CO-NH-CH₂- (O-CH₂-CH₂) ₇-OC _13/15 alkyl
CH₂ = CH-CO-NH-CH₂- (O-CH₂-CH₂) ₃-OC _13/15 alkyl
CH₂ = CH-CO-NH-CH₂- (O-CH₂-CH₂) ₁₁-OC _13/15 alkyl
CH₂ = CH-CO-NH-CH₂- (O-CH₂-CH₂) ₃₀-OC _13/15 alkyl
CH₂ = C (CH₃) -CO-NH-CH₂- (O-CH₂-CH₂) ₇-OC _13/15 alkyl
CH₂ = CH-CO-NH-CH₂- (O-CH₂-CH₂) ₂₅-OC _16/18 alkyl
CH₂ = C (CH₃) -CO-NH-CH₂- (O-CH₂-CH₂) ₃-OC _13/15 alkyl
CH₂ = C (CH₃) -CO-NH-CH₂- (O-CH₂-CH₂) ₁₁-OC _13/15 alkyl
CH₂ = C (CH₃) -CO-NH-CH₂- (O-CH₂-CH₂) ₁₁-OC _16/18 alkyl
CH₂ = C (CH₃) -CO-NH-CH₂- (O-CH₂-CH₂) ₈₀-O-CH₃

CH₂ = CH-CO-NH-CH₂- (O-CH₂-CH₂) ₉-O-oleyl
CH₂ = CH-CO-NH-CH₂- (O-CH₂-CH₂) ₉₀-O-oleyl

CH₂ = CH-CO-NH-CH₂- (O-CH₂-CH₂-CH₂-CH₂) ₁₀-OC _13/15 alkyl
CH₂ = CH-CO-NH-CH₂- (O-CH₂-CH₂-CH₂-CH₂) ₁₅-O-oleyl
The above-mentioned amide groups of structure I monomers are polymerized either alone to form homopolymers or with one another to form copolymers. According to the invention, these polymers are used as additives for detergents and cleaning agents, as are copolymers of the carbonamide groups of structure I with other ethylenically unsaturated monomers. For example, copolymers are considered

• a) 10 to 99 wt .-% of N- (alkyloxy-polyalkoxymethyl) carbonamides monoethylenically unsaturated C₃- to C₈-carboxylic acids with amide groups of structure I and
• b) contain 90 to 1% by weight of other monoethylenically unsaturated monomers in copolymerized form. Suitable monomers of group b) are, for example, monoethylenically unsaturated C₃ to C₈ carboxylic acids, their esters with C₁ to C₂₈ alcohols, esters of monoethylenically unsaturated C₃ to C₈ carboxylic acids with reaction products of C₁ to C₂ aus alcohols and ethylene oxide, propylene oxide and / or butylene oxide in a molar ratio of 1: 1 to 1: 100, amides, N-C₁ to C₁₈-alkyloxy-methylamides and nitriles of monoethylenically unsaturated C₃-to C₈-carboxylic acids, vinyl esters of saturated carboxylic acids with 1 to 20 C atoms, C₁ - Up to C₂₈ alkyl vinyl ether, styrene or mixtures thereof.

Suitable monoethylenically unsaturated C₃- to C₈-carboxylic acids are, for example, acrylic acid, methacrylic acid, vinyl acetic acid, 2-ethyl acrylic acid, maleic acid, fumaric acid, crotonic acid and itaconic acid. Acrylic acid, methacrylic acid and maleic acid are preferred.

Suitable esters of the above-mentioned carboxylic acids with C₁ to C₂₈ alcohols are, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, tert-butyl acrylate Butyl ester of methacrylic acid, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-octyl acrylate, isobutyl acrylate, isobutyl methacrylate, palmitylacrylate, palmityl methacrylate, stearyl acrylate, stearyl methacrylate, maleate dimethyl ester, maleate diethyl ester, maleate maleate diethyl ester Maleic acid esters of cyclohexanol, dodecyl alcohol and octadecyl alcohol, half esters of maleic acid, such as monomethyl maleate, monocyclohexyl maleate, mono-2-ethylhexyl maleate, monooctadecyl maleate, the corresponding fumaric acid esters and half esters of saturated C₁ to C₂₈ Alcohols, itaconic acid dimethyl ester, itaconic acid diethyl ester and itaconic acid di-n-propyl ester or isopropyl ester.

Also suitable are polymers which contain copolymerized as comonomers of group b) esters of monoethylenically unsaturated C₃- to C₈-carboxylic acids and polyhydric alcohols, for example hydroxylethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl acid and acrylic methacrylate, and the ester of methacrylate and methacrylate 1,6-hexanediol.

Suitable esters of monoethylenically unsaturated C₃- to C₈-carboxylic acids with reaction products from alcohols and alkylene oxides are, for example, the esters of acrylic acid and methacrylic acid with ethoxylated C₁- to C₂ ein--alcohols, the one or one by adding 1 to 100 moles of ethylene oxide to 1 mole polyhydric alcohol. Mixtures of alkylene oxides can also be used in the ethoxylation of the alcohols, e.g. Mixtures of ethylene oxide, propylene oxide and / or butylene oxide. In this case, statistical additions of the alkylene oxides to the alcohols are obtained. Further variations are possible by first adding ethylene oxide to the alcohols, for example, and then changing propylene oxide and / or butylene oxide or the order in which the alkylene oxides are added to the alcohols. Such a stepwise addition of alkylene oxides to alcohols gives alkoxylated alcohols which contain the added alkylene oxides in the form of blocks in copolymerized form. Of the addition products of the alkylene oxides to alcohols, not only the esters of acrylic acid or methacrylic acid come into consideration, but also the esters of the other carboxylic acids mentioned above, e.g. the maleic, fumaric and itaconic esters of the add-on products. Both the mono- and the diesters of the dibasic carboxylic acids come into consideration.

Other suitable monomers of group b) are C₁ to C₂₈ alkyl vinyl ethers, for example methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, sec-butyl vinyl ether, tert-butyl vinyl ether, dodecyl vinyl ether and octadecyl vinyl ether. Styrene can also be used as the monomer of group b).

Of the amides and nitriles of monoethylenically unsaturated C₃- to C₈-carboxylic acids, especially acrylamide, methacrylamide, acrylonitrile and methacrylonitrile come into consideration.

N-Alkyloxymethyl-carboxamides with C₁ to C₁₈ alkyl radicals serve as starting products for the preparation of the monomers a) by reaction with alkoxylated alcohols and as a monomer of group b). Examples of such starting products are: N-methoxymethylacrylamide, N-methoxymethyl methacrylamide, N-ethoxymethylacrylamide, N-ethoxymethyl methacrylamide, N-propoxymethylacrylamide, N-propoxymethyl-methacrylamide, N-iso-propoxymethylacrylamide, N-iso-propoxymethyl methacrylamide, N-iso-propoxymethyl methacrylamide Btuoxymethyl methacrylamide, N-iso-butoxymethylacrylamide, N-iso-butoxymethyl methacrylamide, N-tert-butoxymethylacrylamide, N-tert-butoxymethyl methacrylamide, as well as higher homologues such as N-decyloxymethylacrylamide, N-decyloxymethyl methacrylamide, N-octadoxyl amyl acrylamide, N-octadoxyl amyl acrylate , N-isotridecanoxymethyl methacrylamide but also with C₃- to C₁₈ alkenyl radicals, such as N-propenyloxymethylacrylamide, N-propenyloxymethyl methacrylamide, N-butenyloxymethylacrylamide, N-butenyloxymethyl methacrylamide, N-oleyloxymethylacrylamide and methacrylamide, N-oleyloxymethyl acrylamide

Of the N-alkoxymethyl carboxamides, N-butoxymethylacrylamide, N-butoxymethyl methacrylamide, N-iso-butoxymethylacrylamide and N-iso-butoxymethyl methacrylamide are preferably used. Suitable vinyl esters of saturated carboxylic acids having 1 to 20 carbon atoms are, for example, vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate and vinyl stearate.

Other suitable monomers of group b) are: N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinyl acetamide and monomers containing sulfo groups, such as acrylamidopropanesulfonic acid, allylsulfonic acid, vinyl sulfonic acid and their alkali metal and ammonium salts.

The monomers of group b) can be used either alone or in the form of mixtures in the preparation of the polymers. The polymers can, for example, contain copolymerized acrylic acid and maleic acid or methacrylic acid and maleic acid as a monomer of group b). Other preferred monomer combinations that may be considered are, for example, acrylic acid and vinyl acetate, acrylic acid and vinyl propionate, acrylic acid and ethyl acrylate, acrylic acid and ethyl methacrylate, acrylic acid and methyl acrylate, acrylic acid and methyl methacrylate, and also acrylic acid and N-butoxymethylacrylamide, acrylic acid and N-butoxymethyacrylamide, acrylic acid and n-butoxymethyl acrylamide -Butoxymethylacrylamid, acrylic acid and N-iso-Butoxymethylmethacrylamid as well as acrylic acid and vinyl propionate. The monomers of group b) are preferably 1 to 90% by weight involved in the construction of the copolymers.

The polymers can optionally contain, as group c), polymerized monomers having at least two ethylenically unsaturated double bonds. Such suitable chain extenders are, for example, diacrylates or dimethacrylates of at least dihydric saturated alcohols, for example ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,2-propylene glycol diacrylate, 1,2-propylene glycol dimethacrylate, butanediol-1,4-diacrylate, butanediol-1,4-dimethacrylate , Hexanediol diacrylate, hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methylpentanediol diacrylate and 3-methylpentanediol methacrylate. Acrylic acid and methacrylic acid esters of alcohols with more than two hydroxyl groups are also suitable chain extenders, for example Trimethylolpropane triacrylate or trimethylolpropane trimethacrylate. Another class of chain extenders are the acrylates and the methacrylates of polyethylene glycols or polypropylene glycols with molecular weights which are preferably in the range from 400 to 2000 each. In addition to the diacrylates and dimethacrylates of the homopolymers of ethylene oxide or propylene oxide, block copolymers of ethylene oxide and propylene oxide or static copolymers of ethylene oxide and propylene oxide are also suitable, each of which is esterified in the α, ω position with acrylic acid, methacrylic acid, maleic acid or itaconic acid. Chain extenders of this type are, for example, esters of glycols with maleic acid in a molar ratio of 1: 2, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate and / or tetraethylene glycol dimethacrylate as well as the diacrylates or dimethacrylate of a polyethylene glycol group of polyglycols which are also suitable for use as polyethylene glycols ethylenically unsaturated C₃- to C₆-carboxylic acids, for example vinyl acrylate, vinyl methacrylate or vinyl itaconate. Also suitable are vinyl esters of saturated carboxylic acids containing at least 2 carboxyl groups and the di- and polyvinyl ethers of at least dihydric alcohols, for example divinyl adipate, butanediol divinyl ether and trimethylolpropane trivinyl ether. Further monomers of group c) are, for example, allyl esters of ethylenically unsaturated carboxylic acids, for example allyl acrylate and allyl ether, triallylsucrose and pentaallylsucrose. Methylenebisacrylamide, methylenebismethacrylamide and N-divinylethyleneurea, divinylbenzene, divinyldioxane, tetraallylsilane and tetravinylsilane are also suitable as monomers of group c). If the monomers of group c) are used in the preparation of the polymers, they are present in the polymers in amounts of from 0.01 to 20, preferably 0.05 to 10,% by weight in polymerized form. The monomers of group c) can be used either alone or as a mixture with one another.

The polymers to be used according to the invention can be obtained by polymerizing the monomers a) alone or in a mixture with at least one monomer from group b) and / or from group c). They can be prepared by all customary polymerization processes, for example by bulk, solution, precipitation or suspension polymerization. The copolymers are preferably obtained by solution polymerization. In all polymerization processes, the initiators which break down into free radicals under polymerization conditions are used. The polymerization temperatures are in the range from 20 to 200, preferably 30 to 150 ° C.

The mono- and dicarboxylic acids of the monomers of group b) can be used both as free carboxylic acids, in partially or completely neutralized form in the copolymerization. The degree of neutralization - especially when using dicarboxylic acids as the monomer of group b) - can have a considerable influence on the course of the polymerization, e.g. Turnover, speed, molecular weight and residual monomer content in the copolymer. To neutralize the carboxylic acids, inorganic or organic bases can be used, for example sodium hydroxide solution, potassium hydroxide solution, ammonia, amines, such as dimethylamine, triethanolamine, triethylamine, trimethylamine, tributylamine, ethanolamine or diethanolamine. Mixtures of different bases can also be used for neutralization, e.g. Mixtures of sodium hydroxide solution and triethanolamine. If the copolymerization is carried out in aqueous solutions, the monomers from group b) containing acid groups are preferably used in neutralized form. The pH of the aqueous monomer solution is preferably above 6.5, e.g. in the range of 7 to 11 or even above. The non-neutralized carboxylic acid can also be used in anhydrous media.

All known radical donors can be used as initiators. These initiators can be soluble or insoluble in water. Water-soluble initiators are, for example, inorganic peroxides, such as potassium, sodium and ammonium peroxodisulfate and hydrogen peroxide. Also suitable as initiators are organic peroxides, hydroperoxides, peracids, ketone peroxides, perketals and peresters, for example methyl ethyl ketone hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide, 1,1- (di-tert-butyl peroxy) cyclohexane, di- (tert-butyl) peroxide, tert-butyl oxyperpivalate, ethylhexyl peroctoate, tert-butyl monoperoxy maleate, dicyclohexyl peroxydicarbonate, dibenzoyl peroxide, diacetyl peroxide, didecanoyl peroxide and mixtures of peroxides. Redox systems are also suitable which contain a reducing component in addition to a peroxy compound. Suitable reducing components are, for example, cerium III and iron II salts, sodium sulfite, sodium hydrogen sulfite, Sodium dithionite, ascorbic acid and sodium formaldehyde sulfoxylate. Suitable initiators are preferably selected by using compounds which form free radicals and which have a half-life of less than 3 hours at the polymerization temperature chosen in each case. If the polymerization is initially started at a lower temperature and ends at a higher temperature, it is advisable to work with at least two initiators which disintegrate at different temperatures, namely firstly an initiator which already disintegrates at a lower temperature for the start of the polymerization and then the Complete the main polymerization with an initiator that decomposes at a higher temperature. By adding heavy metal salts, for example copper, cobalt, manganese, iron, nickel and chromium salts to peroxidic catalysts, the decomposition temperature of the peroxidic catalysts can be reduced. Suitable initiators are also azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis (2,4 -dimethylvaleronitrile) and dimethyl-2,2'-azobisisobutyrate. Hydrogen peroxide, potassium, sodium and ammonium peroxodisulfate, tert-butyl perpivalate, 2,2'-azobis (2,4-dimethylvaleronitrile) and di-tert-butyl peroxide are particularly preferably used as initiators in the polymerization. Based on the monomers to be polymerized, usually 0.5 to 10, preferably 1 to 8% by weight of an initiator or a mixture of polymerization initiators is used. As is known, the amount of initiator used has a considerable influence on the molecular weight of the homopolymers and copolymers formed.

As already stated above, the polymerization is preferably carried out in the presence of a diluent. These can be solvents for the monomers and the polymers or only solvents for the monomers. Suitable solvents for solvent polymerization are, for example, aromatic hydrocarbons, such as toluene, xylene, cumene and tetralin, aliphatic hydrocarbons, such as hexane, heptane, octane, cyclohexane and isooctane, and preferably ethers, such as diethyl ether, dibutyl ether, diisobutyl ether, methyl tert-butyl ether , Cyclic ethers, such as tetrahydrofuran and dioxane, mono- or dialkyl ethers of mono- or polyethylene glycols, for example ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethyl glycol dimethyl ether, diethylene glycol dibutyl ether, monoalkyl ethers of mono- or polyethylene glycol acetates, such as methyl glycol acetate, methyl ethylene glycol acetate, butyl glycol acetate, butyl glycol acetate, butyl glycol acetate, butyl glycol acetate, butyl glycol acetate, butyl glycol acetate, methyl acetate glycol, butyl glycol acetate, butyl glycol acetate, methyl acetate glycol, butyl glycol acetate, butyl glycol acetate, methyl acetate glycol, butyl glycol acetate, butyl glycol acetate, butyl glycol acetate, up to 4 carbon atoms on alcohols or alkylphenols. The molecular weights of these addition products can be up to 8000, preferably up to 6000.

If at least 2 different alkylene oxides are used to prepare the addition products, the alkylene oxide units in the reaction products can be randomly distributed or can be in the form of blocks. Such reaction products are components of liquid detergents. Since the polymers are used in detergents, they are advantageously prepared as solvents in the addition products described and the resulting polymer solution can be used directly to prepare the detergent formulation.

Preferred solvents for the polymerization are e.g. Reaction products of monohydric C₁ to C₂₈ aliphatic alcohols or C₁ to C₁₈ alkylphenols with ethylene oxide, propylene oxide and / or butylene oxide, e.g. the addition products of 3 to 11 moles of ethylene oxide to one mole of a C₁₃ / C₁₅ alcohol, addition products of 5 to 15 moles of ethylene oxide to 1 mole of nonylphenol, addition products of 7 to 11 moles of ethylene oxide and 3 to 5 moles of propylene oxide to 1 mole of oleyl alcohol and addition products of 5 to 15 moles of ethylene oxide with 1 mole of stearyl alcohol or tallow fatty alcohol. The addition products of ethylene oxide, propylene oxide and butylene oxide with polyhydric alcohols, e.g. Glycol, diethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, block copolymers of ethylene oxide and propylene oxide, glycerol and oligoglycerols. From this group of compounds, diethylene glycol is particularly preferred.

Other suitable solvents are C₁ to C₆ alcohols, such as methanol, ethanol, isopropanol, n-propanol, butanols, n-hexanol and cyclohexanol, ketones, e.g. Acetone, ethyl methyl ketone and cyclohexanone, esters, e.g. Ethyl acetate, and water and mixtures of water with water-soluble organic solvents. If an inert solvent is used in the polymerization, the concentrations of the monomers therein are 10 to 90, preferably 15 to 70% by weight.

The polymerization of the monomers of groups a) to c) can optionally also be carried out in the presence of regulators. Suitable regulators are, for example, mercapto compounds, such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptoacetic acid, mercaptopropionic acid, butyl mercaptan and dodecyl mercaptan. Also suitable as regulators are allyl compounds, such as allyl alcohol, aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde and isobutyraldehyde, formic acid, ammonium formate, propionic acid, hydroxylammonium sulfate and butenols. Regulators are used in particular when larger amounts of monomers from group c) are used in the polymerization. In such cases, the use of the regulators gives water-soluble polymers or Polymers that are easily dispersible in water. If the polymerization is carried out in the presence of regulators, 0.05 to 20% by weight, based on the monomers to be polymerized, are used.

The polymerization is carried out in conventional devices which are provided with mixing elements. For example, flasks, kettles, autoclaves and cylindrical reactors equipped with stirrers are suitable. The polymerization can also be carried out in vessels, cascades or in interconnected polymerization devices. The polymerization can be carried out batchwise or continuously. Kneaders are also suitable as the polymerization device. If water-soluble monomers are used in the polymerization, the polymerization can also be carried out by the reverse suspension polymerization method or by the water-in-oil emulsion polymerization method. However, the polymerization is preferably carried out as solution polymerization. The production of polymers by the precipitation polymerization method can be of interest for special applications. In addition to the catalytic action of compounds which decompose into radicals under the polymerization conditions, the polymerization can also be initiated by the action of high-energy radiation, e.g. by UV radiation or by exposure to α, β or γ rays. At temperatures above the boiling point of the solvent or solvent mixture used in each case, the polymerization is usually carried out in apparatus designed to be pressure-tight. The polymerization is preferably carried out in the absence of oxygen in an inert gas atmosphere, e.g. under nitrogen, argon, helium or carbon dioxide at normal pressure.

In the case of smaller polymerization batches in which the heat of polymerization can be dissipated sufficiently quickly, it is possible to charge the monomers to be polymerized together with at least one polymerization initiator and to polymerize by heating to the polymerization temperature required in each case. However, it is more advantageous if initially only some of the monomers and the initiator are initially introduced into the polymerization device and the remaining monomers and the initiator are added continuously or batchwise in accordance with the progress of the polymerization. The monomers of components a) and b) can be introduced into the polymerization reactor either in the form of a solution or without a diluent. In a particularly preferred embodiment, the monomers of groups a) and b) to be polymerized are mixed and metered in the form of a solution in an inert solvent continuously or batchwise into a polymerization reactor. However, the monomers can also be introduced into the polymerization reactor in bulk or in the form of a solution. Depending on the selection of the monomers and the polymerization conditions, homopolymers or copolymers are obtained which have K values from 8 to 200, preferably 10 to 100.

If polymerization is carried out in organic solvents, it is expedient to first neutralize the copolymers and only then to convert them into aqueous solutions or dispersions, which are then used as additives in detergents and cleaning agents. If it is necessary to separate off the organic solvents, it can be done, for example, by distillation.

The polymers described above, which contain the essential monomer N (alkyloxy-polyalkoxymethyl) carboxamides, monoethylenically unsaturated C₃- to C₈-carboxylic acids with amide groups of structure I, are used as additives to detergents and cleaners in order to reduce the primary and secondary washing power of the Increase detergent and cleaning agent formulations. In addition to the polymers described above, which are used in an amount of 0.1 to 20% by weight, the detergents and cleaning agents contain at least one anionic surfactant, a nonionic surfactant or mixtures thereof as essential components. The detergents and cleaning agents can be in the form of a powder or a liquid formulation. The copolymers to be used according to the invention are particularly suitable for the preparation of liquid detergent formulations.

Suitable anionic surfactants are, for example, sodium alkylbenzenesulfonates, fatty alcohol sulfates and fatty alcohol polyglycol ether sulfates.

Individual compounds of this type are, for example, C₈ to C₁₂ alkyl benzene sulfonates, C₁₂ to C₁₆ alkane sulfonates, C₁₂ to C₁₆ alkyl sulfates, C₁₂ to C₁₆ alkyl sulfosuccinates and sulfated ethoxylated C₁₂ to C₁₆ alkanols. Also suitable as anionic surfactants are sulfated fatty acid alkanolamides, fatty acid monoglycerides or reaction products of 1 to 4 moles of ethylene oxide with primary or secondary fatty alcohols or alkylphenols. Other suitable anionic surfactants are fatty acid esters or fatty acid amides of hydroxy or amino carboxylic acids or sulfonic acids, such as, for example, the fatty acid sarcosides, glycolates, lactates, taurides or isethionates. The anionic surfactants can be organic in the form of the sodium, potassium and ammonium salts and also as soluble salts Bases such as mono-, di- or triethanolamine or other substituted amines are present. The anionic surfactants also include the usual soaps, ie the alkali salts of the natural fatty acids.

As nonionic surfactants (Nonionics) e.g. Addition products of 3 to 40, preferably 4 to 20, moles of ethylene oxide and 1 mole of fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkanesulfonamide can be used. The addition products of 5 to 16 moles of ethylene oxide with coconut oil or tallow fatty alcohols, with oleyl alcohol or with synthetic alcohols with 8 to 18, preferably 12 to 18 carbon atoms, and with mono- or dialkylphenols with 6 to 14 carbon atoms in are particularly important the alkyl residues. In addition to these water-soluble nonionics, non-fully or not fully water-soluble polyglycol ethers with 1 to 4 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble nonionic or anionic surfactants. Furthermore, the non-ionic surfactants which can be used are the water-soluble adducts of ethylene oxide with 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups with polypropylene glycol ether, alkylene diaminopolypropylene glycol and alkyl polypropylene glycols with 1 to 10 C atoms in the alkyl chain, in which the polypropylene glycol ether chain acts as a hydrophobic residue.

Nonionic surfactants of the amine oxide or sulfoxide type can also be used.

The foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants. A reduction can also be achieved by adding non-surfactant-like organic substances.

The liquid, aqueous detergents contain 10 to 50% by weight of surfactants. You can contain an anionic or nonionic surfactant in the amount specified. However, it is also possible to use mixtures of anionic and nonionic surfactants. In such a case, the content of anionic surfactants in the liquid detergent is chosen from 10 to 30% by weight and the content of nonionic surfactants in the liquid detergent from 5 to 20% by weight, based on the total detergent formulation.

Liquid detergents contain, as an essential component, the copolymers to be used according to the invention in amounts of 0.1 to 20, preferably 1 to 10 wt .-% and optionally water in amounts of 10 to 60, preferably 20 to 50 wt .-%.

Liquid detergents may also contain other substances for modification. These include, for example, alcohols, such as ethanol, n-propanol and isopropanol. If used, these substances are used in amounts of 3 to 8% by weight, based on the total detergent formulation. The liquid detergents may also contain hydrotropes. This includes compounds such as 1,2-propanediol, cumene sulfonate and toluene sulfonate. If such compounds are used to modify the liquid detergent, their amount, based on the total weight of the liquid detergent, is 2 to 5% by weight. In many cases, addition of complexing agents has also proven to be advantageous for modification. Complexing agents are, for example, ethylenediaminetetraacetic acid, nitrilotriacetate and isoserinediacetic acid, and phosphonates, such as aminotrismethylenephosphonic acid, hydroxyethane diphosphonic acid, ethylenediaminetetramethylenephosphonic acid and their salts. The complexing agents are used in amounts of 0 to 10% by weight, based on the liquid detergent. The liquid detergents can also contain citrates, di- or triethanolamine, opacifiers, optical brighteners, enzymes, perfume oils and dyes. If they are used to modify the liquid detergents, these substances are present together in amounts of up to 5% by weight. The liquid detergents are preferably phosphate-free. However, they can also contain phosphates, e.g. Pentasodium triphosphate and / or tetrapotassium pyrophosphate. If phosphates are used, the proportion of the phosphates in the total formulation of the liquid detergent is 10 to 25% by weight, calculated as pentasodium triphosphate.

The liquid detergents described above have the advantage over the powder detergents that they are easy to dose and have a very good fat and oil dissolving power at greasy soiled laundry at lower washing temperatures. Liquid detergents contain high levels of detergent substances, which remove dirt from the textile fabric at washing temperatures of 40 to 60 ° C. The dispersing properties of polymers have hitherto not been able to be used in aqueous liquid detergents because, as a result of high electrolyte concentrations in the detergents, it was not possible to obtain stable solutions with the polymers. With the homopolymers and copolymers to be used according to the invention, it is now possible to produce stable aqueous solutions of liquid detergents and the washing properties of liquid detergents to improve significantly. The effectiveness of the homopolymers and copolymers to be used according to the invention in liquid detergents is demonstrated in the examples with the aid of the primary and secondary washing action of these detergents. The primary washing effect is the actual removal of dirt from the textile material. The difference in the degree of whiteness between the unwashed and the washed textile material after washing is determined as the degree for dirt removal. Cotton, cotton / polyester and polyester fabrics with standard soiling are used as the textile test material. After each wash, the degree of whiteness of the fabric in% remission is determined in an Elrephophotometer from Zeiss.

Secondary washing is understood to mean the effects which arise from the re-accumulation of the dirt detached from the fabric on the fabric in the wash liquor. The secondary washing effect can only take place after several washes, e.g. 3, 5, 10 or even 20 washes become visible, which becomes increasingly gray (noticeable), i.e. Accumulation of dirt from the wash liquor on the fabric. To determine the tendency to graying, standard soiling fabric is washed several times together with white test fabric and the soiled fabric is renewed after each wash. The dirt detached from the dirt fabric, which is drawn onto the white test fabric during washing, causes a drop in the degree of whiteness that is measured. The homopolymers and copolymers to be used according to the invention in detergents or their water-soluble salts can also be used for the formulation of powder detergents.

The composition of powder detergent formulations can vary widely. The same applies to the composition of detergent formulations. Detergent and cleaning agent formulations usually contain surfactants and optionally builders. This information applies to both liquid and powder detergent formulations. Examples of the composition of detergent formulations which are common in Europe, the USA and Japan can be found, for example, in Chemical and Engn. News, Vol. 67, 35 (1989) in tabular form and in Ullmann's Encyclopedia of Industrial Chemistry, Verlag Chemie, Weinheim 1983, 4th edition, pages 63-160.

The percentages in the examples are% by weight. The K values were determined according to H. Fikentscher, Zellulosechemie, Vol. 13, 58-64 and 71-74 (1932).

The K values of the water-soluble polymers were measured in aqueous solution at 25 ° C., a pH of 7.5 and a polymer concentration of 1% by weight.

The K values of the water-dispersible polymers were measured as 1% solutions in the unneutralized form in tetrahydrofuran (THF) at 25 ° C. The K values determined in this way are in all cases between 8 and 200, preferably between 10 and 100.

Examples Preparation of the polymers

• Acrylamidderivat 1:
  CH₂=CH-CO-NH-CH₂-(O-CH₂-CH₂)₇-O-C_13/15-Alkyl
• Acrylamidderivat 2:
  CH₂=CH-CO-NH-CH₂-(O-CH₂-CH₂)₃-O-C_13/15-Alkyl
• Acrylamidderivat 3:
  CH₂=CH-CO-NH-CH₂-(O-CH₂-CH₂)₁₁-O-C_13/15-Alkyl
• Acrylamidderivat 4:
  CH₂=CH-CO-NH-CH₂-(O-CH₂-CH₂)₂₅-O-C_16/18-Alkyl

The following compounds were used as monomers of group a):

• Acrylamide derivative 1:
  CH₂ = CH-CO-NH-CH₂- (O-CH₂-CH₂) ₇-OC _13/15 alkyl
• Acrylamide derivative 2:
  CH₂ = CH-CO-NH-CH₂- (O-CH₂-CH₂) ₃-OC _13/15 alkyl
• Acrylamide derivative 3:
  CH₂ = CH-CO-NH-CH₂- (O-CH₂-CH₂) ₁₁-OC _13/15 alkyl
• Acrylamide derivative 4:
  CH₂ = CH-CO-NH-CH₂- (O-CH₂-CH₂) ₂₅-OC _16/18 alkyl

Polymer 1

125 g of tetrahydrofuran are placed under a nitrogen atmosphere in a 500 ml round-bottomed flask equipped with a stirrer, reflux condenser, nitrogen inlet and feed devices and heated to boiling under reflux. A solution of 37.5 g of acrylic acid in 35 g of tetrahydrofuran, a solution of 37.5 g of acrylamide derivative 1 in 35 g of tetrahydrofuran and a solution of 1 within 2 hours are then simultaneously added to this template from 3 feed vessels within 1 hour. 5 g of 2,2'-azobis (2,4-dimethylvaleronitrile) in 20 g of tetrahydrofuran. After the initiator addition has ended, the reaction mixture is heated to boiling under reflux for a further 2 hours, cooled to 20 ° C. and neutralized by adding a mixture of 124 g of triethanolamine and 50 g of tetrahydrofuran. The wax-like flask contents are mixed with 300 g of water and the solution obtained is freed from tetrahydrofuran by distillation. A slightly yellowish, clear, aqueous, viscous solution with a solids content of 27% and a K value of 32 (measured in aqueous solution) is obtained.

Polymer 2

200 g of diethylene glycol dimethyl ether are placed in the apparatus described in Example 1 and heated to 140 ° C. under a nitrogen atmosphere. At this temperature, a mixture of 70 g of acrylic acid and 30 g of acrylamide derivative 1 is then added dropwise over the course of 2 hours, and a solution of 4 g of di-tert-butyl peroxide in 50 g of diethylene glycol dimethyl ether is simultaneously added within 2.5 hours. The reaction mixture is then cooled to 20 ° C. and neutralized by adding 78 g of a 50% strength aqueous sodium hydroxide solution. The reaction mixture is then concentrated in a water jet vacuum and the copolymer is precipitated by adding 1 l of cyclohexane. The polymer is filtered off and dried in vacuo at 100 ° C. A 35% aqueous solution with a K value of 18 (measured in aqueous solution) is prepared by adding water.

Polymer 3

500 g of isopropanol are placed in a 2 l polymerization apparatus which is provided with a stirrer, nitrogen inlet and nitrogen outlet and feed vessels and heated to reflux. At the start of boiling, 150 g of acrylic acid and 150 g of acrylamide derivative 1 in 125 g of isopropanol are metered in from 3 feed vessels over 3 hours, and 6 g of 2,2'-azobis (2,4-dimethylvaleronitrile) in 75 g of isopropanol are added over 4 hours. After the initiator addition has ended, the reaction mixture is heated to reflux for a further hour, cooled and through Addition of 83 g of a 50% aqueous sodium hydroxide solution neutralized. Isopropanol is then distilled off and replaced with water to give a clear solution with a solids content of 46%. The K value of the copolymer is 20.5 (measured in aqueous solution).

Polymer 4

An aqueous solution of 135 g of acrylic acid in 150 g of water is neutralized with 227 g of 50% strength aqueous potassium hydroxide solution and a solution of 67 g of the acrylamide derivative 1 in 200 g of isopropanol is added. The resulting clear solution is continuously added over a period of 1 hour and simultaneously a solution of 2 g of mercaptopropionic acid in 20 g of water and 20 g of isopropanol in the polymerizer described in the preparation of polymer 3 and polymerized at a bath temperature of 90.degree 6.7 9 30% aqueous hydrogen peroxide dissolved in 30 g of water and 30 g of isopropanol are added as the polymerization initiator within 2 hours. After the hydrogen peroxide has been added, the reaction mixture is refluxed for a further 2 hours and the excess isopropanol is distilled off. A cloudy solution with a solids content of 38% is obtained. The K value of the polymer is 26 (measured in aqueous solution). The 38% aqueous solution becomes clear and colorless when diluted to a solids content of about 15% by weight.

Polymers 5 to 12

100 g of tetrahydrofuran are placed in the apparatus described for the preparation of polymer 3 and heated to boiling under reflux. After the start of boiling, a solution of 140 g of acrylamide derivative 1 and 60 g of acrylic acid in 100 g of tetrahydrofuran is metered into the initial charge within 2 hours and a solution of 8 g of 75% tert-butyl perpivalate in 50 g of tetrahydrofuran within 2.5 hours. After the initiator addition has ended, the reaction mixture is heated to boiling for a further hour, cooled and then neutralized by adding 67 g of 50% strength aqueous sodium hydroxide solution and 400 g of water. The tetrahydrofuran is then distilled off and the solids content of the aqueous solution is then adjusted to 15% by adding water. The 15% aqueous solution has a viscosity of 1062 mPas at a temperature of 20 ° C. The K value is 25.6 (measured in aqueous solution).

Polymers 6 to 12 are prepared in accordance with the process specification given above using the starting materials shown in Table 1.

Polymer 13

In the apparatus described in the preparation of polymer 1, 60 g of tetrahydrofuran are placed under a nitrogen atmosphere and heated to reflux. At the start of refluxing, a solution of 30 g of the acrylamide derivative 3, 70 g of hydroxyethyl acrylate in 50 g of tetrahydrofuran and a solution of 2 g of 75% tert-butyl perpivalate in 50 g of tetrahydrofuran are added dropwise within 2 hours and the reaction mixture is heated to reflux for a further 2 hours after the peroxide addition has ended. The reaction mixture is then evaporated to dryness in a vacuum from the water jet pump. 106 g of a colorless resin with a K value of 14 (determined on aqueous polymer solutions) remain as the residue.

Polymer 14

200 g of tetrahydrofuran are placed in the apparatus described for the preparation of polymer 3 and heated to boiling under reflux. A solution of 70 g of the acrylamide derivative 1, 25 g of vinyl acetate and 5 g of acrylic acid in 100 g of tetrahydrofuran are added dropwise to the boiling solution within 2 hours and a solution of 4 g of 75% tert-butyl perpivalate in 50 g of tetrahydrofuran within from 3 hours to. After the peroxide has been added, the reaction mixture is heated to boiling for a further 3 hours and cooled. Then 5.5 g of 50% aqueous sodium hydroxide solution and 350 g of water are added and the tetrahydrofuran is distilled off. A homogeneous solution with a solids content of 30% and a viscosity of 1229 mPas is obtained. The K value of the polymer in the unneutralized form is 12.1 (determined on solutions of the polymer in THF).

Polymer 15

The procedure for the preparation of polymer 14 is repeated, except that acrylamide derivative 3 is used instead of acrylamide derivative 1. A 30% solution with a viscosity of 9788 mPas is then obtained. The K value of the polymer in the unneutralized form is 16.8 (determined on solutions of the polymer in THF).

Polymer 16

The procedure is as described for the preparation of polymer 14, except that 50 g of acrylamide derivative 3, 40 g of vinyl acetate and 10 g of acrylic acid in 100 g of tetrahydrofuran are polymerized with 4 g of 75% tert-butyl perpivalate in 50 g of tetrahydrofuran. After the polymerization, 11 g of 50% strength are added aqueous sodium hydroxide solution in 200 g of water. After distillation and dilution of the mixture with water, a 30% strongly cloudy polymer solution with a viscosity of 12833 mPas is obtained. The K value of the polymer in the unneutralized form is 20.3 (determined on solutions of the polymer in THF).

Polymer 17

30 g of tetrahydrofuran are placed in the apparatus used for the preparation of polymer 1 and heated to boiling. Then 50 g of acrylamide derivative 2, which is dissolved in 50 g of tetrahydrofuran, are added within 2 hours and a solution of 1 g of 75% tert-butyl perpivalate, which is dissolved in 50 g of tetrahydrofuran, is added within 3 hours. After the initiator addition has ended, the reaction mixture is heated to boiling under reflux for a further 2 hours and then evaporated in vacuo at 10 mbar and the residue is dried to constant weight. This gives 51 g of a colorless resin with a K value of 18.5 (determined in 1% solution in tetrahydrofuran). The polymer only partially dissolves in water, but well in tetrahydrofuran, isopropanol and ethyl acetate.

Polymer 18

As described for the preparation of polymer 14, 50 g of acrylamide derivative 3, 40 g of N- (isobutoxymethyl) acrylamide and 10 g of acrylic acid in 100 g of tetrahydrofuran are polymerized with 4 g of 75% tert-butyl perpivalate in 50 g of tetrahydrofuran and then polymerized with 11 neutralized g 50% sodium hydroxide solution and diluted by adding 200 g water. After the tetrahydrofuran has been distilled off, a slightly cloudy solution with a solids content of 38% and a viscosity of 3420 mPas is obtained. The K value is 19.1 (determined on solutions of the polymer in THF).

Polymer 19

As described for the preparation of polymer 14, 50 g of acrylamide derivative 3, 40 g of N- (isobutoxymethyl) acrylamide and 10 g of acrylic acid in 100 g of tetrahydrofuran are polymerized with 4 g of 75% tert-butyl perpivalate in 50 g of tetrahydrofuran and added by adding 11 g of 50% sodium hydroxide solution neutralized. 200 g of water are then added and, after distillation, a very cloudy solution in the warm state and only a slightly cloudy solution in the cold state with a solids content of 40% and a viscosity of 2432 mPas. The K value is 18.2 (determined on aqueous polymer solutions).

Polymer 20

As described in the preparation of polymer 14, 50 g of acrylamide derivative 1 and 50 g of N- (isobutoxymethyl) acrylamide in 100 g of tetrahydrofuran are polymerized with 4 g of 75% tert-butyl perpivalate in 50 g of tetrahydrofuran. When the polymerization is complete, 200 g of water are added, the tetrahydrofuran is distilled off and 150 g of isopropanol are added. A cloudy suspension with a solids content of 26.7% and a viscosity of 18 mPas is obtained. The K value is 15.1 (measured on 1% polymer solution in THF).

Polymer 21

130 g of a reaction product of 7 mol of ethylene oxide and 1 mol of a C _13/15 oxo alcohol are placed under nitrogen and heated to 70 ° C. in a 2 l reaction vessel with a good mechanical stirrer, nitrogen connection and metering vessels. 60 g of acrylic acid, a mixture of 15 g of acrylamide derivative 1 and 60 g of a reaction product of 7 mol of ethylene oxide and 1 mol of a C _{13 /} C₁₅-oxo alcohol and a solution of 2 g of 75% strength tert.- Butyl perpivalate in 20 g polypropylene glycol (molecular weight 600). Then another 0.5 g of 75% tert-butyl perpivalate is added in one portion and the mixture is stirred at 70 ° C. for a further hour. After cooling to 20 ° C., the mixture is neutralized by adding 124 g of triethanolamine and 350 g of water. The solution obtained contains 26.3% neutralized copolymer, the K value of which is 60.2 (measured 1% in water).

Polymer 22-27

According to the instructions given for the preparation of polymer 21, the polymers 22-27 were produced using the starting materials listed in Table 2.

Polymer 28

60 g of tetrahydrofuran are placed in a mechanically stirred 250 ml round-bottomed flask with a reflux condenser and metering devices and heated to boiling. A solution of 20 g of acrylamide derivative 1 and 60 g of acrylic acid in 50 g of tetrahydrofuran and 20 g of N-vinylpyrrolidone, dissolved in 20 g of tetrahydrofuran, are metered into this template within 30 minutes. At the same time, an initiator solution consisting of 2 g of 75% tert-butyl perpivalate and 30 g of tetrahydrofuran is added dropwise within 40 minutes. The mixture is refluxed for a further hour, allowed to cool and neutralized with 140 g of 25% strength aqueous sodium hydroxide solution. The tetrahydrofuran is distilled off and the resulting solution of the copolymer is adjusted to 30% by weight solids content by adding water. The K value is 48.3 (measured in a 1% strength aqueous solution).

Polymer 29

125 g of tetrahydrofuran are placed in a 500 ml 4-necked flask with stirrer, reflux condenser and 4 metering devices and heated to boiling. 53 g of acrylic acid and simultaneously 23 g of acrylamide derivative 4 dissolved in 35 g of tetrahydrofuran are metered in over the course of 2 hours, and a solution of 1.5 g of 2,2'-azobis (2,4-dimethylvaleronitrile) in 20 g of tetrahydrofuran is added within 2.5 hours . The mixture is refluxed for a further hour and cooled. 109 g of triethanolamine are added to the solution of the copolymer within 30 minutes and the mixture is diluted with 100 g of water. After the tetrahydrofuran has been distilled off, a solids content of 40% is established. The K value (measured in a 1% aqueous solution) is 27.8.

Application testing of the polymers as detergent additives Washing conditions: Primary washing effect and graying

tissue White fabric: Cotton / polyester fabric Polyester fabric Dirt tissue: WFK 20 D (laundry research Krefeld) (renewed after every wash)
Whiteness measurement in Elrepho in% remission
Whiteness of unwashed fabrics: Cotton polyester 80.4 polyester 78.0 WFK 20 D 37.8

The whiteness differences on the individual fabrics are given before and after washing.

The greater the difference in whiteness on the WFK 20 D dirt fabric, the higher the primary washing effect.

The smaller the differences on the white fabrics, the better the graying inhibition.

A polymer-free detergent formulation was tested for comparison.

Liquid detergent: Formulation A

10% sodium dodecylbenzenesulfonate, 50% in water
3% of the reaction product from 1 mol of C _13/15 oxo alcohol and 7 mol of ethylene oxide
2% polypropylene glycol MW 600
77% water
8% polymer according to the invention

Formulation B

13.5% sodium dodecylbenzenesulfonate, 50% in water
17% of the reaction product from 1 mol of C _{13 /} C₁₅ oxo alcohol and 7 mol of ethylene oxide
14% coconut fatty acid
0.7% citric acid
7% triethanolamine
1% KOH
7% isopropanol
3% polypropylene glycol MW 600
8% polymer according to the invention
28.8% water

Testing of polymers in formulation A Primary washing effect and graying

The whiteness differences in% remission between washed and unwashed fabric are given in each case Example No. when using polymer no. Primary washing action WFK 20 D Graying polyester Cotton / PES 1 1 21.2 7.2 9.8 2nd 2nd 20.3 4.0 8.2 3rd 3rd 24.3 5.2 10.2 4th 4th 16.8 3.5 13.7 5 5 22.1 3.1 8.5 6 6 21.4 2.8 9.5 7 7 22.4 2.9 11.1 8th 8th 22.9 5.2 8.4 9 9 24.2 6.1 10.9 10th 10th 22.7 4.1 12.2 11 11 22.3 4.5 14.2 12th 12th 26.3 4.3 12.7 13 13 20.8 4.8 13.7 14 14 24.4 2.3 11.6 15 15 24.7 3.9 11.7 16 16 26.5 7.7 13.5 17th 18th 23.9 8.3 13.7 18th 20th 17.0 7.5 14.1 Comparative example 1 without addition 11.4 7.8 14.3

Testing of polymers in formulation B Primary washing effect and graying

The whiteness differences in% remission between washed and unwashed fabric are given in each case Example No. when using polymer no. Primary washing action WFK 20 D Graying polyester Cotton / PES 19th 1 18.1 6.2 11.7 20th 2nd 23.7 11.7 17.5 21 3rd 23.2 10.6 14.6 22 4th 19.3 7.7 16.4 23 5 20.6 6.9 11.3 24th 6 20.6 6.7 12.2 25th 7 23.3 6.0 13.5 26 8th 21.5 6.2 10.9 27 9 23.8 6.6 11.6 28 10th 25.9 6.7 11.9 29 11 22.7 7.5 13.6 30th 12th 27.4 6.9 12.7 31 13 21.9 8.4 15.5 32 14 23.0 7.5 15.2 33 15 23.2 8.0 12.2 34 16 24.4 9.0 10.9 35 18th 18.3 8.3 14.7 36 20th 21.3 9.0 15.2 37 22 20.1 6.3 10.7 38 23 19.9 7.4 13.1 39 24th 18.9 7.3 12.5 40 25th 21.9 6.7 12.7 41 26 20.3 8.0 10.3 42 27 19.5 8.0 14.0 43 28 19.5 6.6 13.4 44 29 20.3 5.9 14.1 Comparative Example No. when using polymer no. Primary washing action WFK 20 D Graying polyester Cotton / PES 2nd without addition 15.8 9.1 15.8 3rd Add 8% of a reaction product of 7 moles of ethylene oxide and 1 mole of C _13/15 oxo alcohol 16.5 8.7 14.7

As can be seen from the examples, the polymers to be used according to the invention significantly improve the primary washing action of the detergent formulations. At the same time, an improvement in the graying inhibition is observed. The polymers to be used according to the invention can be incorporated into the detergent formulations A and B without problems and result in stable, homogeneous solutions.

Claims (7)

1. The use of a polymer containing as essential monomer at least 5% by weight of N-(alkyloxypolyalkoxymethyl)carboxamides of monoethylenically unsaturated C₃-C₈-carboxylic acids having amide groups of the structure
   
   
   
           -CO-NH-CH₂-R,   (I)
   
   
   
   where

   

   
   
           R¹-O-(CH₂-CH₂-CH₂-CH₂-O)_m-
   
   
   

   R¹ =   C₁-C₂₈-alkyl, C₃-C₂₈-alkenyl, phenyl or C₁-C₁₈-alkylphenyl,

   R² and R³   are each H, CH₃ or C₂H₅,

   n   is from 1 to 200 and

   m   is from 1 to 100

   as copolymerized units, as an addition to low-phosphate and phosphate-free detergent and cleaner compositions, in amounts of from 0.1 to 20% by weight, based on the detergent and cleaner compositions.
2. A use as claimed in claim 1, wherefor the polymer contains

   (a) from 10 to 99% by weight of N-(alkyloxypolyalkoxymethyl)carboxamides of monoethylenically unsaturated C₃-C₈-carboxylic acids having amide groups of the structure I and

   (b) from 90 to 1% by weight of other monoethylenically unsaturated monomers

   as copolymerized units.
3. A use as claimed in claim 1 or 2, wherefor the polymer contains as comonomers

   (b) monoethylenically unsaturated C₃-C₈-carboxylic acids, esters thereof with C₁-C₂₈-alcohols, esters of monoethylenically unsaturated C₃-C₈-carboxylic acids with reaction products of C₁-C₂₈-alcohols and ethylene oxide, propylene oxide and/or butylene oxide in a molar ratio of from 1:1 to 1:100, amides, N-C₁-C₁₈-alkyloxymethylamides and nitriles of monoethylenically unsaturated C₃-C₈-carboxylic acids, vinyl esters of saturated carboxylic acids of from 1 to 20 carbon atoms, C₁-C₂₈-alkyl vinyl ethers, styrene or mixtures thereof as copolymerized units.
4. A use as claimed in claim 1 or 2, wherefor the polymer additionally contains as monomer (c) from 0.01 to 20% by weight of compounds having at least two ethylenically unsaturated nonconjugated double bonds, as copolymerized units.
5. A use as claimed in claim 1, wherefor homopolymers of N-(alkyloxypolyalkoxymethyl)carboxamides of monoethylenically unsaturated C₃-C₈-carboxylic acids having amide groups of the structure I or copolymers of these monomers with one another are used.
6. A use as claimed in any one of claims 1 to 5, wherefor polymer solutions are used which are obtainable by polymerizing the monomers in addition products of alkylene oxides of from 2 to 4 carbon atoms with C₁-C₂₈-alcohols or C₁-C₁₈-alkylphenols.
7. Detergent and cleaner compositions containing as essential constituents

   (1) at least one anionic surfactant, a nonionic surfactant or a mixture thereof and

   (2) from 0.1 to 20% by weight of a polymer containing as essential monomer at least 5% by weight of N-(alkyloxypolyalkoxymethyl)carboxamides of monoethylenically unsaturated C₃-C₈-carboxylic acids having amide groups of the structure
   
   
   
           -CO-NH-CH₂-R,   (I)
   
   
   
   where

   

   
   
           R¹-O-(CH₂-CH₂-CH₂-CH₂-O)_m-
   
   
   

   R¹ =   C₁-C₂₈-alkyl, C₃-C₂₈-alkenyl, phenyl or C₁-C₁₈-alkylphenyl,

   R²   and R³ are each H, CH₃ or C₂H₅,

   n   is from 1 to 200 and

   m   is from 1 to 100

   as copolymerized units.