DE2814329A1 - Washing agents contg. N-vinyl-oxazolidone polymers - inhibiting transfer of dyes from coloured textiles onto white textiles - Google Patents

Abstract

The agents contain anionic and/or non-ionic tensides, builders and the usual additives, together with 0.1-10(0.2-5) esp. 0.5-4%, w.r.t. the total wt. of the agent, of a water-soluble or -dispersible N-vinyloxazolidone homo- or copolymer. Pref. this homo- or copolymer has a mol.wt. of 10-10000, esp. 20-5000, and has a specific viscosity as a 1% aq. soln. at 20 degrees C of 0.01-5, esp. 0.1-1. The presence of the polymer inhibits the transfer of dye from coloured textiles onto white or light-coloured textiles when they are being washed together.

Description

Laundry detergent with a content of discoloration-inhibiting additives

The present invention is a detergent and cleaning agent, in addition to surfactants, framework salts, Bleach and other accompanying substances contain a compound that causes dye transfer from colored textiles to white or light-colored textiles during a joint Counteracting washing. From DE-OS 22 32 353 such means are already known, wherein the dye transfer inhibiting agent is polyvinylpyrrolidone consists. However, these means have disadvantages that are once that the effect on a number of dyeings or textiles is very low and on the other hand, that the use of the inhibitor is limited to such detergents that do not contain anionic surfactants. However, anionic surfactants count because of them versatile application-related advantages to the most important or most common Detergent ingredients.

The disadvantages indicated are eliminated by the present invention avoided. The invention relates to a washing and cleaning agent containing anionic and / or nonionic surfactants, builders and other common ones Detergent additives, characterized by one based on the total weight of the agent based content of 0.1 to 5 wt .-% of a water-soluble or dispersible Homo- or copolymers of N-vinyl oxazolidone.

The degree of polymerization of the polymers can be within wide limits are and is, for example, 10 to 10,000, but preferably 20 to 5000. Since the determination of the molecular weight and thus the degree of polymerisation is multiple is difficult, the specific viscosity is usually considered Measure for indicated the degree of polymerization. According to the invention, polymers and are well suited Copolymers with a 1% by weight aqueous solution at 20 ° C determined specific viscosity from 0.01 to 5 and in particular from 0.1 to 1. The preparation the polymers, for which no protection is sought, can in a known manner by radical initiated take place in aqueous solution or in an organic solvent can be worked.

Except for the homopolymeric poly-N-vinyloxazolidone, which has proven to be very has proven effective, linear and crosslinked copolymers come into question. For education compounds having an olefinic double bond which are suitable for linear copolymers are: hydrocarbons such as ethylene, propylene and styrene; Vinyl or allyl compounds, such as vinyl methyl ether, vinyl ethyl ether, allyl methyl ether, allyl ethyl ether, vinyl acetate and propionate (which may be wholly or partially saponified after copolymerization can be), allyl acetate, allyl alcohol, N-vinylpyrrolidone and N-vinyloxazolidone as well as derivatives of acrylic or ethacrylic acid, e.g. their methyl or ethyl esters, Amides and nitriles; Derivatives of olefinic dicarionic acids, such as the methyl and ethyl esters, Diamides and nitriles of maleic acid and fumaric acid. Particularly suitable copolymerizable ones Compounds are N-vinylpyrrolidone, N-vinyloxazolidone, vinyl acetate and (MetI) -acrylamide. Several of the aforementioned copolymerizable compounds can also be used in one Copolymers are used Particularly suitable terpolymers are e.g. the des N-Vinyloxazolidons with N-Vinylimidazole and N-VinylpyrroliLon. in the copolymers should the proportion of N-Vinyloxazolläons at least 25 I6l%, preferably at least 30 ZQ] --q and in particular at least 50 mol%. In such copolymers in their production so '..? ohl of N-Vinylox @ zolidon as well as of N-vinylimidazole It is assumed that the molar proportion of N-vinyloxazolidone should be greater than that of N-vinylimidazole.

Examples of particularly suitable copolymers are accordingly those from N-vinyloxazolidone and N-vinylpyrrolidone in a molar ratio of 1: 2 to 100: 1, des N-vinyl oxazolidone and N-vinyl imidazole in a molar ratio of 1: 0.99 to 100: 1 and the ternary copolymer of N-vinyloxazolidone, N-vinylpyrrolidone and N-vinylimidazole in a molar ratio of 1: 1: 0.99 to 100: 1: 1 or 100: 100: 1 or 100: 1: 99.

Finally, the copolymers can also be used with compounds with 2 or more copolymerizable double bonds. Because such copolymerizable compounds to three-dimensionally crosslinked polymers with high Viscosity and decreasing water solubility lead, their proportion should be less than 10 mol%, preferably less than 5 mol%, based on the total amount of polymerizable Connections amount. Examples of suitable compounds are methylene-bis-acrylamide, Divinylbenzene, triallyl cyanurate and tetraallyloxyethane.

The content of the agents according to the invention in the homo- or

Copolymers of N-vinyl oxazolidone is 0.1 to 10, preferably 0.2 to 5 and in particular 0.5 to 4% by weight.

In addition to the polymers mentioned, the agents according to the invention contain also anionic and / or nonionic surfactants and detergency enhancing agents or structural substances that bind alkaline ions. Suitable further ingredients are Washing alkalis, neutral salts, bleaching agents, anti-graying agents, optical ones Brighteners, enzymes and stabilizers as well as others, usually in detergents Auxiliaries and additives used are suitable anionic washing active substances those of the sulfonate or sulfate type, for example alkylbenzene sulfonates, in particular n-Vodecylbenzenesulfonate, also Olefinsul fonate, h'-sulfofatty acid ester, primary and secondary alkyl sulfates as well as the sulfates of ethoxylated or propoxylated higher molecular weight alcohols.

Other compounds of this class that may be used in detergents are the higher molecular weight sulfated partial ethers and partial esters of polyhydric alcohols, such as the alkali salts of the monoalkyl ethers or the mono-fatty acid esters of glycerol monosulfuric acid or

of 1,2-dioxypropanesulfonic acid. Furthermore, sulfates come from ethoxylated or propoxylated fatty acid amides and alkylphenols and fatty acid taurides and Fettäureisät'nionate in question. Other suitable anionic detergent raw materials are Alkaline soaps of fatty acids of natural or synthetic origin, e.g. sodium soaps of coconut, palm kernel or tallow fatty acids.

The anionic detergent raw materials can be in the form of sodium, potassium and ammonium salts and as salts of organic bases, such as mono-, di- or triethanolamine, are present. If the anionic and zwitterionic compounds mentioned have a have an aliphatic hydrocarbon radical, this should preferably be straight-chain and have 8 to 22 carbon atoms. In compounds with an araliphatic The preferably unbranched alkyl chains contain hydrocarbon radicals on average 6 to 15 carbon atoms.

As nonionic surface-active washing-active substances come in primarily polyglylcol ether derivatives of alcohols, fatty acids and alkylphenols in question, the 3 to 30 glycol ether groups and 8 to 20 carbon atoms in Kohlern "hydrogen radical contain. Polyglykolther derivatives in which the number of Ethylene glycol ether groups is 5 to 15 and their hydrocarbon radicals of straight-chain, primary alcohols with 12 to 18 carbon atoms or of alkylphenols derive with a straight-chain alkyl chain having 6 to 14 carbon atoms.

Other suitable non-ionic washing raw materials are the water-soluble, 20 to 250 ethylene glycol ether groups and 10 to tC3 propylene glycol ether groups containing polyethylene oxide adducts with polypropylene glycol> ethylenediamine polypropylene glycol and alkyl polypropylene glycol having 1 to 10 carbon atoms in the alkyl chain. the Verbirdungen mentioned usually contain 1 to per propylene glycol unit 5 ethylene glycol units.

Also non-ionic compounds of the amine oxide and sulfoxide type, which can optionally also be ethoxylated can be used.

Zwitterionic washing active substances can also be used such as alkyl betaines and alkyl sulfobetaines, e.g.

3- (N, N-dimethyl-N-alkylammonium) propane-1-sulfonate and 3- (N , N-dimethyl-N-alkylammonium) -2-hydroxypropane-1-sulfonate.

Phosphates, such as pentasodium triphosphate, can be used as builder substances and its mixtures with its hydrolysis products, i.e. tiatrium pyro and orthophosphates or the acidic and neutral detergents, which are particularly suitable for the production of liquid detergents Potassium pyrophosphates.

Other suitable builder substances are complexing aminopolycarboxylic acids. These include, in particular, alkali salts of nitrilotriacetic acid and alpha-ethylenediaminetetraacetic acid. The salts of diethylenetriaminopentaacetic acid and the higher salts are also suitable Homologues of the aminov mentioned polycarboxylic acid. These homologues can for example by polymerizing an ester, amide or nitrile of N-acetic acid aziridine and subsequent saponification to carboxylic acid salts or by reaction of polyethyleneimine made with chloroacetic acid or bromoacetic acid salts in an alkaline medium will. Other suitable aminopolycarboxylic acids are poly (N-succinic acid) ethyleneimine, Poly (N-tricarballylic acid) ethyleneimine and poly (N-butane-2,3,4-tricarboxylic acid) ethyleneimine, which are obtainable analogously to the N-acetic acid derivatives, can also be complexing active polyphosphonic acid salts be present, e.g. the alkali salts of aminopolyphosphonic acids, in particular aminotri (methylene phosphonic acid), 1-hydroxyethane-1, 1 -diphosphonic acid, Methylenediphosphonic acid, ethylenediphosphonic acid and salts of the higher homologues of the polyphosphonic acids mentioned. Also mixtures of the aforementioned Koniplexierungsmittel are usable.

Of particular importance are the nitrogen- and phosphorus-free, Polycarboxylic acids forming complex salts with calcium ions, including carboxyl groups containing polymers include. Citric acid, tartaric acid and benzene hexacarboxylic acid are suitable and tetrahydrofuran tetracarboxylic acid. Also containing carboxymethyl ether groups Polycarboxylic acids are useful, such as 2, Z'-oxydisuccinic acid, as well as with glycolic acid partially or completely etherified polyhydric alcohols or hydroxycarboxylic acids, for example Triscarboxymettylglycerin, Biscarboxymethylglycerinsaure and carboxymethyl-lated or oxidized polysaccharides. The polymeric carboxylic acids are also suitable with a molecular weight of at least 350 in the form of the water-soluble sodium or xaluminum salts, such as polyacrylic acid, polmethacrylic acid, polyhydroxyacrylic acid Polymaleic acid, polyitaconic acid, polymesaconic acid, polybutenetricarboxylic acid as well the copolymers of the corresponding monomeric carboxylic acids with one another or with ethylenically unsaturated compounds such as ethylene.

Propylene, isobutylene, vinyl methyl ether or furan.

Complexing agents which are insoluble in water can also be used. These include phosphorylated cellulose and graft polymers of acrylic acid or methacrylic acid on cellulose, which can be in the form of woven or non-woven fabrics. Furthermore are spatially cross-linked and thus water-insoluble copolymers of acrylic, methacrylic, Crotonic and maleic acid and other polymerizable polycarboxylic acids, optionally with other ethylenically unsaturated compounds in the form of sodium or potassium salts suitable as a sequestering agent. These insoluble copolymers can be used as fleece, Sponges or in the form of finely ground, specifically light foams with open-celled ones Structure.

Alkali aluminum silicates are also suitable as water-insoluble builder substances and AL> aliborosilicates, which may contain bound water and a Have calcium binding capacity of at least 50 mg CaO / g active substance. For this include in particular compounds of the formula (Na 2 O) Al 2 O 3 (SiO 2) y in which x is a number from 0.7 to 1.5 and y is a number from 1.3 to 4. Also mixtures of the aforementioned water-soluble and water-insoluble builder substances can be used.

The carbonates, bicarbonates, borates and are suitable as washing alkalis Silicates of sodium and potassium, in particular sodium carbonate and sodium silicates with a ratio of Na2O: SiO2 such as 1: 1 to 1: 3.5.

Oxygen-releasing bleaches are used as bleaching agents, such as alkali perborates, percarbonates, perpyrophosphates and persilicates as well as urea perhydrate in question.

Sodium perborate is preferred in anhydrous form or as tetrahydrate used. To stabilize the per compounds, the agents can use magnesium silicate contain, for example in amounts of 3 to 2b wt .-%, based on the amount of Perborate. Agents to be used for washing textiles at temperatures below 70 ° C, so-called cold detergents, bleach activators from the class of N or Contain O-acyl compounds with hydrogen peroxide in aqueous solution taking React formation of peracids.

Preferred bleach activators are tetraacetylmethylenediamine, the Tetraacetylethylenediamine and the Tetraacetylglykolunl. The ones from the bleach activator or powder particles consisting of the per compound can be coated with coating substances, like water-soluble polymers or fatty acids coated to interact between the per connection and the activator during storage.

Instead of the bleaching per compounds and their mixtures with bleach activators Active chlorine-containing bleaches, for example sodium hypochlorite, lithium hypochlorite, Na or K dichloroisocyanurate or trichloroisocyanuric acid or mixtures of Alkali persulphates and alkali chlorides which, when used, form hypochlorite react, are combined with the detergents according to the invention.

This combination can already be done during the manufacture of the detergent or immediately before or during the application. To avoid The active chlorine compounds can also lose losses with inorganic or organic compounds Coating substances be coated or granulated.

The detergents can also contain optical brighteners, in particular Derivatives of diaminostilbene disulfonic acid or

their alkali metal salts. For example, salts of 4,4'-bis (-2 "-anilino-4" -morpholino-1,3,5-triazinyl-6 "-amino) are suitable -stilbene-2,2'-disulfonic acid or similarly structured compounds that instead of the morpholino group -a diethanol- amino group, a methylamino group or carry a ß-methoxyethylamino group. Polyamide fibers are also used as brighteners those of the diarylpyrazoline type in question, for example 1 - (- p-sulfonamidophenyl) -3- (p-chlorophenyl) - # ²-pyrazoline and similarly structured compounds that replace the sulfonamido group carry a carboxymethyl or acetylamino group. Substituted ones can also be used Aminocoumarins, e.g. 4-methyl-7-dimethylamino- or 4-methyl-7-diethylaminocoumarin. The compounds 1- (2-benzimidazolyl) -2- (1-hydroxyethyl-2-benzimidazolyl) -ethylene are also used as polyamide brighteners and 1-ethyl-3-phenyl-7-diethylamino-carbostyril can be used. As a brightener for polyester and polyamide fibers are the compounds 2,5-di- (2-benzoxazolyl) -thiophene, 2- (2-benzoxazolyl) -naphtho- [2,3-b] -thiophene and 1,2-di- (5-methyl-2-benzoxazolyl) -ethylene are suitable. Also know about brighteners of the substituted diphenylstyrile type be present. Also mixtures of the aforementioned Brighteners can be used Suitable as graying inhibitors in particular carboxymethyl cellulose, methyl cellulose, and also water-soluble ones Polyesters and polyamides made from polybasic carboxylic acids and glycols or diamines, the free carboxyl groups, betaine groups or sulfobetaine groups capable of salt formation as well as polymers or copolymers of vinyl alcohol which are colloidally soluble in water, Vinyl pyrrolidones, acrylamides and acrylonitrile.

The agents can also include enzymes from the class of the sample, lipases and amylases or mixtures thereof. Bacterial strains are particularly suitable or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus obtained enzymatic active ingredients.

Neutral salts, especially sodium sulfate, are also used as well as biocides such as halogenated diphenylmethanes, salicylanilides, carbanilides and Phenols into consideration. Liquid agents can also contain hydrotropes and solvents contain, such as alkali salts of benzene, toluene or xylene sulfonic acid, urea, Glycerine, polyglycerine, di- or triglylcol, polyethylene glycol, ethanol, i-propanol and ethereal alcohols.

If necessary, known foam inhibitors, such as saturated Fatty acids and their alkali soaps with 20 to 24 C "atoms, trialkyl melamines, hydrocarbons and silicones, be present.

The quantitative composition of the detergents according to the invention can fluctuate within wide limits, preferably within the following (in percent by weight): 0.1-10%, preferably 0.2-596 polymer according to the invention 0.5-30, preferably 1 - 20 soap and resp.

or sulfate or sulfonate surfactant, 0.5-30%, preferably 1-20 f nonionic surfactant, 0 - 60, preferably 5 - 50% phosphorus-free framework sub punch, O - 60%, preferably 10 - 50% phosphorus-containing structural substance, O - 25 % Washing alkalis, 0 - 30%, preferably 10 - 25 of oxygen-releasing bleaches, in particular Na perborate and its combination with bleach activators and stabilizers, 0 -%, preferably 0.5 - 2% of anti-graying substances, 0 - 1% optical Brighteners, dyes and fragrances, as well as antimicrobial substances, 0-3%, preferably 0.2-2 9d of foam inhibitors.

Examples A. Preparation of the polymers 1. For the preparation of poly-N-vinyloxazolidone are in a 500 ml flask 150 g of xylene, 30 g of N-Vinyloxazolidon and 1 g of azoisobutyric acid dinitrile under a nitrogen atmosphere for 3 hours with stirring heated to 95 ° C, the polymer precipitates in the form of a white powder. To After cooling, the poly-N-vinyloxazolidone is filtered off and washed several times with xylene and dried in a vacuum oven at 50 ° C.

The specific visosity determined at 20 OC in 1% solution was 0.10.

2. For the preparation of an N-vinyloxazolidone-N-vinylimidazole copolymer (Molar ratio 1: 0.9) are 12.2 g of N-vinyl oxazolidone and 9.4 g of N-vinyl imidazole in 120 g of methanol, which is obtained by soaking for one hour under a nitrogen atmosphere Has been deoxygenated, 15 g of N-vinyloxazolidone, 15 g of N-vinylimidazole and Dissolved 0.6 g of azoisobutyric acid dinitrile and the solution for 6 hours with stirring and Bubbling nitrogen through heated to boiling. After cooling, the polymer will through Pour the reaction mixture into approx.

4 1 ether precipitated, filtered off and placed in a vacuum cabinet at 50 OC dried. Specific viscosity: 0.26.

3. For the purpose of producing an N-vinyloxazolidone-N-vinylpyrrolidone copolymer (Molar ratio 1: 1) 10 g of N-vinyl oxazolidone and 10 g of N-vinyl pyrrolidone in the manner indicated in Example 2 in the presence of 0.6 g of azoisobutyric acid dinitrile polymerized in 120 g of methanol and isolated the copolymer by precipitation. Spec. Viscosity: 0.28.

4. A copolymerization of 12.2 g of N-vinyloxazolidone, 11.1 g N-vinylpyrrolidone and 9.4 g of N-vinylimidazole (molar ratio 1.1: 1: 1) according to the example 2 had a specific viscosity of 0.4.

B. Washing tests Textile samples made of cotton were made with the following dyes colored.

a) Cibacron brilliant orange 2GE b) Naphthol AS-OL Variamin blue salt B c) Sirius light scarlet BN d) Indanthrene brilliant green GG e) Sirius light blue BL These dyed textile samples were used along with various ones below listed colorless test fabrics washed in the launderometer.

I) Cotton II) Refined cotton (wash and ear equipment) III) Mixture of polyester and refined cotton (1: 1) IV) Polyester fabric V) Polyurethane fabric (Lycra% the weight ratio of dyed cotton fabric to white test fabric was 2: 1. 7.5 g / l of a detergent was obtained as follows Composition used (in% by weight) 4.0% polymer according to the invention 8.5% Na-n-dodecylbenzenesulfonate 2.5% tallow alcohol, 14-fold ethoxylated 1.5% tallow alcohol, 5 times ethoxylated 3.5% Na soap (tallow fatty acid to coconut fatty acid 9: 1) 40.0% Sodium tripolyphosphate 5.5% sodium silicate (Na20: SiO2 = 1: 3.3) 1.5% magnesium silicate 0.5% Na ethylenediaminotetraacetate 1.5% Na carboxymethyl cellulose 20.0% sodium perborate 0.3 t optical brighteners and fragrances, residual sodium sulfate when using the cotton test fabric (I) the liquor ratio (textile weight in g to washing liquor in ml) was 1: 12 and the washing temperature 90 ° C. The remaining test fabrics were at a liquor ratio Washed at 1:30 and a temperature of 60 ° C, after heating the Wash liquor to the specified temperatures a washing time of 15 minutes each was adhered to. After washing, it was rinsed 3 times with tap water. the Water hardness was 16 ° dH.

First of all, the experiments in the presence of AX were made according to the invention using polyraeren discoloration inilibitors carried out and the occurred Color transfer measured photometrically.

The experiment was then repeated in the presence of the polymer and again the remission of the test tissue photometrically certainly. The difference ER of the two reflectance values is a measure of the "discoloration inhibition", i.e. the protective effect of the polymer in question. All in the following table The difference values listed are the average values from 5 parallel tests. the The results are compiled in the following table. The designations aI) bII) -bIII) etc. stand for the combinations of dye a) with textile material I), dye b) with textile material II, dye b) with textile material III) etc. The device tElrepho "from Carl Zeiss in Used in combination with the following filters.

Dye a) filter 46/5 "b) n 40/9 nc) n 46/5" d) "46/2" e) "40/9 The results show that the polymers used according to the invention are suitable for measurable color transfer to decrease. #R Dye Example 1 Example 2 Example 3 Example 4 Textile material a I 12 21 16 19 b II 2 4 - 4 b III 4 6 2 5 c III 8 6 2 7 d IV 10 10 9 9 e V 17 16 17 19

Claims (12)

"Detergents with a content of discoloration-inhibiting additives" P a t e n t a n s p r ü c h e 1. Detergents and cleaning agents, containing anionic and / or nonionic surfactants, builders and other common detergent additives, characterized by a content based on the total weight of the agents 0.1 to 10 wt .-% of a water-soluble or dispersible homo- or Copolymers of N-vinyl oxazolidone. 2. Means according to claim 1, characterized in that the degree of polymerization of the homo- or copolymer contained therein 10 to 10,000, preferably 20 to 5000 amounts to. 3. Means according to claim 1 and 2, characterized by a content of homopolymeric N-vinyloxazolidone. 4. Means according to claim 1 and 2, characterized in that the therein Polymers contained from a 'copolymer of N-Vinyloxazolidons with a one copolymerizable compound having an olefinic double bond. 5. Means according to claim 1, 2 and 1, characterized in that the Polymers contained therein a copolymer of N-Vinyloxazolidons with a copolymerizable Olefin, vinyl, allyl, acrylic or methacrylic compound. 6. Means according to claim 4 and 5, characterized in that the proportion of the N-vinyl oxazolidone on the copolymer is at least 25 mol%. 7. Means according to claim 4 and 5, characterized in that the proportion of the N-vinyl oxazolidone on the copolymer is at least 50 mol%. 8. Composition according to claim 4 to 7, characterized in that the copolymerizable Compound consists of N-vinylpyrrolidone and / or N-vinylimidazole, the molar The proportion of N-vinyl oxazolidone is greater than that of N-vinyl imidazole. 9. Composition according to claim 4 to 7, characterized in that the copolymerizable Compound consists of vinyl acetate. 10. Means according to claim 4 to 7, characterized in that the copolymerizable compound consists of acrylamide and / or methacrylamide. 11. means according to claim 4 to 10, characterized in that the copolymerizable compound up to 5 mol% of a compound with at least 2 copolymerizable double bonds. 12. Means according to claim 1 to 11, characterized in that its Content of homo- or copolymers of N-vinyloxazolidone 0.2 to 5, in particular 0.5 to 4 wt. T.