GB1584562A - Washing agents - Google Patents

Abstract

In order to make possible washing of textiles at a temperature between 10 and 30 DEG C, in particular 15 and 25 DEG C, the detergent, in addition to at least one anionic, non-ionic or zwitterionic surfactant, contains a water-soluble hydroxyalkylated polyamide which contains to at least half of its weight of bound ethylene oxide and/or glycidol and/or propylene oxide or butylene oxide. The weight ratio of the surfactant to the hydroxyalkylated polyamide is between 50:1 and 2:1.

Description

(54) WASHING AGENTS (71) We, HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN, a German Company, of 67 Henkelstrasse, 4000 Dusseldorf-Holthausen, Federal Republic of Germany, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The present invention relates to a novel textile washing agent which can also be used particularl with cold water, a method of manufacturing the washing agent, and a washing method.

It is necessary to wash with warm washing liquors in order to obtain a satisfactory washing result. Thus, the availability of hot water from hot water appliances or washing machines having heating devices is not only a prerequisite for a satisfactory washing result but is also an important cost factor when washing. Owing to changed consumer habits and owing to the increasing popularity of easily washed textiles made from synthetic fibres, there has been a tendency in recent times for conventional boiling washing to be replaced to an increasing extent by the so-called 60"C wash, this undoubtedly being associated with a saving of energy.

The object of the present invention is to provide, for cold washing, a washing agent which gives a satisfactory washing result even with non-heated water, that is with water of from 10 to 30"C, particularly from 15 to 25"C, such as generally comes from the water mains, in order to save more thermal energy when washing.

Accordingly the present invention provides a washing agent which comprises a combination of at least one surfactant of the group of the anionic, non-ionic and zwitterionic surfactants and a water-soluble alkoxylated polyamide which contains bound ethyleneoxide and/or glycidol and/or propyleneoxide and/or butyleneoxide in a quantity equal to at least half, preferably at least two-thirds of the weight of the polyamide, the quantity ratio of the surfactant to alkoxylated polyamide being 50:1 to 2:1, preferably 20: 1 to 2 1.

The water-soluble alkoxylated polyamides used in the washing agents in accordance with the invention are preferably those products of reaction whose water solubility is characterised by a turbidity point in water (determined in accordance with DIN 53917) in excess of 20"C.

Known commercially available polyamides may be used to manufacture the alkoxylated polyamides used in accordance with the invention. Suitable polyamides of this type can be obtained in a known manner by polycondensation of a, (ss-c2-cl2-diaminoalkanes such as tertra-, penta- or hexamethylenediamine, or cycloaliphatic diamines such as 4,4'-diamino1,1'-dicyclohexyl-methane, and C4-C,2 dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid and terephthalic acid.Further starting materials suitable for the production of polyamides are the polyamide-forming (ss-aminocarboxylic acids having 4 to 12 carbon atoms such as o-aminobutyric acid, o-aminocaproic acid, o-aminocaprylic acid and (ss-aminocapric acid, or the lactams corresponding to these (o-aminocarboxylic acids. Thestarting materials capable of forming polyamide may also be used in the form of mixtures. The polyamides generally have an average molecular weight of between 500 and 30,000.

The polyamides are alkoxylated in a known manner with the polyamides in a pulverulent or granulated form. Work may be carried out in the presence or absence of a suspension or swelling agent such as acetone, dioxan, tetrahydrofuran and toluene, and with or without a catalyst. When more than one epoxide, such as the combination ethyleneoxide/ propyleneoxide, glycidol/propyleneoxide or glycidol/ethyleneoxide, is used during alkoxylation, it is preferable in the first instance to react with one epoxide and to react the second epoxide component only after the first epoxide component had been added. Products of reaction having two different epoxides are manufactured particularly by first adding the more hydrophilic component and then adding the more hydrophobic component.Turbidity point measurements for determining the water-solubility of the substances were carried out up to 100"C. When the substance was soluble in boiling water, > 100"C was specified for the turbidity point.

Unexpectedly, it was found that even a small quantity of the alkoxylated polyamide with the surfactant or surfactant mixture cause a synergistic increase in the washing powder which is particularly effective in the cold washing liquor. Consequently, the washing agents in accordance with the invention contain 0.5 to 2.5 percent by weight of the alkoxylated polyamide together with a surfactant content of 5 to 50 percent by weight which preferably comprises synthetic anionic surfactants of the sulphonate and sulphate type, and/or non-ionic surfactants and/or zwitterionic surfactants.

Preferably, the washing agents in accordance with the invention contain at least one further conventional washing agent constituent selected from inorganic and/or organic builder substances, foam inhibitors, optical brighteners, dirt carriers, enzymes, antimicrobial effective substances, dyes and perfumes. Liquid embodiments can contain, in addition to, or instead of, water, low molecular organic solvents miscible with water, particularly from the group of the aliphatic alcohols, diols and ether alcohols.

When using cold water, such as is directly available from the water mains, the washing agents in accordance with the invention render it possible to obtain satisfactory results with conventional manual washing operations and when using a washing machine. The agents in accordance with the invention can also contain bleaching additives comprising peroxy compounds acting as active oxygen carriers, particularly sodium perborate, stabilizers and, if required, activators. Thus, an additional bleaching effect is obtained when washing at elevated temperatures, that is when washing at 600C and when boiling the washing. The hydroxyalkylated polyamides used in accordance with the invention contribute to the total washing effect in an advantageous manner even when washing at these elevated temperatures in a washing machine.

By way of example, the following commercially available polyamide types can be used for the production of the alkoxylated polyamides used in accordance with the invention: A polycondensate from hexamethylenediamine and adipic acid, melting point approx mately 260"C (Ultramid A3 manufactured by the firm BASF); A polycondensate from hexamethylenediamine, adipic acid and E-caprolactam, melting point approximately 185"C (Ultramid 6A, BASF); A poly-r-caprolactam, melting point approximately 220"C (Ultramid B3, BASF); A polycondensate from hexamethylenediamine, adipic acid, E-caprolactam and 4,4' diamino-1,1'-dicyclohexyl-methane, melting point approximately 185"C (Ultramid 1C, BASF);; A polycondensate from hexamethylenediamine and sebacic acid, melting point approximately 215"C (Ultramid, S4, BASF).

Alkoxylation of the preferably granulated or pulverized polyamide with ethyleneoxide is carried out preferably in the presence of a dispersing or swelling agent such as dioxan and an alkaline catalyst. Suitable catalysts are, for example, the compounds sodium methylate, sodium hydroxide, sodium hydrocarbonate, triethylamine or trimethylbenzylammoniumhydroxide (Triton (Registered Trade Mark) B). Preferably, sodium methylate is used.

Preferably, reaction with ethyleneoxide is effected in an agitating autoclave by pressurising the calculated quantities of ethyleneoxide in portions in a nitrogen atmosphere at the selected reaction temperature of from 100 to 200"C, preferably from 150 to 1800C, and maintaining them at reaction temperature for a period of time after the pressure had stabilised. The reaction mixture is removed from the autoclave after cooling, and a furher organic solvent in which the product is soluble, such as dioxan or ethanol, is added thereto.

The reaction mixture is then neutralized with diluted hydrochloric acid, drawn from the insoluble in the heat, and the filtrate is reduced in vacuo until dry. In the case of alkoxylation with glycidol, the polyamide, which is as fine-particulate as possible, is mixed with a portion of the glycidol at room temperature. The air in the reaction vessel is then replaced by nitrogen and the preparation is heated to approximately 200"C. After the reaction with the glycidol present has been completed, the rest of the glycidol is added, under agitation and the passing-through of nitrogen, drop-by-drop at a rate at which the internal temperature remains constant. Thus, when reacting with glycidol, work is carried out without an additive of an organic solvent and a catalyst.When alkoxylating the polyamides with two different epoxides, the second epoxide, such as the propyleneoxide, is reacted when the addition reaction with the first epoxide, such as ethyleneoxide, has ended.

Preferably, products of reaction of the polyamides with ethyleneoxide and with ethyleneoxide/propyleneoxide are used in the stated quantity ratios in the agents in accordance with the invention. These alkoxylated polyamides combine ready accessibility with a great increase in the washing powder.

The composition of the washing agent in accordance with the invention can be subjected to certain variations according to the purpose for which it is used. If the preparations in accordance with the invention are to be universally usable, and can also be used as boiling washing agents, this is achieved by adding a peroxy compound, particularly sodium perborate, which, together with a stabilizer and, if required, an activator for the peroxy compound, can amount to 10 to 40, particularly 15 to 35 percent by weight of the total washing agent.

In general, the composition of the washing agent in accordance with the invention lies in the range of the following formulation: (a) 5 - 50, preferably 5 to 25 percent by weight of at least one surfactant from the group of the sulphonate and sulphate surfactants and the non-ionic surfactants of the ethoxylated alcohols, alkenols and alkylphenols type.

(b) 0.5 - 2.5 percent by weight of the alkoxylated polyamide defined above, the constituents (a) and (b) being present preferably in the ratio 20 1 to 2 (c) 0 - 8, preferably 0.2 to 5 percent by weight of a foam inhibitor from the group of the alkali soaps having essentially Cl8-C22 fatty acid radicals, and the non-surfactant foam inhibitors, (d) 50 - 94.5, preferably 55 to 90 percent by weight of pulverulent and/or liquid carrier substances from the group of the pulverulent organic and inorganic builder substances, the water-soluble low alcohols, diols and ether alcohols and water, optionally including a bleaching component, and (e) 0 - 10 preferably 0.5 to 10 percent by weight of conventional additives for washing agents from the group of the optical brighteners, enzymes, dirt carriers, textile softeners, antimicrobial effective substances, dyes and perfumes.

Washing agents in accordance with the invention, . which exhibit a particularly pronounced washing power both in the cold as well as at an increased temperature or at boiling washing temperature, contain, as the surfactant component (a), a sulphonate surfactant together with a non-ionic surfactant, particularly of the ethoxylated aliphatic C10-C20 alcohols type. Preparations in accordance with the invention, whose surfactant component (a) exclusively comprises non-ionic surfactants, particularly ethoxylated aliphatic C,(,-C20 alcohols, are also preferred.

A particularly satisfactory washing effect is observed when these non-ionic ethoxylation products are present in the form of mixtures of products having differing average degrees of ethoxylation and, in these mixtures, the ratio of the products of addition of 8 to 20 mol of ethyleneoxide to one mol of an aliphatic C1()-C2() alcohol to the ethoxylation products with 2 to 7 mol of ethyleneglycol per mole of alcohol is 5 : 1 to 1 : 3.

Washing agents in accordance with the invention, having a low foaming capacity, contain 0.2 to 0.8 percent by weight of a non-surfactant-like foam inhibitor or 0.5 to 5 percent by weight of a alkali soap of essentially C18-C22 fatty acids, or a mixture of the non-surfactant-like foam inhibitor and the soap in a quantity of from 0.2 to 5 percent by weight.

The washing agents in accordance with the invention are present in the form of pulverulent, pasty or liquid preparations.

Preferably, the liquid to pasty preparations are manufactured by dissolving the surfactant component (a) in the solvent (d), then 'adding the alkoxylated polyamide (b), homogenizing the mixtures by agitation and, if required, heating, and intermixing any further components (c) and (e) provided and finally intermixing any pulverulent builder substances in accordance witch (d) which are provided.

Pourable, pulverulent preparations can be produced in accordance with the conventional methods, for example by cold and hot spray-drying. Preferably, the alkoxylated polyamides (b) which are pasty or wax-like at room temperature, are applied to the powder particles of the rest of the constituents of the preparation, preferably by spraying (in the form of an alcoholic solution, for example) onto a portion of the builder substances, sodium triphosphate- and sodium sulphate forms having bulk weights of from 200 to 500 g/l being particularly suitable for this purpose, or, in the case of preparations containing bleaching agents, by spraying onto finely pulverulent sodium perborate.

Furthermore, the invention relates to a method of washing textiles with the use of the washing agents in accordance with the invention. This method is characterised in that the textiles are agitated, manually or in a machine, in an aqueous washing liquor at a temperature between 10 and 30"C, particularly 15 to 250C, for 10 to 60 minutes, wherein this washing liquor contains the above-defined washing agent in quantities of from 1.0 g/l to 12.0 g/l, preferably 4.0 g/l to 10.0 g/l, and that the textiles are subsequently removed from the washing liquor and are rinsed with fresh water until the constituents of the washing liquor have been fully removed.

When the washing liquor contains a peroxy compound acting as a bleaching agent, a desired bleaching effect on the textiles can be obtained, following the washing process in the cold washing liquor, by heating this washing liquor to temperatures of preferably 60 to 95"C for a period of from 5 to 30 minutes.

The most important constituents contained in the washing agents in accordance with the invention, classified according to classes of substance, will now be further described.

The surfactants contain, in the molecule, at least one hydrophobic organic radical and one anionic, zwitterionic or non-ionic group which renders them water-soluble. The hydrophobic radical is usually an aliphatic hydrocarbon radical having 8 to 26, preferably 10 to 22, and particularly 12 to 18 carbon atoms, or an alkylaromatic radical having 6 to 18, preferably 8 to 16 aliphatic carbon atoms.

By way of example, soaps from natural or synthetic, preferably saturated fatty acids and optionally from resinic or naphthenic acids, are usable as anionic surfactants. Suitable synthetic anionic surfactants are those of the sulphonates, sulphates and synthetic carboxylates type.

Suitable surfactants of the sulphonate type are alkylbenzene sulphonates (Cg~15-alkyl), olefin sulphonates, mixtures of alkene- and hydroxyalkane sulphonates as well as disulphonates such as those obtained, for example, from C12-C18 monoolefins having an end position or inner position double bond by sulphonation with gaseous sulphurtrioxide and subequent alkaline or acid hydrolysis of the sulphonation products. Alkane sulphonates are also suitable which are obtainable from Cl2-Cl8 alkanes by sulphochlorination or sulphoxidation and subsequent hydrolysis or neutralization, or by adding bisulphate to olefins, as well as the esters of a-sulpho fatty acids, such as a-sulphonated methyl- or ethyl esters of hydrated coconut-, palm kernel- or stearic fatty acids.

Suitable surfactants of the sulphate type are the sulphuric acid monoesters of primary alcohols (for example from coconut fatty alcohols, tallow fatty alcohols or oleyl alcohol) and those of secondary alcohols. Also suitable are sulphated fatty acid alkanolamides, sulphated fatty acid monoglycerides or sulphated reaction products of 1 to 4 mol of ethyleneoxide with the primary or secondary alcohols or alkylphenols.

Further suitable anionic surfactants are the fatty acid esters or -amides of hydroxy- or amino-carboxylic acids or -sulphonic acids, such as the fatty acid sarcosides, -glycolates, -lactates, -taurides or - isethionates.

The anionic surfactants may be present in the form of sodium-, potassium- and ammonium salts thereof, as well as soluble salts of organic bases such as mono-, di- or triethanolamine.

Products of addition of 1 to 40, preferably 2 to 20 mol of ethyleneoxide to 1 mol of fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkane sulphonamide are usable as non-ionic surfactants. Particularly important are the products of addition of 8 to 20 mol of ethylene alcohol to coconut- or tallow fatty alcohols, to oleyl alcohol or to secondary alcohols having 8 to 18, preferably 12 to 18 carbon atoms, and to mono- or dialkylphenols having 6 to 14 carbon atoms in the alkyl radicals. However, in addition to these water-soluble non-ionics, polyglycol ethers which are not water-soluble or which are not fully water-soluble, having 2 to 7 ethyleneglycol ether radicals in the molecule, are of interest, particularly when they are used together with water-soluble non-ionic or anionic surfactants.

Furthermore, non-ionic surfactants which are usable are the water-soluble products of addition, containing 20 to 250 ethyleneglycol ether groups and 10 to 200 propyleneglycol ether groups, of ethyleneoxide to polypropyleneglycol, alkylene diamine polypropyleneglycol and to alkylpolypropyleneglycols having 1 to 10 carbon atoms in the alkyl chain, in which the polypropyleneglycol chain acts as a hydrophobic radical. Non-ionic surfactants of the amine oxides or sulphoxides type are also usable, such as the compounds N-coconut alkyl-N ,N-dimethylamine oxide, N-hexadecyl-N,N-bis(2,3-dihydroxypropyl) amine oxide, N-tallow alkyl-N,N-dihydroxyethylamine oxide.

Consequently, the term "non-ionic surfactants (non-ionics)" does not embrace the hydroxyalkylated polyamides used in accordance with the invention.

The zwitterionic surfactants are preferably derivatives of aliphatic quaternary ammonium compounds in which one of the aliphatic radicals comprises a C8-Cl8 radical and contains a further anionic carboxy-, sulpho- or sulphato group rendering them water-soluble. Typical representatives of such surface-active betaines are, for example, the compounds 3-(N hexadecyl-N,N-dimethylammonio)-propane sulphonate; 3-(N-tallow alkyl-N,N dimethylammonio)-2-hydroxy-propane sulphonate; 3-(N-hexadecyl-N,N-bis(2 hydroxyethyl)-ammonio)-2-hydroxypropyl sulphate; 3-(N-coconut alkyl-N ,N-bis(2,3 dihydroxypropyl)-ammonio)-propane sulphonate; N-tetradecyl-N ,N-dimethyl-ammonio acetate; N-hexadecyl-N ,N-bis(2,3-dihydroxypropyl)-ammonio acetate.

The foaming capacity of the surfactants can be increased or reduced by combining suitable types of surfactants. A reduction in the foaming capacity can also be obtained by additives of non-surfactant-like organic substances. A reduced foaming capacity, desirable when working in machines, is frequently obtained by combining various types of surfactants, for example by combining sulphates and/or sulphonates with non-ionics and/or with soap. The foam-inhibiting action in the case of soaps increases with the degree of saturation and the C number of the fatty acid radical. Thus, soaps of saturated C20-24 fatty acids are particularly suitable as foam inhibitors.

The non-surfactant-like foam inhibitors are generally water-insoluble compounds which usually contain aliphatic C8-C22 carbon radicals. Suitable non-surfactant-like foam inhibitors are, for example, the N-alkylamoniotriazines, i.e. products of reaction of 1 mol of cyanuric chloride with 2 to 3 mol of a mono- or dialkylamine having essentially 8 to 18 carbon atoms in the alkyl radical.Propoxylated and/or butoxylated aminotriazines are also suitable, such as the products of reaction of 1 mol of melamine with 5 to 10 mol of propyleneoxide and additionally 10 to 50 mol of butyleneoxide as well as the aliphatic C18-C40 ketones such as stearone, the fatty ketones of hardened train oil fatty acid or stearic fatty acid etc, as well as paraffins and halogenated paraffins having melting points below 100 C and silicon oil emulsions based on polymeric silicon-organic compounds.

Suitable organic and inorganic builder substances are slightly acid, neutral or alkaline reacting salts, particularly alkali salts which are able to precipitate calcium ions or to combine them in a complex manner. Particularly important inorganic complex-forming salts are the water-soluble alkalimeta- or alkali-polyphosphates, particularly pentasodium triphosphate. These phosphates may be entirely or partially replaced by inorganic complex formers for calcium ions. The organic complex formers include components of the aminopolycarboxylic acids type, such as nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid as well as higher homologues.Suitable organic complex formers containing phosphorus are the water-soluble salts of alkanepolyphospho nic acids, amino- and hydroxyalkanepolyphosphonic acids and phosphonopolycarboxylic acids such as the compounds methanediphosphonic acid, dimethylaminomethane-1,1 diphosphonic acid, aminotrimethylenetriphosphonic acid, 1-hydroxyethane-l , 1- diphosphonic acid, 1-phosphonoethane- 1 ,2-dicarboxylic acid, 2-phosphonobutane-1 ,2,4- tricarboxylic acid.

Particularly important organic builder substances are the N-free and P-free polycarboxy lic acids forming complex salts with calcium ions, also including polymers containing carboxyl groups. By way of example, citric acid, tartaric acid, benzenehexacarboxylic acid and tetrahydrofurantetracarboxylic acid are suitable. Polycarboxylic acids containing ether groups are also usable, such as 2,2'-oxydisuccinic acid, as well as polyvalent alcohols partially or fully etherified with glycolic acid, or hydroxycarboxylic acids such as biscarboxymethylethyleneglycol, carboxymethyloxysuccinic acid and carboxymethylated or oxygenated polysaccharides.Furthermore, polymeric carboxylic acids having a molecular weight of at least 350 are also suitable in the form of water-soluble salts, such as polyacrylic acid, poly-a-hydroxyacrylic acid, polymaleic acid, as well as the copolymers of the corresponding monomeric carboxylic acids one with another or with ethyleneically unsaturated compounds such as ethylene, propylene, isobutylene, vinylmethyl ether or furan.

Suitable inorganic, non-complex-forming salts are the bicarbonates, carbonates, borates, sulphates or silicates of alkalis; the alkali silicates which are primarily usable are the sodium silicates having a ratio of Na2O . SiO of 1 . 1 to 1 . 3.5.

Further builder substances, which are generally used in liquid agents owing to their hydrotropic properties, are the salts of the non-capillary-active sulphonic acids, carboxylic acids and sulphocarboxylic acids containing 2 to 9 carbon atoms, such as the alkali salts of alkane-, benzene-, toluene, xylene- or cumene-sulphonic acids, of sulphobenzoic acids, sulphophthalic acid, sulphoacetic acid, sulphosuccinic acid, as well as the salts of acetic acid or lactic acid. Acetamide and urea are also suitable as dissolving intermediaries.

The preparations may also contain dirt carriers which hold the dirt, released from the fibres, in suspension in the liquor and thus prevent greying. Water-soluble colloids, usually of an organic nature, are suitable for this purpose, such as the water-soluble salts of polymeric carboxylic acids, glue, gelatines, salts of ethercarboxylic acids or ethersulphonic acids of starch or cellulose, or salts of acid sulphuric acid esters of cellulose or of starch.

Water-soluble polyamides, containing acid groups, are also suitable for this purpose.

Furthermore, soluble starch preparations and others can be used as the above-mentioned starch products, such as peptized starch and aldehyde starches. Polyvinylpyrrolidone is also usable.

Particularly important compounds which act as bleaching agents, and which yield H202 in water, are sodium perborate-tetrahydrate (NaBO2 . H202 . 3 H20) and -monohydrate (NaBO2 . H202). However, other borates which yield H202 are usable, such as perborate Na2B407 . 4 H202. These compounds can be partially or fully replaced by other active oxygen carriers, particularly by peroxyhydrates such as peroxycarbonates (Na2CO3 . 1.5 H202), peroxypyrophosphates, citrateperhydrates, urea-H202- or melamine- H202 compounds, and by peracid salts which yield H202, such as caroates (KHSO5), perbenzoates and peroxyphthalates.

It is advisable to incorporate, together with the peroxy compounds, quantities of from 0.25 to 10 percent by weight of conventional, water-soluble and/or water-insoluble stabilizers for the peroxy compounds. Suitable water-insoluble stabilizers, which, for example, amount to 1 to 8, preferably 2 to 7%, of the weight of the total preparation, are the magnesium silicates, usually obtained by precipitation from aqueous solutions, MgO SiO2 = 4 : 1 to 1: 4, preferably 2 1 to 1: 2 and particularly 1:1. They can be replaced by other alkaline earth metal- or tin silicates of corresponding composition. Oxides of tin containing water are also suitable as stabilizers.Water-soluble stabilizers, which can be present together with water-insoluble stabilizers, are the organic heavy metal complex formers which may be present in quantities of from 0.25 to 5, preferably 0.5 to 2.5% of the weight of the total preparation.

Preferably, bleaching components containing activators are incorporated in the prepara tions in order to obtain a satisfactory bleaching action when washing at temperatures below 80"C, particularly in the range of from 40 to 60"C.

Activators for percpmpounds yielding H202 in water are specific N-acyl- or O-acyl compounds which form organic peracids with the H202, particularly acetyl-, propionyl- or benzoyl compounds, as well as carbonic acid ester or pyrocarbonic acid ester. Usable compounds include:N-diacylated and N,N'-tetraacylated amines such as N,N,N', N'-tetraacetyl-m-ethylene diamine or -ethylene diamine, N,N-diacetylaniline and N,N diacetyl-p-toluidine or 1,3-diacylated bydantoins, alkyl-N-sulphonyl-carbonamides, such as N-methyl-N-mesyl-acetamide, N-methyl-N-mesyl-benzamide, N-methyl-N-mesyl-p nitrobenzamide, and N-methyl-N-mesyl-p-methoxybenzamide, N-acylated cyclic hydra zides, acylated triazoles or urazoles such as monoacetyl maleic acid hydrazide, O,N,N trisubstituted hydroxylamines such as O-benzoyl-N,N-succinyl-hydroxyl amine, O-acetyl N,N-succinyl-hydroxylamine, O-p-methoxybenzoyl-N,N-succinyl-hydroxylamine, O-p- nitrobenzoyl-N,N-succinylhydroxylamine and O,N,N-triacetyl-hydroxylamine, N,N' diacyl-sulphuryl amides, such as N,N'-dimethyl-N,N'-diacetyl-sulphuryl amide, and N,N' diethyl-N,N'-dipropionyl-sulphurylamide, triacylcyanurates such as triacetyl- or tribenzoyl cyanurate, carboxylic acid anhydrides such as benzoic acid anhydride, m-chlorobenzoic acid anhydride, phthalic acid anhydride, 4-chlorophthalic acid anhydride, sugar esters such as glucosepentaacetate, 1,3-diacyl-4,5-diacyloxy-imidazolidines, such as the compounds 1,3 diformyl-4,5-diacetoxy-imidazolidine, 1 ,3-diacetyl-4,5-diacetoxy-imidazolidine, 1,3 diacetyl-4,5-dipropionyloxy-imidazolidine, acylated glycolurils such as tetrapropionylglyco luril or diacetyl-dibenzoyl-glycoluril, diaceylated 2,5-diketopiperazines such as 1,4-diacetyl 2,5-diketopiperazine, 1 4-dipropionyl- 1 5-diketopiperazine, 1 ,4-dipropionyl-3 ,6-dimethyl- 2,5-diketopiperazine, acylation or benzoylation products of propylene diurea or 2,2 dimethyl-propylene diurea (2,4,6,8-tetraazo-bicyclo-(3,3,1)-nonane-3,7-dione or 9,9 dimethyl derivative thereof), sodium salts of p-(ethoxy carbonyloxy)- benzoic acid and p-(propoxycarbonyloxy)-benzene sulphonic acid.

The washing agents can contain, in particular, derivatives of diaminostilbene disulphonic acid or alkali metal salts thereof, as optical brighteners for cotton. By way of example, salts of 4,4' -bis(2-anilino-4-morpholino- 1,3 ,5-triazine-6-yl-amino)-stilbene-2,2' -disulphonic acid are suitable, or compounds which are built up in a similar manner and which carry a diethanolamino group, a methylamino group or a 2-methoxyethylamino group instead of the morpholino group.Suitable brighteners for polyamide fibres are those of the 1,3-diaryl-2-pyrazolines type, for example the compound 1-(p-sulphamoylphenyl)-3-(p chlorophenyl)-2-pyrazoline as well as compounds which are built up in a similar manner and which carry, for example, the methoxycarbonyl-, 2-methoxy-ethoxycarbonyl-, the acetylamino- or the vinylsulphonyl group instead of the sulphamoyl group. Furthermore, usable polyamide brighteners are the substituted aminocumarines such as 4-methyl-7dimethylamino- or 4-methyl-7-diethylamino cumarine. Furthermore, the compounds 1-(2-benzimidazolyl)-2-(1-hydroxyethyl-2-benzimidazolyl)-ethylene and 1-ethyl-3-phenyl7-diethylamino-carbostyril are usable as polyamide brighteners.Suitable brighteners for polyester and polyamide fibres are the compounds 2,5-di-(2-benzoxazolyl)-thiophen, 2-(2-benzoxazolyl)-naphtho [2,3,-b] -thiophen and 1,2-di-(5-methyl-2-benzoxazolyl)ethylene. Furthermore, brighteners of-the substituted 4,4'-distyryl-diphenyl type may be present, such as the compound 4,4'-bis(4-chloro-3-sulphostyryl)-diphenyl. Mixtures of the above-mentioned brighteners may also be used.

Suitable water-soluble organic solvents are the lower alcohols, ether alcohols, glycol or ketones having 1 to 6 carbon atoms, such as methanol, ethanol, propanol, isopropylalcohol, ethyleneglycol, propyleneglycol, diethyleneglycol, methylglycol, ethylglycol, butylglycol or acetone and methylethylketone.

Examples The production of some of the alkoxylated polyamides, usable in accordance with the invention, will be described in the first instance.

The ethoxylation or ethoxylation/propoxylation of the polyamides was carried out in accordance with the following directions: The ethyleneoxide and, optionally, propyleneoxide in differing quantities further specified in the individual products were pressed with nitrogen onto a mixture of 56.3 g of the polyamide (0.5 mol relative to the monomeric unit), 200 ml of dioxan and 0.3 g of sodium methylate in a 2000 ml agitating autoclave in portions of approximately 20 g under agitation at a temperature of approximately 150 to 1750C. In the event of a further reaction with propyleneoxide, the latter was reacted in the same manner after the pressure had stabilised, or was maintained at the reaction temperature for a further hour after the pressure stability had been attained. After cooling, 600 ml of dioxan were added to the reaction product.The mixture was subsequently neutralized with diluted hydrochloric acid and the insoluble portion was removed while hot. The filtrate was evaporated on a rotary evaporator until dry. The reaction products were slightly yellowish compositions which are obtained in the form of pasty or wax-like products after the solvent has been drawn off. The turbidity points were determined in water in accordance with DIN 53917.

Product I The production of reaction of polyamide from hexamethylenediamine, adipic acid and r-caprolactam (Ultramid 6A) with ethoxyleneoxide in the weight ratio 1:1.37; turbidity point > 100"C.

Product II The product of reaction of 56.3 g of the polyamide Ultramid 6A and 66 g of ethyleneoxide; turbidity point > 100"C.

Product III The product of reaction of 56.3 g of the polyamide Ultramid 6A firstly with 48 g of ethyleneoxide and subsequently with 87 g of propyleneoxide; weight ratio polyamide epoxides is 1 : 24; turbidity point 37 to 390C.

Product IV The product of reaction of 56.3 of the polyamide Ultramid 6A firstly with 385 g of ethyleneoxide and subsequently with 103 g of propyleneoxide; weight ratio polyamide epoxides is 1 . 8.6; turbidity point > 100"C.

Product V The product of reaction of 56.3 g of the polyamide Ultramid 6A firstly with 77 g of ethyleneoxide and subsequently with 103 g propyleneoxide; turbidity point 47 to 490C.

Product VI The product of reaction of the polyamide from hexamethylenediamine, adipic acid, r-caprolactam and 4,4' -diamino-1 1 '-dicyclohexylmethane (Ultramid 1C) with ethyleneoxide in the weight ratio 1 . 1:56; turbidity point > 100"C.

Product Vll The product of reaction of the polyamide from hexamethylene-diamine and adipic acid (Ultramid A3) with ethyleneoxide in the weight ratio 1: 4.1; turbidity point > 100"C.

Product VILLI The product of reaction of the polyamide from E-caprolactam (Ultramid B3) with ethyleneoxide in the weight ratio 1 : 4.4; turbidity point > 1000C.

Product 1X The product of reaction from a poly--caprolactam and ethyleneoxide, with an ethyleneoxide content of approximately 77 percent by weight; turbidity point > 1009C (Commercial product Lurotex A25 of the firm BASF).

Product X The product of reaction of the polyamide from hexamethylenediamine and sebacic acid (Ultramid S4) with ethyleneoxide in the weight ratio 1: 5.3; turbidity point > 100"C Working instructions for the reaction with glycide; Approximately 20 g of the granulated polyamide, together with approximately 10 ml of glycide, were placed into a 250 ml three-necked flask with agitator, thermometer, reflux cooler and dropping funnel. The air in the apparatus was then replaced by nitrogen and the reaction vessel was immersed in an oil bath pre-heated to approximately 200"C. After the reaction had been completed, the remaining quantity of glycide was added drop-by-drop under agitation and with the passing-through of nitrogen such that the internal temperature remained constant.The reaction mixture was subsequently maintained at 2000C for approximately 1/2 hour and was then cooled. The glycidation products were obtained in the form of yellowish, wax-like compositions which were fully soluble in water or alcohol (turbidity points > 100"C).

Product XI The product of reaction from 22.6 g (0.2 mol) of the polyamide Ultramid 6A and 107.5 g (1.45 mol) of glycidol; weight ratio 1 : 4.75; reaction temperature 200 to 205"C.

Product Xll The product of reaction of the polyamide Ultramid 6A with glycidol; weight ratio 1: 2.75; reaction temperature 235 to 240"C.

Product XIlI The reaction product of the polyamide Ultramid 1C with glycidol; weight ratio 1: 3.54; reaction temperature 200 to 2050C.

Product XIV The product of reaction of the polyamide Ulramid 1C with glycidol; weight ratio 1: 2.41; reaction temperature 240 - 245"C.

Product XV The reaction product of the polyamide Utramid B3 with glycidol; weight ratio 1: 6.6; reaction temperature 195 to 205"C.

Product XVI The reaction product of the polyamide Ultramid B3 with glycidol; weight ratio 1: 4.2; reaction temperature 235 to 250"C.

The present invention will now be further described by means of the following Examples which describe the composition and action of some of the washing agents in accordance with the invention, and the carrying out of the washing method in accordance with the invention. The hydroxyalkylated polyamides I to XHI described above were used as effective substances.

Example 1 This Example describes the composition of a foam-inhibited cold washing agent which is particularly suitable for washing in a machine.

6.0 percent by weight of sodium dodecylbenzene sulphonate; 1.0 percent by weight of an adduct of 1 mol of tallow alcohol and 14 mol of ethyleneoxide; 1.0 percent by weight of an adduct of 1 mol of oleyl-/cetylalcohol and 10 mol of ethyleneoxide; 1.0 percent by weight of alkoxylated polyamide 3.0 percent by weight of soap (sodium salt of C18-C22 fatty acids); 60.0 percent by weight of sodium triphosphate; 2.0 percent by weight of water glass (Na2O - 3.35 SiO2); 0.2 percent by weight of sodium ethylenediamine tetraacetate; 1.2 percent by weight of carboxymethyl cellulose sodium salt; Remainder sodium sulphate and water.

Launderometer tests with the alkoxylated polyamides were carried out under the following conditions in order to demonstrate the cold washing ability; Washing temperature 20"C; water hardness 16"d; washing agent concentration 4.0 g/l; liquor ratio 1: 30 with finished cotton and polyester/cotton fabric; washing duration 30 minutes. A comparison was made with a washing agent which additionally contained 1 percent by weight of sodium sulphate or 1 percent by weight of sodium dodecylbenzene sulphate instead of the hydroxyalkylated polyamide. The marked improvement in the washing ability when using the washing agent in accordance with the invention is clearly shown by the following numerical values of the degree of brightness measured on the test fabrics.

TABLE 1 Washing agent in % Reflectance accordance with Finished Finished Example 1 cotton cotton/polyester la) With 1% Product VI 61.9 47.8 lb) With 1% Product VIII 65.8 49.8 ld) With 1% of sodium 53.8 44.6 dodecylbenzene sulphonate le) With 1% sodium sulphate 53.2 44.3 Further examples of washing and cleaning agents in accordance with the invention will now be given in a Table. The salt-like constituents of the washing or cleaning agents (salt-like surfactants, other organic salts and inorganic salts) mentioned in the Examples are present in the form of sodium salts, unless otherwise stated.The designations and abbreviations in the Examples have the following meanings: "ABS": the salt of an alkylbenzene sulphonic acid, obtained by the condensing of straight chain olefins with benzene and sulphonation of the alkylbenzene produced, and having 10 15, essentially 11 - 13 carbon atoms in the alkyl chain; "Olefin sulphonate": a mixture of hydroxyalkane-, alkane- and disulphonates obtained by sulphonation of a-olefins having 12 - 18 carbon atoms with S03 and hydrolyzing the product of sulphonation with caustic soda; "Fs ester sulphonate": a sulphonate obtained from hydrogenated palm kernel fatty acid methylester by way of sulphonation with S03; "Alkane sulphonate": a sulphonate obtained by way of sulphoxidation of C12-18 paraffins; "Soap": a soap produced from a hardened mixture of equal parts by weight of stearic fatty acid and rape oil fatty acid (iodine number = 1); "TA+x EO": the products of addition of ethyleneoxide (EO) to tallow fatty alcohol (TA) (iodine number 0.5), wherein the numerical data for x characterise the molar quantity of ethyleneoxide added to 1 mol of alcohol; "Bleaching activator": the compound tetraacetylglycoluril; "Perborate": a technical product of the approximate composition NaBO2 . H202 3 H20.

"EDTA": the salt of ethylenediamine tetraacetic acid; "NTA": the salt of nitrilotriacetic acid; "CMC": the salt of carboxymethyl cellulose.

The constituents of the washing agents in accordance with the invention, particularly the builder substances, are chosen such that the preparations react neutral to distinctly alkaline, so that the pH value of a 1% solution of the preparation lies in the range of from 7 to 12.

Fine washing agents have a neutral to slightly alkaline reaction (pH value = 7 to 9.5), while soaking, pre-washing and boiling washing agents are adjusted so as to have a stronger alkaline reaction (pH value = 9.5 to 12, preferably 10 to 11.5).

In the Examples given in the following Table 2, Examples 2, 3 and 9 involve pulverulent washing agents having a bleaching action, Examples 4 and 5 involve pulverulent pre- and main washing agents without a bleaching action, while Examples 6 to 8 constitute a pulverulent fine washing agent or a liquid washing agent or a pulverulent washing agent free from phosphate. The desired improvement in the washing power is also obtained when other alkoxylated polyamides in accordance with the invention are used in the washing agent formulations of Table 2.

TABLE 2 Constituents Washing agent constituents in % for Examples 2 3 4 5 6 7 8 9 ABS 6.0 - - - 6.5 - 6.0 6.0 TA + 14 EO 1.0 - 1.0 1.5 - 4.0 1.0 2.5 TA + 5 EO 1.0 1.5 1.0 - - - 1.0 1.5 Fs ester sulphonate - - 3.0 6.0 - - - Alkane sulphonate - - - - - 8.0 - Olefin sulphonate - 6.0 3.0 - - - - Tallow alcohol-3EO- - - - - 4.0 - - sulphate Soap 3.5 3.5 2.5 3.0 0.5 - 3.0 3.0 Potassium- - - - - - 4.0 - toluene sulphonate Alkoxylated Product II 1.0 - - - 1.5 1.5 - 1.5 Product V - - 1.0 - - 1.8 - polyamide Product IX - 1.0 - - - - 1.5 Na5P3O10 40.0 30.0 60.0 55.0 40.0 - - 40.0 NTA - 5.0 - 5.0 - - - K4P2O7 - - - - - 10.0 - EDTA 0.2 0.2 - - - - 0.2 0.2 Perborate 15.0 15.0 - - - - 20.0 25.0 Bleaching 15.0 15.0 - - - - - activator Water glass 3.0 3.0 4.0 5.0 3.5 - 15.0 3.0 Soda - - 3.0 3.0 - - 6.0 Mg silicate 2.0 2.0 - - - - 2.0 2.0 CMC 1.5 1.8 1.5 1.4 - - 1.2 1.5 Isopropylalcohol - - - - - 5.0 - Remainder: Nasulphate, enzymes, Remainder optical brighteners, water perfume, water

Claims (17)

WHAT WE CLAIM IS:

1. A textile washing composition comprising a combination of at least one anionic, non-ionic or zwitterionic surfactant and a water-soluble alkoxylated polyamide which contains bound ethyleneoxide and/or glycidol and/or propyleneoxide and/or butyleneoxide in a quantity equal to at least half of the weight of the polyamide, the weight ratio of the surfactant to hydroxyalkylated polyamide being from 50 : 1 to 2 : 1.

2. A composition as claimed in claim 1 in which the water-soluble alkoxylated polyamide contains bound ethyleneoxide and/or glycidal and/or propyleneoxide and/or butyleneoxide in a quantity equal to at least two-thirds of the weight of the polyamide.

3. A composition as claimed in claim 1 or 2 in which the weight ratio of surfactant to alkoxylated polyamide is from 20 : 1 to 2 : 1.

4. A composition as claimed in claim 1, 2 or 3 in which the water-soluble alkoxylated polyamide has a turbidity point in water (determined in accordance with DIN 53917) in excess of 20"C.

5. A composition as claimed in any one of claims 1 to 4, containing 0.5 to 2.5 percent by weight of the hydroxyalkylated polyamide together with a surfactant content of 5 to 50 percent by weight.

6. A composition as claimed in claim 5 in which the surfactant comprises a synthetic anionic surfactant of the sulphonate or sulphate type, with or without a non-ionic surfactant and/or a zwitterionic surfactant.

7. A composition as claimed in any one of claims 1 to 6, in which the alkoxylated polyamide is the reaction product of a polyamide with ethyleneoxide and/or with ethyleneoxide and subsequently propleneoxide in the ratio defined in claim 1.

8. A composition as claimed in any one of claims 1 to 7, having the following composition: (a) 5 - 50 percent by weight of at least one surfactant selected from sulphonate and sulphate surfactants and non-ionic surfactants of the ethoxylated alkanols, alkenols and alkylphenols type, (b) 0.5 - 2.5 percent by weight of the alkoxylated polyamide as defined in claim 1, (c) 0 - 8 percent by weight of a foam inhibitor selected from alkali metal soaps having essentially C,8-C22 fatty acid radicals, and non-surfactant foam inhibitors, (d) 50 - 94.5 percent by weight of pulverulent and/or liquid carrier substances selected from pulverulent organic and inorganic builder substances, water-soluble low alcohols, diols and ether alcohols and water, optionally including a bleaching component, and (e) 0 - 10 percent by weight of additives for washing agents selected from optical brighteners, enzymes, dirt carriers, textile softeners, antimicrobial effective substances, dyes and perfumes.

9. A composition as claimed in claim 8 in which component (a) is present in an amount of from 5 to 25 percent by weight.

10. A composition as claimed in claim 8 or 9 in which component (c) is present in an amount of from 0.2 to 5 percent by weight.

11. A composition as claimed in claim 8, 9 or 10 in which component (d) is present in an amount of from 55 to 90 percent by weight.

12. A composition as claimed in any one of claims 8 to 11 in which component (e) is present in an amount of from 0.5 to 10 percent by weight.

13. A method of washing textiles comprising contacting the textiles with an aqueous washing liquor containing a washing composition as claimed in any one of claims 1 to 12, agitating the textiles, manually or in a machine, at a temperature between 10 and 30"C for 10 to 60 minutes, the washing composition being present in the aqueous liquor in an amount of from 1.0 to 12.0 gull, removing the textiles from the washing liquor and rinsing said textiles with fresh water to remove the constituents of the washing liquor.

14. A method as claimed in claim 13 in which the washing composition is present in the aqueous liquor in an amount of from 4.0 to 10.0 g/l.

15. A method as claimed in claim 13 or 14 in which the washing temperature is from 15 to 250C.

16. A composition as claimed in claim 1 and substantially as hereinbefore described with reference to any one of the Examples.

17. A method as claimed in claim 13 and substantially as hereinbefore described with reference to any one of the Examples.