DE1922450A1 - Detergents and cleaning agents - Google Patents

Description

Henkel & Cie GmbH Düsseldorf, April 30, 1969

Patent department ■ HenkeIstr. 67

Dr. Wa / Ml 1922450

Patent application D 386O

"Detergents and cleaning agents"

It is known detergents and cleaning agents that are surface-active Contain compounds to add substances that improve the dirt-carrying capacity of the detergent liquors. Such, hereinafter referred to as graying inhibitors Substances prevent the detached dirt from being resorbed on the cleaned surfaces. It deals are mostly polyanionic polymers, which are either made from natural substances, such as cellulose, gelatin or glue or by polymerizing vinyl compounds such as acrylic acid, methacrylic acid, maleic acid and their mixtures with copolymers isable olefins are produced. The polysulfonates of vinyl polymers have also been used to inhibit graying Additives to detergents and cleaning agents recommended. Of the compounds in question, however, only carboxymethyl cellulose has gained greater technical importance, especially since it inhibits graying Effect surpasses all known synthetic polymers. The carboxymethyl cellulose and also those mentioned However, synthetic polymers have the disadvantage that their anti-graying effect is limited to cellulose fibers is while they are washing synthetic fiber material, chemically modified or refined cellulose Cotton are largely ineffective. This disadvantage is particularly evident in relation to white textiles made of polyester or polyolefin fibers, non-iron finished cotton as well as blended fabrics from the named synthetic

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Noticeable fibers with cellulose fibers, which turn gray when used despite frequent washing and are therefore unsightly can be.

The object was to develop a means which does not have the disadvantages mentioned above.

The invention relates to detergents and cleaning agents with a content of surface-active washing raw materials and, if necessary, of non-surface-active structural salts and cleaning w reinforcing compounds, which are characterized in that they contain 0.1 to 20 percent by weight, based on the amount of solids present, of water-soluble or water-dispersible polyamides which are obtainable by reacting polyethyleneimine or polypropyleneimine with an average molecular weight of 300 to 600O with 2 to 10 carbon atoms in the molecule containing di- and / or tricarboxylic acids and in which the molar ratio of alkyleneimine unit to polybasic carboxylic acid is 100: 1 to 5 J 1.

The polyamides * contained in the new detergents are on known way available. Polyäthylenimines are preferably used as starting materials, the average molecular weight 500 to 60000, in particular 500 to J5000. As polycarboxylic acids aliphatic or cycloaliphatic, saturated or unsaturated and aromatic di- and tricarboxylic acids are suitable, such as oxalic, malonic, succinic, glutaric, adipic, pimeline, cork, azelaic, sebacic, maleic and fumaric acid, Benzene dicarboxylic acids, citric acid, tricarballylic acid, trimesic acid and cyclohexanetrarboxylic acids, as well as polyvalent ones Carboxylic acids containing heteroatoms, in particular Xther, thioether and amino groups. Examples of such multivalued

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Carboxylic acids are diglycolic acid, thiodiglycolic acid, iminodiacetic acid and nitrilotriacetic acid. Mixtures too of the above-mentioned carboxylic acids can be used. The reaction products of polyethyleneimine with dicarboxylic acids are preferred.

The polyamides are prepared in a known manner, for example by heating the acid for several hours and polyalkyleneimine existing mixture in vacuo or in the presence of a solvent with which the water of reaction can be distilled off azeotropically. Instead of the free di- or tricarboxylic acids, their reactive ones can also be used Derivatives, e.g. the anhydrides, chlorides or bromides are used as starting materials. Per alkylenimine unit preferably such amounts of dicarboxylic or tricarboxylic acid applied that a macromolecule consisting of polyalkyleneimine is at least one mole of a di- or tricarboxylic acid. Depending on the average molecular weight of the polyalkylenimine, the molar ratio of alkylenimine to polybasic carboxylic acid in the preferred range of 50: 1 up to 10: 1.

The polyamides produced in the manner suggested are of a resinous consistency and in water or detergent solutions soluble or dispersible. They can still contain minor amounts of unreacted raw materials, which are removed by extraction with organic solvents and optionally reacted again can be. However, since these compounds do not impair the cleaning properties of the agents, separation is necessary not mandatory. As a result of the insolubility of the high molecular weight compounds in organic solvents and

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Because of their content of low molecular weight fractions, the usual methods of determining molecular weight fail. The degree of polymerization and molecular weight of the polyamides can therefore not be satisfactory Specify accuracy.

In addition to the polyamides, the detergents according to the invention contain and cleaning agents, the surface-active substances customary in such agents, such as anionic, nonionic or zwitterionic washing active substances. Furthermore, non-surface-active inorganic and / or organic structural ■ Salts as well as compounds must be present, which the cleaning power increase the means or the whiteness of the treated textiles.

Suitable detergent raw materials are those of the sulfonate or sulfate type, for example alkylbenzenesulfonates, in particular n-Dodecylbenzenesulfonate, also olefin sulfonates, such as them for example by sulfonating primary or secondary aliphatic monoolefins with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis, as well as alkyl sulfonates, such as those obtained from n-alkanes by Sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by addition of bisulfite to olefins are available. Also suitable are -sulfo fatty acid esters, primary and secondary alkyl sulfates and the sulfates of ethoxylated or propoxylated higher molecular weight Alcohols.

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Further compounds of this class, which may possibly be present in the detergents, are the higher molecular weight silfated ones Partial ethers and partial esters of polyhydric alcohols, such as the alkali metal salts of the monoalkyl ethers or the Monofatty acid ester of glycerol monosulfuric acid ester or 1,2-dioxypropanesulfonic acid. There are also sulfates of ethoxylated or propoxylated fatty acid amides and Alkylphenols as well as fatty acid taurides and fatty acid isethionates are possible.

Other suitable anionic washing raw materials are alkali soaps of fatty acids of natural or synthetic origin, e.g. the sodium soaps made from coconut, palm kernel or tallow fatty acids. As zwitterionic washing raw materials come alkyl betaines and especially alky sulfobetaines possible, e.g. 3- (N, N-dimethyl-N-alkylammonium) -propane-1-sulfonate and 3- (N, N-dimethyl-N-alkylammonium) -2-hydroxypropane-1-sulfonate.

The anionic detergent raw materials can be in the form of the sodium, potassium and ammonium salts as well as organic salts Bases such as mono-, di- or triethanolamine are present. If the mentioned anionic and zwitterionic Compounds have an aliphatic hydrocarbon radical, this should preferably be straight-chain and to 22 carbon atoms. Contained in the compounds with an araliphatic hydrocarbon radical the preferably unbranched alkyl chains have an average of 6 to 16 carbon atoms.

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Suitable nonionic surfactants washing-active substances in particular polyglycol ether derivatives of alcohols, fatty acids and alkylphenols suitable which contain from 3 up JO glycol ether groups and 8 to 20 carbon atoms in the hydrocarbon radical. Polyglycol ether derivatives in which the number of ethylene glycol ether groups is 5 to 15 and whose hydrocarbon radicals are derived from straight-chain, primary alcohols with 12 to 18 carbon atoms or from alkylphenols with a straight-chain alkyl chain having 6 to 14 carbon atoms are particularly suitable. By adding 3 to 15 moles of propylene oxide to the last-mentioned polyethylene glycol ethers or by converting them into acetals, detergents are obtained which are distinguished by a particularly low foaming power.

Other suitable nonionic washing raw materials are the water-soluble 20 to 250 ethylene glycol ether groups and polyethylene oxide adducts containing 10 to 100 propylene glycol ether groups with polypropylene glycol, ethylene diamino polypropylene glycol and alkyl polypropylene glycol having 1 to 10 carbon atoms in the alkyl chain. The mentioned Compounds usually contain per propylene glycol unit 1 to 5 ethylene glycol units. Also non-ionic compounds of the amine oxide and sulfoxide type, which can optionally also be ethoxylated can be used.

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Suitable components of the mixture are also inorganic cleaning salts, especially condensed phosphates, such as pyrophosphates, triphosphates, tetraphosphates, trimetaphosphates, tetrameta phosphates and more highly condensed phosphates in the form of the neutral or acidic sodium, potassium or ammonium salts. Alkali metal triphosphates and their mixtures with pyrophosphates are preferably used. Furthermore, silicates are possible, in particular sodium silicate, in which the ratio of NapO: SlOp is 1: 2.5 to 1 ' 1.

The condensed phosphates can also be wholly or partially replaced by organic, cleansing, nitrogen- or phosphorus-containing complexing agents. These include the alkali or ammonium salts of nitrilotriacetic acid, ethylenediaminotetraacetic acid, diethylenetriaminopentaessic acid and the higher homologues of the aminopolycarboxylic acid mentioned. Suitable homologs can be prepared, for example, by polymerizing an ester, amide or nitrile of N-acetic acid aziridine and subsequent saponification to carboxylic acid salts or by reacting polyamines with a molecular weight of 500 to 100,000 with chloroacetic acid or bromoacetic acid salts in an alkaline medium. Further suitable aminopolycarboxylic acids are poly (N- * ß-proplonic acid) -ethylenimines with an average molecular weight of 500 to 200,000, which are obtainable analogously to the N-acetic acid derivatives. Useful phosphorus-containing complexing agents are the alkali metal and Ammoniumsalse of aminopolyphosphonic acids, in particular aminotri (methylenephosphonic acid), ßthylendiarainotetra- (raeth5 ^r lGnphosphonsäure), 1-hydroxyethane-l, 1-diphosphonic acid, methylenediphosphonic of said polyphosphonic acids, Xthylendiphösphonsäure as well as the higher homologues "Mixtures the aforementioned complexing agents can be used.

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ORIGINAL

Henkel & CIe GmbH page "to the patent application D

Neutral salts are also used as components of the mixture, such as sodium sulfate and sodium chloride, as well as substances for regulating the pH value, such as bicarbonates, Carbonates, borates and hydroxides of sodium or potassium, as well. Acids such as lactic acid and citric acid. The crowd ■ the alkaline reacting substances including the alkali silicates and phosphates should be dimensioned so that the pH value of a usable lye is 9 to 12 for coarse washing and 6 to 9 for heavy washing. ■

Through a suitable combination of different surface-active detergent raw materials or builder salts with one another, increases in effectiveness, for example improved washing power or reduced foaming power, can be achieved in many cases. Such improvements are possible, for example, by combining anionic with nonionic and / or zwitterionic compounds with one another, by combining different nonionic compounds with one another or by mixtures of detergent raw materials of the same type, which differ in terms of the number of carbon atoms or the number and position of double bonds or Differentiate chain branches in the hydrocarbon. Likewise, synergistic mixtures of inorganic and organic synthesis salts can be used or combined with the mixtures mentioned above. _s .

Depending on their intended use, the agents can contain oxygen-releasing bleaches, such as hydrogen peroxide, alkali perborates, alkali percarbonates, alkali perphosphates, urea perhydrate and alkali persulfates or compounds containing active chlorine, such as Al: - potassium hypochlorites, chlorinated trisodium phosphate and chlorinated cyanuric acid or its alkali salts. The per compounds can be mixed with bleach activators and Stabilizers such as magnesium silicate are present.

Henkel & Cie GmbH Since · 9 for patent application D

Suitable optical brighteners are those of the bis (triazinyl) ~ 4,4 ^r -diaminostilbene disulfonic acid type of the formula:

in which X and Y have the following meanings: NHp, NH-CH- ,, "NH-CH ₂ -CH ₂ OH, CH ₅ -N-CH ₂ -CH ₂ OH, N (CH ₂ -CH ₂ OH) ₂ , Morpholine), Dimethylmorpholi.no, NH-CgH ₅ , NH-CgPI ₂₁ -SO ₅ H, OCH ₅ , Cl, where X and Y can be the same or different. Those compounds in which X is an anilino and Y represent a diethanolamino or morpholine group.

Optical brighteners of the diarylpyrazoline type are also used the following formula is possible;

Ar-C-CH ₀

■ ι ι ² ·

N CH ₀
²

Ar

In this formula, Ar and Ar ¹ denote aryl radicals, such as phenyl, diphenyl or naphthyl, which can carry further substituents, such as hydroxy, alkoxy, hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, sulfonic acid and sulfonamide groups or Halogen atoms. A 1,3-diarylpyrazoline derivative is preferably used in which the radical Ar is a p-sulfonamidophenyl group and the radical Ar 'is a p-chlorophenyl group. In addition, whiteners suitable for lightening other types of fibers may also be present, for example those of the naphthotriazole stilbene sulfonate, ethylene-bis-benzimidazole, ethylene-bis-benzoxazole, thiophene-bis-benzoxazole, dialkylaminocoumarins and cyanoanthracene type. These brighteners bzv /. Their mixtures can be contained in the agents in amounts of 0.01 to 1.5% by weight, preferably 0.1 to 1% by weight.

Henkel & CIe GmbH s · »· 10 _for avoiding ponmon d 3860

In order to increase the dirt-carrying capacity, further known graying inhibitors can be added, such as sodium cellulose glycolate or the water-soluble alkali salts of polyesters and polyamides containing free carboxyl groups or vinyl polymers. These include the polyesters or polyamides made from tricarboxylic and tetracarboxylic acids and divalent ones Alcohols or diamines, as well as polymeric acrylic, methacrylic, maleic, fumaric, itaconic, citraconic and aconitic acids as well the copolymers of the unsaturated carboxylic acids mentioned or their copolymers with olefins.

Agents intended for use in drum washing machines suitably contain known foam-suppressing agents, for example saturated fatty acids or their alkali soaps with 20 to 2k carbon atoms or triazine derivatives, which are obtained by reacting 1 mole of cyanuric chloride with 2 to 5 moles of an aliphatic, straight-chain, _v branched or cyclic primary monoamine or by propoxylation or butoxylation of melamine.

To further improve the dirt-releasing properties of the agents according to the invention, they can also contain enzymes from the class of proteases, lipases and amylases. The enzymes can be of animal and vegetable origin, for example from digestive enzymes or yeasts, such as pepsin, pancreatin, trypsin, papain, catalase and diastase. Preferably from bacterial strains or fungi such as Bacillus subtilis and Streptomyces griseus, Enzymatic active substances obtained used, to alkali, compounds and anionic detersive substances are relatively resistant be .and not inactivated appreciably at temperatures between k5 and 70 ⁰ C.

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The detergents and cleaning agents can be liquid, pasty or solid, for example powdery, granulated or lumpy form. Liquid preparations can contain solvents miscible with water, in particular xthanol and i-propanol as well as solubilizers, such as the alkali salts of benzene, toluene, xylene or xethylene benzene sulfonic acid. To increase foaming power and improving skin tolerance If necessary, alkylolamides, such as fatty acid mono- and diethanolamides, can be added. Also can the mixtures of dyes and fragrances, bactericidal agents, agents with a finishing effect and fillers, for example urea.

The preparation of the agents according to the invention can be carried out in a conventional manner Way by mixing, granulating or spray drying. If enzymes are used, it is recommended themselves, these with non-ionic detergent raw materials and possibly fragrances to mix or to disperse in the melt of a salt containing water of crystallization, e.g. Glauber's salt and then these premixes with the remaining powder ingredients to unite. As a result, the enzymes are cemented to the remaining powder particles, so that the mixtures do not tend to form dust or separate.

The qualitative and quantitative composition of the invention Means largely depends on their area of application. The content of polyamide from polycarboxylic acid and polyalkyleneimine is 0.1 to 20, preferably 0.2 to 10 percent by weight. The difference from 80 to 99 »1 * preferably 90 to 99 # 8 percent by weight applies to other detergent ingredients, the quantitative composition of which can correspond to the following scheme (data in percent by weight):

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1 to 40 % of at least one compound from the class of anionic, nonionic and zwitterionic washing active substances,

10 to 80 # of at least one non-surface active, cleaning-enhancing or complexing building salt,

10 to 50 % of a per-compound, in particular sodium perborate containing water of crystallization or anhydrous, and mixtures thereof with stabilizers and activators, 0.1 to 20 % other auxiliaries and additives.

The washing active substances can consist of up to 100%> preferably 5 to 70 % from compounds of the sulfonate and / or sulfate type, up to 100 %, preferably 5 to 40 % from nonionic compounds of the polyglycol ether type and up to 100 %, preferably 10 to 50% % consist of soap. The synthesis salts can contain up to 100 % , preferably 25 to 95% of alkali metal triphosphates and mixtures thereof with alkali metal pyrophosphates, up to 100%, preferably 5 to 50 % of an alkali metal salt of a complexing agent from the class of polyphosphonic acids, nitrilotriacetic acid, ethylenediaminotetraacetic acid and up to 100% % t preferably 5 to 75 % be composed of at least one compound from the class of the alkali metal silicates, alkali metal carbonates and alkali metal borates. f

The other auxiliaries and additives include, in addition to the optical brighteners, in particular the foam inhibitors, which can be present in the agents according to the invention in an amount of up to 5 % , preferably in an amount of 0.2 to 3%, and also the enzymes which are present in an amount of up to 5 %, preferably 0.2 to 5 % , and the additional graying inhibitors, the proportion of which can be up to 5 %, preferably 0.2 to 3 % .

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Henkel & Cie GmbH soap 13 «ir patent application D 86

The following is a recipe that has proven particularly successful in practice.

Examples

A. Powdered, low-foaming detergent:

- 15 % sulfonate detergent raw material from the class of alkylbenzenesulfonates, olefin sulfonates and n-alkanesulfonates,

0.5 - 5 % alkyl polyglycol ether (C ^ -C ^ g-alkyl) or alkylphenol polyglycol ether (Cg-C ^ -alkyl) with 5 to 10 ethylene glycol ether groups, - 5 % soap C ₁₂ -C ₁ Q,

0.2 - 5 #> foam suppressants from the class of trialkylmelamines and saturated fatty acids or their alkali soaps with 20 - 24 carbon atoms,
- 50 % of a condensed alkali metal phosphate

the class of pyro- or tri-polyphosphates,

0.1 - 5 $> Polyamide made from polyethyleneimine and di- or tricarboxylic acids

- 5 % sodium silicate,

- 35 % sodium perborate tetrahydrate, 5 % enzyme,

0.05 - 1% of at least one optical brightening agent from the class of the diaminostilbene disulfonic acid or DiaryIpyrazoline derivatives,

0.1 - 30 % of an inorganic salt from the class

of carbonates, bicarbonates, borates, sulfates and chlorides of alkali metals, 4 % magnesium silicate,

0.5-3 % sodium cellulose glycolate. .

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The graying-inhibiting effect of the compounds described in the following examples was tested by the known "soil redeposition" method [see H. STÜPEL "Textil-Praxis" Vol. 3, page 264 (1954) 1. In a laboratory washing machine (Lounder-Ometer ^ H ATMS, Chicago USA) 4 lobes from the tissue to be examined with a total weight of 8.3 g together with 1.3 g of an artificially soiled cotton yarn are washed up to three times for 30 minutes. Then the reflection value is measured with a photometer (Elrepho ^ der Pa. <
Filters No. 6).

meter (Elrepho ^ the Pa. CARL ZEISS, using the

The practical dust / fluff combination used to soil the cotton yarn consists of a mixture of kaolin, black iron oxide, soot and synthetic skin fat (from 1/3 fatty acids, 1/3 ^v 'jit and 1/3 hydrocarbons). After soiling, the cotton yarn contains approx. 11 % pigments and approx. 2 % skin fat «

Was a detergent used with the compositions in percent by weight)?

8 % n-dodecylbenzenesulfonate (sodium salt)

3 % oleyl alcohol with 10 ethylene glycol ether groups

3 % Na soap from saturated Cg-C ^ -fatty acids

40 % pentasodium triphosphate

22 f> sodium perborate

3.5 % sodium silicate (Na ₃ O: SiO ₂ = Ii3.3)

2.5 % magnesium silicate

$ 0.2> Na nitrilotriacetate

0.3 fo optical brighteners

4 % of graying inhibitors were added to this agent. The difference up to 100 % was due to sodium sulfate.

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The use concentration of the detergents was 5 g / l * the hardness of the water 10 ° dH. The textile samples of synthetic fabric (polyester fiber) and mixed fabrics (cotton, polyester fiber with enriched polypropylene fiber Rait cotton) were stirred at 6O ⁰ C, the washed out of refined Baunwolle at 90 ⁰ C. The weight ratio of textile to the wash liquor was 1:50. After a washing time of 50 minutes, the textile samples were rinsed four times with distilled water. After three washing treatments, the whiteness of the samples was determined photometrically.

For the production of the graying inhibitors according to the invention became a solution of polyethyleneimine and polybasic carboxylic acid heated to boiling in xylene until 2 mol V / water per mole of polyvalent carboxylic acid distilled off azeotropically was. The resin remaining after the solvent had been distilled off could be used without further aftertreatment.

The average molecular weight of the Polyäthyleniminsj used the carboxylic acid used and the molar ratio (mol of ethyleneimine units to mol of di- or tricarboxylic acid) can be found in the table below, as are the reflectance values of the washed textiles. Washing tests were carried out for comparison without using a graying inhibitor or under Use of sodium cellulose glycolate is carried out. the Results show a clear superiority of the invention Middle.

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Seto

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to the Palent application O

Graying inhibitor Molver Remission values of the polyester Textile samples cotton 56.7 Refined Molecular dicarboxylic acid ratio polyester refined with polypropylene 65.7 59.8 cotton weight of the with cotton 65.3 54.1 Beijp. Poly «thy -
lenimini 14 il 60.5 60.2 8Ο.1 2 600 oxalic acid 28: 1 58.9 66.6 53.8 80.5 3 1200 * 42: 1 60.9 57.0 58.3 81.7 4th 1800 " 14 il 58.7 61.4 59.9 80.3 5 600 succinic acid 28: 1 58.9 74.7 63.0 78.6 6th 1200 " 42: 1 56.0 76.3 62.4 82.6 7th 1800 14 ti 58.6 63.9 59.4 79.4 8th 600 adipic acid 28: 1 58.2 66.4 57.6 75.2 9 1200 " 42: 1 59.3 61.1 58.9 82.5 10 1800 14: 1 60.3 63.9 48.7 80.5 U 600 terephthalic acid 28: 1 60.8 75.3 50.2 77.6 12th 1200 " 42: 1 67.2 76.6 50.5 82.5 IS 1800 14 ti 62.1 74.3 35.6 81.4 14th 600 citric acid 28: 1 57.6 53.1 36.0 82.0 15th 1200 " 42: 1 58.7 53.4 81.8 16 1800 59.7 60.7 A. without graying inhibitor 38.7 60.5 B. Nitrium cellulose glycolate 38.9

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Claims (17)

Henkel & CIe GmbH since "17" for PotinNmmtldune D patent claims 1. Washing and cleaning agents with a content of surface-active substances Washing raw materials and possibly non-surface-active builder salts and cleaning-enhancing effects Compounds, characterized in that they contain 0.1 to 20 percent by weight, based on the amount of solids present, of water-soluble or water-dispersible polyamides obtained by reacting polyethyleneimine or polypropyleneimine with an average molecular weight of 500 to 6000 with 2 to 10 carbon atoms in the molecule Di- and / or tricarboxylic acids are available. and in which the molar ratio of alkylenimine unit to polyvalent carboxylic acid is 100: 1 to 5 5 1. 2. Agent according to claim 1, characterized by a content of polyamides obtainable from polyethyleneimine from the middle Molecular weight 500 to 5000 and polybasic carboxylic acids. 3. Means according to claim 1 and 2, characterized by a Content of polyamides, obtainable from dicarboxylic acids and polyethyleneimine. 4. Means according to claim 1 and 2, characterized by a content of polyamides, obtainable from citric acid and polyethyleneimine. 5 · Means according to claim 1 to 4, characterized by a Content of polyamides in which the molar ratio of xthylenimine units to polybasic carboxylic acid is 50: 1 to 10: 1 amounts to. 6. Composition according to claim 1 to 5, characterized in that the polyamide content, based on solids content, 0.2 to 10 percent by weight. - 18 009845/1700 Henkel Λ CIe GmbH s · »· l8 _zur Pot.ntanm.w _U n _e D 386Ο 7. Composition according to claim 1 to 6, wherein the components not consisting of the polyamide consist of 1 to 40 % of at least one compound from the class of anionic, nonionic and zwitterionic washing active substances. 8. Composition according to claim 1 to 6, wherein the constituents which do not consist of the poly amide consist of 10 to 80 % of at least one non-surface-active builder salt. 9. Means according to claim 1 to 6, wherein the constituents not consisting of the polyamide consist of 10 to 50 % of a per compound and mixtures thereof with stabilizers and activators. 10. Means according to claim J, wherein the washing active substances up to 100 %, preferably 25 to 70 % from those of the sulfonate and / or sulfate type, up to 100 %, preferably 5 to 40 % from nonionic compounds of the polyglycol ether type and up to 100 %, preferably 10 to 50 % consist of soap. r 11. A composition according to claim 8, wherein the structure of salt up to 100%, preferably 25 to 95% of alkali metal triphosphates, and mixtures thereof with alkali metal pyrophosphates, up to 100%, preferably 5 to 50 fo, of an alkali metal salt of a complexing agent from the class of polyphosphonic Nitrolotriacetic acid, ethylenediaminotetraacetic acid and up to 100 %, preferably 5 to 75 %, of at least one compound from the class of alkali metal silicates, alkali metal carbonates and alkali metal borates. 12. Composition according to claim 9 * wherein the per compound consists of anhydrous and / or sodium perborate containing water of crystallization. _Q0 9845/1 Henkel & CIe GmbH StH * 19 * vr ftri «tqMung D 86 13. Composition according to claim 1 to 11, characterized in that it contains up to 5 % » preferably 0.2 to 3 % of at least one foam inhibitor from the class of saturated fatty acids containing 20 to 22 carbon atoms and their alkali metal soaps, and the substituted triazines , obtainable by reacting 1 mole of cyanuric chloride with 2 to 3 moles of a primary monoamine or by propoxylation and / or butoxylation of melamine. 14. Composition according to claim 1 to 12, characterized in that they contain up to 5% » preferably 0.2 to 3 # of enzymes ·. 15. Agents according to Claims 1 to 13, characterized in that they contain up to 5% *, preferably 0.2 to 3 #, of graying inhibitors. 16. Composition according to claim 1 to 14, characterized in that they contain 0.01 to 1.5% of optical brighteners. 17. Agent according to example 1. Henkel k Cie. GmbH, i.V. / (Dr. Haas) '' (Dr. Ifegel) 009845/1780