MXPA99004981A - Textile detergent formulation on the basis of quaternized glycine nitriles, bleaching agents, nonionic and/or anionic tensides and calcium ion and/or magnesium ion sequestering compounds - Google Patents

Abstract

Textile detergent formulation containing a) 0.1 - 10 wt%quaternized glycine nitriles, b) 0.5-40 wt%bleaching agents in the form of peroxo compounds and/or peracids, c) 0.5 - 50 wt%non-ionic and/or anionic tensides and d) 5-85 wt%calcium ion and/or magnesium ion sequestering compounds. The formulation is suitable for household and industrial textile washing, in a dosage of over 2g per litre detergent solution, in particular in a textile:detergent solution bath ratio of 1:10 to 1:2.

Description

FORMULATION DETERGENT FOR TEXTILES BASED ON GLYCINE QUATERZED NITRILE, WHITENERS, SURFACTANTS NO IONICS AND / OR ANIONIC AND COMPOUNDS CAPABLE OF KIDNAPPING IONS OF CALCIUM AND / OR MAGNESIUM The present invention relates to a novel formulation of textile detergent based on quaternized glycine nitriles which act as bleach activators, nonionic - and / or anionic surfactant bleach and compounds capable of sequestering calcium and / or magnesium ions. Furthermore, the invention relates to the use of this detergent formulation for textiles for washing textiles in homes and shops using very specific dose and liquor ratios. Detergent formulations for textiles usually contain a bleach system consisting mainly of peroxo active oxygen donor compounds, percents or mixtures thereof and bleach activators. The most frequently used whitening activator is tetraacetyl ethylene diamine ('TAED') in this case, however bleaching systems of the prior art still do not show optimum cleaning and impurities removal action in commonly used detergent formulations for textiles, and Measured values for bleaching action are still unsatisfactory.

The quaternized glycine nitriles included in the present invention have not yet been described in the prior art published for use as a detergent ingredient for textiles. WOA 96/07650 describes a process for the preparation of quaternized glycine nitriles, but this reference does not mention the possible uses of these compounds. An object of the present invention is to provide a detergent formulation for textiles that achieves an optimal washing, cleaning and whitening action by the precise adjustment of the specific bleach system used to the remaining components of the formulation. Accordingly, we have found a detergent formulation for textiles containing: (A) from 0.1 to 10% by weight of at least one quaternized nitrile glycine of the formula Ia or Ib.

R1 A ^ N® -CR2R3 - CN Y® (la) wherein A represents a four-membered to nine-membered saturated ring containing at least one carbon atom and at least one other heteroatom selected from the group consisting of oxygen, sulfur and nitrogen, R defines a C1-C24 alkyl group which can be interrupted by non-adjacent oxygen atoms or may further carry hydroxyl groups, a C4-C24 cycloalkyl group, an alkaryl group of C-C24 or a grouping of the formula CR2R3CN, R2 and R3 independently define hydrogen, alkyl groups of C1-C24, which can be interrupted by non-adjacent oxygen atoms or can furthermore hydroxyl groups, or define C4-C24 cycloalkyl groups, or C7-C24 alkaryl groups, R defines an alkylene group of C1-C75 which can be interrupted by non-adjacent oxygen and / or sulfur atoms, and Y represents a counterion, (B) from 0.5 to 40% by weight of bleach in the form of peroxo and / or perished compounds, (C) from 0.5 to 50% by weight of surfactants n or ionic and / or anionic in the form of peroxo and / or permeable compounds, (D) from 5 to 85% by weight of at least one compound capable of sequestering calcium and / or magnesium ions. The preferred amounts for the four mentioned components are: (A) from 0.5 to 7% by weight, particularly from 1 to 6% by weight (B) from 5 to 30% by weight, particularly from 10 to 25% by weight (C) ) from 5 to 30% by weight, particularly from 10 to 25% by weight (D) from 10 to 70% by weight, particularly from 15 to 60% by weight and mainly from 25 to 50% by weight. Particularly suitable saturated, heterocyclic ring structures which are formed in the compounds lb or lb by A together with the N atom of the glycine structure are those which contain not only the N atom from the glycine portion but also one or two of other heteroatoms selected from the group consisting of oxygen and nitrogen. The preferred sizes of the ring are rings of five, six and seven members. Examples of suitable heterocyclic systems are imidazolidine, 1,2,3-triazolidine and piperazine. The quaternized glycine nitriles or Ib, in which A and the N atom of the glycine portion together form a six-membered ring containing 4 carbon atoms and one oxygen atom, are particularly preferred. This particularly includes morpholine systems. The radical R, which usually and formally in actual fact is formed by the alkylation of the N atom, defines, for example: a longer straight chain or branched chain alkyl radical, in particular shorter containing 1 at 24 carbon atoms, unsaturated radicals, particularly unsaturated fatty acid radicals, also being suitable, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, myristyl, cetyl, stearyl or oleyl; Alkoxyalkyl radicals, for example methoxymethyl, 2-methoxyethyl, 3-methoxypropyl, 4-methoxybutyl, 2-ethoxyethyl or 3-ethoxypropyl; - hydroxylalkyl radicals, for example hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxybutyl, or 4-hydroxybutyl; - radicals composed of recurring C2-C4 alkylene oxide units such as ethylene oxide, propylene oxide or butylene oxide, which can be terminated by a hydroxyl group or an alkoxy group, for example, - (C2H4? ) n H or - (C2H4?) nR, - C3HeO) m- H, - (C3H60) m-R5, - (C4H80) kH, or - (C4H80) k-R5, (n is 2 to 11, m is 2 to 7, k is 2 to 5, R5 is methyl, or ethyl); cycloalkyl groups such as cyclopentyl, cyclohexyl or cycloheptyl; alkaryl groups such as benzyl, 2-phenylethyl, 3-phenylpropyl or 4-phenylbutyl; - groupings of the formula CH-CN, -CH (CH 3) -CN, or - C (CH 3) -CN. ? It preferably has the following values: alkyl of C1-C4 and benzyl. 2 3 The values of R and R are basically the same as those provided for R 1 (with the exception of CR2R3CN); 2 3 2 3 R and / or R can also define hydrogen; R and R preferably represent hydrogen, methyl and ethyl and in particular 3 R and R are both hydrogen. The bridging member R in the dimeric compounds lb defines, for example, a straight-chain or branched-chain alkylene group containing from 1 to 24 carbon atoms, in particular from 2 to 12 carbon atoms, while the polymethylene groups of C2 -C12 as -CH2CH2-, - (CH2) 4-, - (CH2) 6- / or - (CH2) 8 ~ are preferred. Other examples of R are the groups terminated by alkylene end groups and compounds of alkylene oxide units of C2-C4 recurring such as ethylene oxide, propylene oxide or butylene oxide, such as - (C2H4O) P-C2H4- or - (C3H6?) Q-C3H6- (p is 1 to 36, q is 1 to 24). A particularly suitable alkylating agent, which is usually responsible for the introduction of the R group in the preparation of the compounds la, is dimethyl sulfate, diethyl sulfate, a methyl or ethyl halide, dimethyl carbonate, diethyl carbonate, methyl tosylate, ethyl tosylate, methyl mesylate, ethyl mesylate, or a benzyl halide. By "halides" 'is meant chloride, bromide, or iodide Therefore, the preferred values of the counterion Y "are also CH3OS03 ~, C2H5OS03-, Cl-, Br",? CH30C02 ~, C2H50C02 ~, p-toliIS03-, and CH3S03 ~. The particularly preferred values of Ri are, therefore, methyl, ethyl and benzyl. Dimethyl sulfate is particularly preferred for use as an alkylating agent. The acid sulfate (bisulfate) HSO4 - and / or sulfate SO42- (in half the stoichiometric amount) can also be presented as counterion Y ", which are partially or completely formed for example in the desired hydrolysis of the compounds or having alkylsulfate counterions The analogous bifunctional alkylating agents can be used in the preparation of the dimeric compounds lb.

The quaternized glycine nitriles which are preferably used as component (A) are those in which R defines a C 1 -C 4 alkyl group or a benzyl radical, and R 2 and R 3 define hydrogen. Sulfate, methylisulfate and / or N-methylmorpholinium acetonitrile acid sulfate are particularly preferred for use as component (A). The described quaternized glycine nitriles or lb of component (A) are preferably used as a (granulated) mixture with inert porous support materials, suitable in the normal proportions. These mixtures, or granulated materials can also be shaped. Particularly suitable support materials are those having a large internal surface area (approximately from 10 to 500 m / g, particularly from 250 to 450 m / g, determined by BET) and an average particle size from 3 nm to 2 mm, particularly from 10 nm to 100 mmm [sic]. The support materials are preferably silica gels, silicic acids, aluminum oxides, kaolins or aluminum silicates. An important characteristic of the detergent formulation for textiles of the invention is the correspondence of the component (A) to the component (D). The representatives selected from the group include zeolites, silicates, alkali metal phosphates, polycarboxylates and amino polycarboxylates are preferably used as components (D), alone or in mixtures. These classes of substances function mainly as improvers or enhancers in the detergent formulation for textiles. In accordance with the present invention, component (D) is present in a relatively high amount in the formulation. The zeolites and silicates can be basically preferred as inorganic ion exchangers. Suitable zeolites (aluminum silicates) are particularly those of types A, P, X, B, HS, and MAP in their sodium form or in forms in which sodium is partially substituted by other cations such as Li, K, Ca, Mg, or ammonium. These zeolites are described, for example, in EP-A 038,591, EP-A 021,491, EP-A 087,035, US-A 4,604,224, GB-A 2,013,259, EP-A 522,726, EP-A 384,070 and WO-A 94/24251 . Suitable amorphous or crystalline silicates, particularly lamellar silicates are mainly amorphous disilicates and crystalline disilicates, such as lamellar silicate SKS 6 (marketed by Hoechst).

The silicates can be used in the form of their alkali metal salts, alkaline earth metal salts or ammonium salts. Preferably Na, Li and Mg silicates are used.

A particularly suitable alkali metal phosphate is trisodium polyphosphate, which can likewise be considered as an inorganic ion exchanger. Suitable low molecular weight polycarboxylates and polypropylene carboxylates for use as component (D) are particularly: - C4-C20 dioic, trioic and tetroic acids such as succinic acid, propane tricarboxylic acid, butacarboxylic acid, cyclopentane-tetracarboxylic acid, and alkylsuccinic and alkenyl succinic acids containing C2-C16 alkyl or alkenyl radicals; - C4-C20 hydroxycarboxylic acids, such as malic acid, tartaric acid, gluconic acid, glucaric acid, citric acid, lactobionic acid and saccharosemonic acid, saccharosedioic acid and saccharosetrioic acid; - the chelating polycarboxylate amines such as nitrile triacetic acid, methyl glycine diacetic acid, β-alanindiacetic acid, ethylenediaminetraacetic acid, serine-diacetic acid or ethylene diamine N, N-disuccinate, preferably in the form of their metal salts alkaline, (particularly sodium) partially or completely neutralized. The polycarboxylates and oligomeric or polymeric polycarboxylate polycarboxylates suitable for use as component (D) are in particular: sligomalic acids as described, for example, in EP-A 451,508 and EP-A 396,303; - copolymers and terpolymers of unsaturated C4-C8 dicarboxylic acids, where the comonomers present in the form of polymerized units can be monoethylenically unsaturated monomers selected from group (i) in amounts in the range up to 95% by weight, selected from the group (ii) ) in amounts in the range up to 60% by weight, selected from group (iii) in amounts in the range up to 20% by weight. In this case, suitable unsaturated C 4 -C 8 dicarboxylic acids are, for example, maleic acid, fumaric acid, itaconic acid and citraconic acid. Maleic acid is preferred. Group (i) consists of monocarboxylic C3-Cs monoethylenically unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid. In group (i), acrylic acid and methacrylic acid are preferably used. Group (ii) consists of C2-C22 monoethylenically unsaturated olefins, vinyl alkyl ethers containing Ci-Cs alkyl groups, styrene, vinyl esters of carboxylic acids of Ci-Cs, (meth) acrylamide and vinyl pyrrolidone. In group (ii), C2-C6 olefins, vinyl alkyl ethers containing C1-C4 alkyl groups, vinyl acetate and vinyl propionate are preferably used. Group (iii) consists of (meth) acrylates of Ci-Cβ alcohols, (meth) acrylonitrile, (meth) acrylamides of C?-C8 amines, N-vinylformamide and vinylimidazole.

If the polymers of group (ii) contain vinyl esters incorporated as polymerized units these can be, if desired, partially or completely hydrolyzed to vinyl alcohol structural units. Suitable copolymers and terpolymers are described, for example, in US-A 3,887,806 and DE-A 4,313,909. Suitable copolymers of the dicarboxylic acids for use as component (D) are mainly: copolymers of maleic acid and acrylic acid present in proportions by weight from 10:90 to 95: 5, particularly those present in proportions by weight from 30:70 at 90:10, particularly those that have molecular weights in the range from 1000 to 150,000; - terpolymers of maleic acid, acrylic acid and a vinyl ester of a C 1 -C 3 carboxylic acid present in a weight ratio of 10 (maleic acid): 90 (acrylic acid + vinyl ester) to 95 (maleic acid): 5 ( acrylic acid + vinyl ester), where the ratio of acrylic acid to vinyl ester, by weight, can vary in a range from 20:80 to 80:20; - terpolymers of maleic acid, acrylic acid and vinyl acetate or vinyl propionate present in a weight ratio from 20 (maleic acid): 80 (acrylic acid + vinyl ester) to 90 (maleic acid): 10 (acrylic acid + vinyl ester), wherein the ratio of acrylic acid to vinyl ester, by weight, can vary in a range from 30:70 to 70:30; - copolymers of maleic acid with C2-C8 olefins present in a molar ratio from 40:60 to 80:20, where copolymers of maleic acid with ethylene, propylene or isobutane present in a molar ratio of about 50:50 are particularly preferred . The graft polymers of unsaturated carboxylic acids in hydrocarbons or hydrogenated hydrocarbons of low molecular weight, see US-A 5,227,446, DE-A 4,415,623 and DE-A 4,313,909 are in the same manner suitable for use as the component (D). Suitable unsaturated carboxylic acids are in this case, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid, and also mixtures of acrylic acid and maleic acid, which they are inserted in amounts from 40 to 95% by weight, based on the component that is used to make the graft. As a modification, in addition up to 30% by weight, based on the component to be grafted, of other monoethylenically unsaturated monomers, it can be present in the form of polymerized units. Suitable modifying monomers are the aforementioned monomers of groups (ii) and (iii). Suitable for use as graft base are degraded polysaccharides such as starches degraded by acid or degraded by enzymes, inulins, or zelulose [sic], polysaccharides degraded by reduction (Hydrogenation or hydrogenating amination), such as mannitol, sorbitol, aminosorbitol and glucamine and also polyalkylene glycols with molecular weights Mw up to ,000, such as poly (ethylene glycol) is, poly (ethylene oxide) -block-poly (propylene oxide) or poly (ethylene oxide) -block-poly (butylene oxide) s, poly (ethylene oxide) ) -block-poly (propylene oxide) s or poly (ethylene oxide) -block-poly (butylene oxide) or alkoxylated monobasic or polybasic alcohols of C3.-C22 / see, US-A 4,746,456. Of this group, grafted or degraded degraded degraded starches and grafted poly (ethylene oxide) s are preferably used, where from 20 to 80% of the monomers, based on the grafting component, are used during the graft polymerization. A mixture of maleic acid and acrylic acid present in a ratio, by weight, from 90:10 to 10:90 is preferably used for the grafting operation. Poly (glyoxylic acid) s for possible use as component (D) are described, for example, in EP-B 001,004, US-A 5,399,286, DE-A 4,106,355 and EP-A 656,914. The terminal groups of the poly (glyoxylic acid) s can have different structures. Polyamidocarboxylic acids and modified polyamidocarboxylic acids for possible use as a component (D) are described in EP-A 454,126, EP-B 511,037, WO-A 94/01486, and EP-A 581,452. Poly (aspartic acid) or co-condensate of aspartic acid with other amino acids, C4-C25 mono- or dicarboxylic acids and / or monoamine or C4-C25 diamines are also preferably used as aminopolycarboxylates for component (D). We particularly prefer to use poly (aspartic acid) s which has been prepared in phosphorous acids and modified with mono- or di-carboxylic acids of C6-C22 or with monoamines or C6-C22 diamines. The products of the condensation of citric acid with hydroxycarboxylic acids or polyhydroxy compounds for use as component (D) are described, for example, in WO-A 93/2362 and WO-A 92/16493. These condensates containing carboxyl groups typically have molecular weights of up to 10,000, preferably up to 5,000. We particularly prefer to use, as component (D) in the detergent formulation for textiles of the invention, from these classes of substances zeolite A, zeolite P, zeolite X, lamellar silicates such as SKS 6, sodium polyphosphate, poly (acid) acrylic-co-maleic acid) (particularly those having molecular weights from 10,000 to 100,000), poly (aspartic acid), citric acid, nitrile triacetic acid, methylglycliciacetic acid and mixtures thereof. Particularly interesting mixtures are those containing zeolites and poly (aspartic acid), zeolites and oligomalieic acids, zeolites and poly (acrylic acid-co-maleic acid), trisodium polyphosphate and lamellar silicates, trisodium polyphosphate and poly (acrylic acid). co-maleic acid) s zeolites and trisodium polyphosphate and also containing zeolites, lamellar silicates and poly (acrylic acid-co-maleic acid) s as the respective major ingredients of component (D). In addition to the quaternized glycine nitriles, the other binder activators may also be present in component (A). The compounds of the following classes of substances are suitable for these purposes: compounds of the following classes of substances are suitable for this purpose: sugars or polyacylated sugar derivatives containing acyl radicals of C? -C? Or, preferably acetyl, propionyl , octanoyl, nonanoyl or benzoyl, particularly acetyl radicals, are suitable for use as bleach activators. The mono- or di-saccharides and also their reduced or oxidized derivatives are suitable for use as sugars or sugar derivatives, preferably glucose, mannose, fructose, sucrose, xylose, or lactose. Particularly suitable bleach activators of this class of substances are, for example, pentaacetyl glucose, xylose, tetraacetate, l-benzoyl-2,3,4,6-tetraacetyl glucose and l-octanoyl-2,3,4,6-tetraacetyl glucose. Other bleach activators that can be used are O-acyloxime esters such as O-acetylacetone oxime, 0-benzoyl acetone oxime, bis (propylimino) carbonate, or bis (cyclohexylimino) carbonate. These acylated oximes and oxime esters are described, for example, in EP-A 028,432 and EP-A 26,704. The bleach activators that may also be used are N-acyl caprolactams, such as N-acetyl caprolactam, N-benzoyl caprolactam, N-octanoyl caprolactam or carbonyl bis caprolactam. Other bleach activators that can be used are: N-diacylated and N, N-tetraacylated amines, for example, N, N, N, N-tetraacetylmethylenediamine and N, N, N, N-tetraacetylethylenediamine (TAED), N, N-diacetyl-aniline, N, N-diacetyl-p-toluidine, or 1,3-diacylated hydantoins, such as 1,3-diacetyl-5,5-dimethylhydantoin; N-alkyl-N-sulfonyl carbonamides, for example, N-methyl-N-mesyl acetamide or N-methyl-N-mesylbenzamide; N-acylated cyclic hydrazides, triazoles or acylated urazoles, for example mono acetylmalic acid hydrazide; 0, N, N-trisubstituted hydroxylamines, for example, 0-benzoyl-N, N-succinylhydroxylamine, O-acetyl-N, N-succinyl hydroxylamine or 0, N, N-triacetal hydroxylamine; N, N-diacyl sulphuryl amides, for example, N, N-dimethyl-N, N-diacetylsulfuryl amide or N, N-diethyl-N, N-dipropionylsulfuryl amide; triacyl cyanurates, for example, triacetyl cyanurate or tribenzyl cyanurate; carboxylic anhydrides, for example, benzoic anhydride, anhydride, M-chlorobenzoic or phthalic anhydride; 1,3-diacyl-4, 5-diacyloxy imidazolines, for example, 1,3-diacetyl-4,5-diacetoxy imidazoline; tetraacetyl glucoluril and tetrapropionyl glucoluril; 2, 5-diacylated diketopiperazines, for example, 1,4-diacetyl-2,5-diketonepiperazine; acylation products of propylene diurea and 2,2-di-ethylpropylene diurea, for example, tetraacetyl propylene diurea; α-acyloxy-polyacyl malonamide, for example, -acetoxy-N, N-diacetylmalonamide; - diacyl dioxo-hexahydro-1,3,5-triazines, for example 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine. Bleach activators that can also be used are 2-alkyl- or 2-aryl- (4H) -3, 1-benzoxazin-4-ones, as described, for example, in EP-B 332,294 and EP-B 502,013 . Particularly useful are 2-phenyl- (4H) -3,1-benzoxazin-4-one and 2-methyl- (4H) 3,1-benzoxazin-4-one. Not only quaternized glycine nitriles la or Ib but also other bleach activators are present, the aforementioned amounts of component (A) refers to the total of all bleach activators. The compounds or lb should, however, represent at least 5% by weight and, in particular, at least 10% by weight of the total of all the bleach activators. The combination of the components lb or lb with TAED is of special interest. Suitable bleaches of component (B) are peroxo compounds that mainly release active oxygen. These peroxo compounds are particularly alkali metal perborates such as sodium perborate tetrahydrate and sodium perborate monohydrate and also alkali metal carbonate perhydrates such as sodium carbonate perhydrate ('sodium percarbonate') and also hydrogen peroxide. In addition to these inorganic peroxo compounds, the bleach system of the detergent formulation can contain inorganic or organic perishes, particularly percarboxylic acids, for example C 1 -C 12 percarboxylic acids, Cs-Ciß dipercarboxylic acids, imidopercaphoic acids or aryldipercapróic acids. of the useful acids are peracetic acid, octane-, nonane-, decane- or dodecane-monoperoxy straight or branched chain acids, decandiperoxy acid and dodecanediperoxy acid, mono- and diperphthalic acids, mono- and diisophthalic acids and mono- and di-terephthalic acids, phthalimidoperca acid protic, and percaproic terephthaloidiamide acid. These percarboxylic acids can be used as free acids or as salts of the acids and preferably as alkali metal salts or alkaline earth metal salts. Other examples of the bleaching system of the detergent formulation for textiles of the invention may comprise not only components (A) and (B) but also bleach catalysts and / or bleach stabilizers. The bleached catalysts used are usually quaternized imines or sulfonimines as described, for example, in US-A 5,360,568, US-A 5,360,569 and EP-A 453,003 and also manganese complexes as described, for example, in WO-A 94/21777. Other bleach catalysts containing useful metals are described in EP-A 458, 397, EP-A 458,398 and EP-A 549,272. Bleach catalysts are usually used in amounts in the range up to 1%, particularly from 0.01 to 0.5% by weight, based on the detergent formulation. Bleach stabilizers are additives that can adsorb, bind or complex heavy metal traces that are an impediment to bleaching. In particular, the normal chelating agents such as ethylenediamine tetraacetate, nitrile triacetic acid, methylglycylactic acid, β-alanindiacetic acid, ethylenediamine-N, N-disuccinate and phosphonates, such as ethylenediamine tetramethylene phosphonate, diethylenetriamine penta ethyl ene phosphonate or hydroxyethylidene 1, 1-diphosphonic in the form of the acids or as partially or completely neutralized alkali metal salts are used for this purpose in amounts in the range up to 1% by weight, particularly from 0.01 to 0.5% by weight, based on the detergent formulation. The component (C) used can be any normal non-ionic or anionic surfactant or a mixture thereof. Suitable anionic surfactants are, for example, sulfonates of fatty alcohols or fatty alcohols containing from 8 to 22, preferably from 10 to 18 carbon atoms, for example, Cg-Cn alcohol sulfates, C12-C13 alcohol sulfates, Cetyl sulfate, myristylsulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate. Other suitable anionic surfactants are ethoxylated, sulphated C8-C2o alcohols (alkyl ether sulphates) or the soluble salts thereof. Compounds of this type are prepared, for example, by first alkoxylating a C-C22 alcohol and preferably a C10-C18 alcohol, for example, a fatty alcohol and subsequently sulfating the product of the alkoxylation. Preferably, ethylene oxide is used for the alkoxylation, from 2 to 50, and preferably from 3 to 20 mol of ethylene oxide being used per mole of fatty alcohol. The alkoxylation of the alcohols may otherwise be carried out using propylene oxide alone or optionally together with butylene oxide. Furthermore, alkoxylated C8-C22 alcohols containing ethylene oxide and propylene oxide or ethylene oxide and butylene oxide are suitable. The alkoxylated C8-C22 alcohols may contain the units of ethylene oxide, propylene oxide and butylene oxide in the form of blocks or in random distribution. Other suitable anionic surfactants are alkanesulphonates such as C8-C24 alkanesulphonates and preferably C10-C18 and also soaps as salts of C8-C24 carboxylic acids. Other suitable anionic surfactants are C9-C20 linear alkylbenzene sulfonates (LAS). Other suitable anionic surfactants are N-acyl sarcosinates containing saturated or unsaturated aliphatic C8-C25 acyl radicals and preferably C10-C20 acyl radicals for example, N-oleoyl sarcosinate. The anionic surfactants are added to the detergent formulation, preferably in the form of salts. Suitable cations in these salts are alkali metal ions such as sodium, potassium and lithium and ammonium ions such as hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium ions. Of the above-mentioned anionic surfactants, linear alkylbenzenesulfonates and fatty alcohol sulfonates are of particular interest. Suitable nonionic surfactants are, for example, alkoxylated C8-C22 alcohols such as fatty alcohol alkoxylates or oxo alcohol alkoxylates. The alkoxylation can be carried out using ethylene oxide, propylene oxide and / or butylene oxide. The surfactants useful in this case are all alkoxylated alcohols containing at least two molecules of an alkylene oxide mentioned as added units. Here again, the block polymers of ethylene oxide, propylene oxide and / or butylene oxide or the addition products containing the alkylene oxides mentioned in random distribution are preferred. For each mole of alcohol, it is usually used from 2 to 50 and, preferably, from 3 to 20 moles of at least one alkylene oxide. The alkylene oxide used is preferably ethylene oxide. The alcohols preferably have from 10 to 18 carbon atoms. Another class of suitable nonionic surfactants comprises the alkylphenol ethoxylates containing C6-C14 alkyl chains and from 5 to 30 moles of ethylene oxide units. Another class of nonionic surfactants consists of alkyl polyglucosides containing from 8 to 22 and preferably from 10 to 18 carbon atoms in the alkyl chain. These compounds usually contain from 1 to 20, and preferably from 1.1 to 5 glucoside units. Another class of nonionic surfactants consists of N-alkylglucamides of the general formula II or III.

Rβ - R8 (ID Rβ N - C- R8 (III) where R is C6-C22 alkyl- R is H or C1-C4 alkyl and R is a polyhydroxylalkyl radical containing from 5 to 12 carbon atoms and at least three hydroxy groups. R is 7-8 preferably Cι-Cis alkyl, R is methyl and R a C5-C6 radical. These compounds are obtained, for example, by the acylation of reduced amine sugars with acid chlorides of C 10 -C 18 carboxylic acids. Nonionic surfactants containing from 3 to 12 moles of ethylene oxide contained in the detergent formulation for textiles of the invention are preferably C10-C16 ethoxylated alcohols, ethoxylated fatty alcohols and / or ethoxylated oxo alcohols. Additional components in the detergent formulation for textiles of the invention may be anti-engrising agents and / or normal impurity-releasing polymers in normal amounts (from about 0.1 to about 2% by weight). The impurity and / or anti-engrossing agents suitable for detergents are, for example: polyesters of polyethylene oxide with ethylene glycol and / or propylene glycol and aromatic dicarboxylic acids or aromatic and aliphatic dicarboxylic acids; Polyesters of poly (ethylene oxide) s that are closed at one end by a terminal group with dihydric and / or polyhydric alcohols and dicarboxylic acid. These polyesters are described, for example, in US-A 3,557,039, GB-A 1,154,730, EP-A 185,427, EP-A 241,984, EP-A 241,985, EP-A 272,033 and US-A 5,142,020. Other suitable impurity-releasing polymers are amphiphilic graft polymers or copolymers of vinyl esters and / or acrylic esters on polyalkylene oxides (see, US-A 4,746,456, US-A 4,846,995, DE-A 3,711,229, US-A 4,904,408, US- A 4,846,944 and US-A 4,849,126) or modified celluloses such as methylcellulose, hydroxypropylcellulose or carboxymethylcellulose. Other additional components in the detergent formulation for textiles of the invention may be the normal dye transfer inhibitors in normal amounts (from about 0.1 to about 2% by weight). The dye transfer inhibitors used are, for example, the homopolymers and copolymers of vinyl pyrrolidone, vinyl imidazole, vinyl oxazolidone, and 4-vinylpyridine-N-oxide having molecular weights in the range of 15,000 to 100,000 and also cross-linked polymers finely divided based on these monomers. The use of these polymers is known, see, DE-B 2,232,353, DE-A 2,814,287, DE-A 2,814,329, DE-A 4, 316, 023. Other additional components in the detergent formulation for textiles of the invention can be enzymes normal (in the normal form) in common amounts (from about 0.1 to about 3% by weight).

Suitable enzymes are mainly proteases, lipases, amylases, cellulases, and peroxidases; Enzymes optimized for detergents that are active in an alkaline medium are preferably used. We prefer to use enzymes that are resistant to bleach. Examples of suitable proteases are alcalase, savinase, durazime, and esperasa, (marketed by Novo), maxatase (marketed by Int. Biosynthetics Inc.), FN-Base (marketed by Genencor) and Opticlean (marketed by MCK). Examples of suitable lipases are lipolase and Lipolase Ultra (marketed by Novo). Examples of suitable cellulases are carezymes and celluzymes (marketed by Novo). Examples of the suitable amylases are termamyl and duramil (marketed by Novo). Other conventional components in the detergent formulation for textiles of the invention may be conventional optical brighteners in normal amounts. Examples of commonly used anionic optical brighteners are: Disodium-4,4'-bis (2-diethanolamino-4-anilino-s-triazin-6-ylamino) stilbene-2, 2'-disulfonate, Disodium-4, -bis (2-morpholino-4-anilino-s-triazin-6-ylamino) stilben-2, 2'-disulfonate, Disodium-4, '-bis (2,4-dianilino-s-triazin-6-ylamino) stilbene-2, 2'-disulfonate, Monosodium-4', 4"-bis (2, 4 -dianilino-s-triazin-6-ylamino) stilbene-2-sulfonate, Disodium-4,4'-bis (2-anilino-4 (N-methyl-n-2-hydroxyethylamino) -s-triazin-6-yl) -amino) stilbene-2, 2'-sulphonate, Disodium-4,4'-bis (4-phenyl-2, l-3-triazol-2-yl) stilbene-2,3'-disulfonate, Disodium-4, '-bis (2-anilino- (1-methyl-2-hydroxyethylamino) -s-triazin-6-yl-amino) stilbene-2, 2'-disulfonate, and Sodium-2- (stilbe-4"(naphtho- 1 ',', 24, 5) -1, 2, 3-triazole) -2-sulfonate. In addition, the detergent formulation for textiles of the invention may contain alkaline additives, particularly sodium carbonate and / or sodium bicarbonate, in amounts of up to 40% by weight, and in particular amounts from 1 to 25% by weight and also agents of adjustment, particularly alkali metal sulfates such as sodium sulfate in amounts up to 60% by weight and, in particular, amounts from 1 to 30% by weight. Other additives for the detergent formulation for textiles of the invention may be: foam suppressors, corrosion inhibitors, clays, bactericides, phosphonates, abrasives, dyes and also encapsulated and non-encapsulated perfumes.

The detergent formulation for textiles of the invention preferably exists in the form of a powder or granules having a density density from 200 to 1100 g / l. Otherwise, liquid formulations are possible. The detergent formulation for textiles of the invention may contain the compounds Ia or Ib incorporated in such form that the compounds Ia or Ib are present as pure components or as components that are premixed with suitable additives and distributed in the powder or granules of the detergent , or in such a way that the compounds lb or lb are present as pure components or as components which are premixed with the suitable additives and which have the form of powdery or granular material which is separated from the remaining detergent ingredients. The incorporation of the compounds Ia or Ib as a powdery material or separated granulate, particularly as a premixed product with suitable additives allows the careful preparation of the detergents showing particularly good stability of the bleach activator. The non-compacted powdery or granular detergents have lower density, usually from 200 to 600 g / l. These may contain a phosphate-based improver system or they may be phosphate-reduced or phosphate-free systems.

Compositions, in percentages by weight, of the powdery or non-compacted granular detergents according to the present invention: The heavy-duty phosphate-based detergents have, for example, the following composition: from 15 to 60% by weight of phosphate, preferably trisodium polyphosphate from 5 to 35% by weight of surfactants from 0.5 to 6% compounds or lb from 5 to 25% peroxo inorganic compounds as bleaches from 5 to 50% of adjusting agents, preferably sodium sulfate ad 100% other ingredients. Detergents of this type are usually used in a dose from 4 to 15 g / l. The heavy-duty reduced phosphate detergents have, for example, the following composition: 0.5 to 40% phosphate, preferably trisodium polyphosphate 2 to 20% zeolites, lamellar silicates, polycarboxylates or aminopolycarboxylates or mixtures thereof De 5 to 35% of surfactants From 0.5 to 6% of compounds the or lb From 5 to 25% of peroxo inorganic compounds as bleach From 5 to 50% of adjusting agents, preferably sodium sulfate ad 100% of other ingredients. Detergents of this type are usually used in a dose from 4 to 15 g / l. The heavy-duty, non-phosphate detergents possess, for example, the following composition: from 15 to 70% of zeolites, lamellar silicates, polycarboxylates or aminopolycarboxylates or mixtures thereof of 5 to 35% surfactants of 0.5 to 6% compounds or Ib of 5 to 25% peroxo inorganic compounds as bleach of 5 to 50% of adjusting agents, preferably sodium sulfate ad 100% of other ingredients. Detergents of this type are usually used in a dose from 4 to 15 g / l. Compact detergents have a higher density, usually from 550 to 1100 g / l. These may have a phosphate-based builder system or they may be phosphate-reduced or phosphate-free systems.

Compositions, in percentages by weight, of powdered detergents or compacted granulates according to the present invention: Compact detergents based on phosphate have, for example, the following composition: from 10 to 60% of phosphate, preferably trisodium polyphosphate of 5%. to 35% of surfactants from 0.5 to 6% of compounds the or lb of 10 to 25% of inorganic peroxo compounds as bleaches ad 100% of other ingredients. Detergents of this type are usually used in a dose from 2.5 to 7 g / l. Compact detergents reduced in phosphate possess, for example, the following composition: from 2 to 40% of phosphate, preferably trisodium polyphosphate from 2 to 20% of zeolites, lamellar silicates, polycarboxylates or aminopolycarboxylates mixtures thereof of 5 to 35% of surfactants from 0.5 to 6% of compounds la or Ib from 10 to 25% of peroxo inorganic compounds as ad 100 bleaches of other ingredients.

Detergents of this type are normally used in a dose of 2.5 to 7 g / l. Compact detergents without phosphate possess, for example, the following composition: from 15 to 70% of zeolites, lamellar silicates, polycarboxylates or "aminocarboxylates, or mixtures thereof of 5 to 35% surfactants of 0.5 to 6% compounds o lb. of 10 to 25% peroxo inorganic compounds as bleaches ad 100% of other ingredients Detergents of this type are usually used in a dose of 2.5 to 7 g / L. The detergent formulation for textiles of the invention It is extremely well suited for domestic and commercial laundry of textiles under washing conditions such as those normally used in Europe, ie, using high detergent doses and low solution ratios.For this reason, the use of the detergent formulation for textiles of the invention in a dose of more than 2 g per liter of wash solution and preferably a dose of 2.5 to 15 g per liter of laundry solution for domestic laundry and commercial of textiles and is also the object of the present invention. This preferred use is carried out at a ratio of products to wash solution from 1:10 to 1: 2 and preferably from 1: 5 to 1: 3. By using the detergent formulation for textiles of the invention, in particular, a significantly improved bleaching action is achieved, particularly also at low wash temperatures from 20 to 60 ° C, this being demonstrated by suitable comparisons with the bleach activator. TAED that is normally used. The detergent formulation for textiles of the invention is substantially insensitive to hard water, particularly at 2_ the hardness of water above 2 mmol Ca [sic] / l. The use of the detergent formulation for textiles of the invention produces high content of active oxygen in the washing solution, which also contributes to good washing results. The normal content of active oxygen is in this case from 100 to 320 ppm and, in particular from 140 to 280 ppm.

Application examples related to the bleaching action of the detergent formulation for textiles of the invention The activity of the compounds of the structure Ia or Ib was tested with reference to N-methylmorpholinium acetonitrile in the form of the salt methyl sulfate ('MMA') The bleaching action was determined in the detergent formulations III and IV (see Tables 1 and 2.) Tables 1 and 2 provide the examples of the detergent formulation for textiles of the invention.

Table 1 Compositions of detergent formulations of the invention (in percent by weight) Table 1 (continued) Table 2 Compositions of detergent formulations of the invention (in percent by weight) Table 2 (continued) AA = acrylic acid MA = maleic acid VAc = vinyl acetate PVP = poly (vinylpyrrolidone) VI = vinyl imidazole VP = vinyl pyrrolidone Polymer 1 free of impurities = vinyl acetate graft polymer on poly (ethylene glycol) (molecular weight 6000) molecular weight of the graft polymer = 24000 Polymer 2 impurities release polymer = poly (ethylene terephthalate) / poly (oxyethylene terephthalate) (molecular weight 8000) Dequest® = ethylene diamine-N, N, N ', N' -tetra (methylene phosphonate) The test was carried out on an Atlas Standard Launder-0 meter under the conditions specified in Table 3.

Table 3 The measurement of the color intensity of the test fabrics was carried out photometrically. The reflectance values obtained in each of the test fabrics at 16 wavelengths in the range from 400 to 700 nm in 20 nm intervals were used to determine the color intensities of the test tinsiones before and after washing by the methods described in A. Kud in 'Seifen, [Ole, Fette, Wachse 119"pp. 590-594 (1993), from which the absolute percentage of the bleaching action Aabs- was calculated.

Table 4: Results of the washing tests carried out using detergents III or IV at a temperature of 22 ° C (the numerical values define the absolute percentage of the bleaching action Aabs Table 5: Results of the washing test carried out using detergents III or IV at a temperature of 38 ° C (the numerical values define the absolute percentage of the bleaching action AabS) The results of the washing tests using MMA show that the bleach activator in the formulations II and IV which are tested by means of the example present an excellent whitening action at a detergent dose of 4.5 g / l over a low temperature range. In comparison with TAED, improvements are made in the case of hydrophilic and hydrophobic impurities. In experiments employing a solution ratio of 1: 4 in a standard domestic washing machine it has been found that the bleaching solution of the aforementioned tests carried out according to a model in a Launder-O-meter using a large ratio of The solution gives results that are comparable to the experiments carried out on the domestic washing machine using a short solution ratio.

Claims (10)

1. CLAIMS 1. A detergent formulation for textiles that contains: (A) from 0.1 to 10% by weight of at least one quaternized nitrile glycine of the general formula la or lb R1 A "~ ^ N® CR2R3 CN Y © (la) wherein A represents a four-membered to nine-membered saturated ring containing at least one carbon atom and at least one other heteroatom selected from the group consisting of oxygen, sulfur and nitrogen, - R defines a C1-C24 alkyl group which can be interrupted by non-adjacent oxygen atoms or can further carry hydroxyl groups, a C4-C24 cycloalkyl group, a C7-C24 alkaryl group or a grouping of the formula CR R CN, R 2 and R3 independently define hydrogen, groups C1-C24 alkyl which may be interrupted by non-adjacent oxygen atoms or may further carry hydroxyl groups, or define C4-C24 cycloalkyl groups or C7-C24 alkaryl groups. R defines an alkylene group of C1-C75 which can be interrupted by non-adjacent oxygen and / or sulfur atoms, and R represents a counterion, (B) from 0.5 to 40% by weight of bleach in the form of peroxo compounds and / or perished, (C) from 0.5 to 50% by weight of nonionic and / or anionic surfactants in the form of peroxo and / or perished compounds, (D) from 5 to 85% by weight of at least one compound capable of sequestering calcium and / or magnesium ions. The detergent formulation for textiles as defined in claim 1, which contains: (A) from 0.5 to 7% by weight of at least one quaternized nitrile glycine of the formula a or lb (B) from 5 to 30% by weight weight of bleach in the form of peroxy compounds and / or percents (C) from 5 to 30% by weight of nonionic and / or anionic surfactants, and (D) from 10 to 70% by weight of at least one compound capable of sequester calcium and / or magnesium ions. 3. The detergent formulation for textiles as defined in claim 1 or claim 2, containing quaternized glycine nitriles or Ib in which A represents a saturated six-membered ring containing four carbon atoms and one oxygen atom. 4. The detergent formulation for textiles as defined in any of claims 1 to 3, which contain quaternized glycine nitriles wherein R defines a C1-C4 alkyl group or a benzyl radical and R2 and R3 define hydrogen. 5. The detergent formulation for textiles as defined in any of claims 1 to 4, which contains, as component (A), the sulfate, methyl sulfate and / or acid sulfate of N-methylmorpholinium acetonitrile. The detergent formulation for textiles as defined in any of claims 1 to 5, which contains the component (A) as a mixture or granules of glycine nitriles la or lb containing suitable inert and porous support materials. The detergent formulation for textiles as defined in any of claims 1 to 6, which contains as component (D) zeolites, silicates, alkali metal phosphates, polycarboxylates and / or aminopolycarboxylates. 8. The detergent formulation for textiles as defined in any of claims 1 to 7 in the form of a powder or granules having a density density from 200 to 1100 g / l. 9. A method of using the detergent formulation for textiles as defined in any of claims 1 to 8 in a dose of more than 2 g per liter of wash solution and preferably a dose of 2.5 to 15 g per liter of solution of washing, for laundry of domestic and commercial textiles. 10. The method of using the detergent formulation for textiles as defined in claim 9 in a ratio of articles to wash solution from 1:10 to 1: 2 and, preferably from 1: 5 to 1: 3.