EP1433839A1 - Optimised wash and cleaning compositions for an improved bleaching effect at low temperatures - Google Patents

Abstract

Detergent composition comprises tetraacetyl ethylenediamine (TAED) and another bleach activator, where the TAED is formulated to give slow peracetic acid release.

Description

The present invention relates to a composition for washing or Detergents that have a bleaching effect at low temperatures to have.

Textile detergent formulations as powder and as pressed molded articles usually contain a bleaching system, which mostly consists of Peroxy compounds, peracids or mixtures which provide active oxygen consists of it and bleach activators. The most used Bleach activator is tetraacetylethylene diamine ("TAED"). The effect of TAED sets in above 40 ° C, so TAED is not sufficient Effect in detergent fleets shows, in which the temperature to Protection of clothing is set below 40 ° C.

Other bleach activators are also known from the prior art. So describes e.g. B. DE 100 38 844 A1 a cationic bleach activator containing detergent and cleaning agent, this cationic Bleach activator an acetonitrile derivative with the anion of Is cumene sulfonic acid. By adding this bleach activator in this application the bleaching effect of aqueous peroxide liquors so far be increased that even at temperatures below 60 ° C in Essentially the same effect as with the peroxide liquor alone 95 ° C can be reached. The registration also describes the simultaneous use of the acetonitrile derivative with an enzyme Increasing the cleaning performance of the detergent and cleaning agent, especially compared to protein-containing, starch-containing and / or colored stains, for use in aqueous washing and Cleaning solutions containing a peroxygen compound. As Enzymes are described in particular those enzymes that have a pH optimum preferably in the alkaline range up to about pH 10. A special bleaching effect at low temperatures is described in this application not considered.

EP 0 941 299 describes a textile detergent formulation which is used as Bleach activators contains quaternized glycine nitriles, moreover Bleach, surfactants and a calcium and / or magnesium sequestering connection with builder or cobuilder function in certain relationships to each other. With this detergent composition will have an improved bleaching effect at low Washing temperatures (from 20 ° C to 60 ° C) achieved, especially at Use this detergent formulation with hard water.

EP 0 778 832 is concerned with a method of manufacture such quaternized glycine nitriles, which act as a bleach activator in Detergent compositions can be used.

Another bleach activator, namely an n-alkyl ammonium acetonitrile salt and its manufacture are described in WO 00/58273 proposed. The German published documents DE 100 38 832 and DE 100 38 845 describe various assemblies of bleach activators of the quaternized aminoalkyl nitrile type, or Acetonitrile derivatives for use in detergents.

However, none of the latter documents deals with the Question of increasing the washing performance at low temperatures.

The object of the present invention was to provide a washing and Provide detergent composition at low Temperatures (below 45 ° C) a good washing and bleaching performance developed.

This problem is solved by a detergent composition, containing at least one bleach activator and at least one TAED with slow peracetic acid release kinetics.

All bleach activators can be used as bleach activators that show an activating effect for the bleaching agent in washing liquors at temperatures below 45 ° C. These are, for example, compounds of the substance classes of polyacylated sugar or sugar derivatives with C ₁ -C ₁₀ -acyl radicals, preferably acetyl, Propionyl, octanoyl, nonanoyl or benzoyl residues, especially acetyl residues. Mono- or disaccharides and their reduced or oxidized derivatives can be used as sugar or sugar derivatives, preferably glucose, mannose, fructose, sucrose, xylose or lactose. Particularly suitable bleach activators of this class of substances are, for example, pentaacetylglucose, xylose tetraacetate, 1-benzoyl-2,3,4,6-tetraacetylglucose and 1-octanoyl-2,3,4,6-tetraacetylglucose.

0-Acyloxime esters such as z. B. 0-acetylactone oxime, 0-benzoylacetone oxime, bis (propylimino) carbonate or bis (cyclohexylimino) carbonate. Such acylated oximes and Oxime esters are described, for example, in EP-A-028 432 and EP-A-267 046.

Also useful as bleach activators are N-acylcaprolactams such as for example N-acetylcaprolactam, N-benzoylcaprolactam, N-octanoylcaprolactam, N-octanoylcaprolactam or carbonyl biscaprolactam.

• N-diacylierte und N,N'-tetracylierte Amine, z. B. N,N,N',N'-Tetraacetylmethyldiamin und -ethylendiamin (TAED), N,N-Diacetylanilin, N,N-Diacetyl-p-toluidin oder 1,3-diacylierte Hydantoine wie 1,3-Diacetyl-5,5-dimethylhydantoin;
• N-Alkyl-N-sulfonyl-carbonamide, z. B. N-Methyl-N-mesyl-acetamid oder N-Methyl-N-mexyl-benzamid;
• N-acylierte cyclische Hydrazide, acylierte Triazole oder Urazole, z. B. Monoacetyl-maleinsäurehydrazid;
• O,N,N-trisubstituierte Hydroxylamine, z. B. O-N,N-trisubstituierte Hydroxylamine, z. B. O-Benzoyl-N,N-succinylhydroxylamin, O-Acetyl-N,N-succinyl-hydroxylamin oder O,N,N-Triacetalhydroxylamin;
• N,N'-Diacyl-sulfurylamide, z. B. N,N'-Dimethyl-N,N'-diacetylsulfurylamid oder N,N'-Diethyl-N,N'-dipropionyl-sulfurylamid;
• Triacylcyanurate, z. B. Triacetylcyanurat oder Tribenzoylcyanurat;
• Carbonsäureanhydride, z. B. Benzoesäureanhydrid, m-Chlorbenzoesäureanhydrid oder Phthalsäureanhydrid;
• 1,3-Diacyl-4,5-diacyloxy-imidazolin, z. B. 1,3-Diacetyl-4,5-diacetoxyimidazolin;
• Tetraacetylglycoluril und Tetrapropionylglycoluril;
• Diacylierte 2,5-Diketopiperazine, z. B. 1,4-Diacetyl-2,5-diketopiperazin;
• Acylierungsprodukte von Propylendiharnstoff und 2,2-Dimethylpropylendiharnstoff, z. B. Tetraacetylpropylendiharnstoff,
• α-Acyloxy-polyacyl-malonamide, z. B. α-Acetoxy-N,N'-diacetylmalonamid;
• Diacyl-dioxohexahydro-1,3,5-triazine, z. B. 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin.

Can also be used as bleach activators

• N-diacylated and N, N'-tetracylated amines, e.g. B. N, N, N ', N'-tetraacetylmethyl diamine and ethylenediamine (TAED), N, N-diacetylaniline, N, N-diacetyl-p-toluidine or 1,3-diacylated hydantoins such as 1,3-diacetyl-5 , 5-dimethylhydantoin;
• N-alkyl-N-sulfonyl-carbonamides, e.g. B. N-methyl-N-mesyl-acetamide or N-methyl-N-mexyl-benzamide;
• N-acylated cyclic hydrazides, acylated triazoles or urazoles, e.g. B. monoacetyl maleic acid hydrazide;
• O, N, N-trisubstituted hydroxylamines, e.g. B. ON, N-trisubstituted hydroxylamines, e.g. B. O-benzoyl-N, N-succinylhydroxylamine, O-acetyl-N, N-succinyl-hydroxylamine or O, N, N-triacetalhydroxylamine;
• N, N'-diacylsulfurylamide, e.g. B. N, N'-dimethyl-N, N'-diacetylsulfurylamide or N, N'-diethyl-N, N'-dipropionylsulfurylamide;
• Triacylcyanurates, e.g. B. triacetyl cyanurate or tribenzoyl cyanurate;
• Carboxylic anhydrides, e.g. B. benzoic anhydride, m-chlorobenzoic anhydride or phthalic anhydride;
• 1,3-diacyl-4,5-diacyloxy-imidazoline, e.g. B. 1,3-diacetyl-4,5-diacetoxyimidazoline;
• Tetraacetylglycoluril and tetrapropionylglycoluril;
• Diacylated 2,5-diketopiperazines, e.g. B. 1,4-diacetyl-2,5-diketopiperazine;
• Acylation products of propylene diurea and 2,2-dimethylpropylene diurea, e.g. B. tetraacetylpropylene diurea,
• α-acyloxy polyacyl malonamides, e.g. B. α-acetoxy-N, N'-diacetylmalonamide;
• Diacyl-dioxohexahydro-1,3,5-triazines, e.g. B. 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine.

Likewise usable as bleach activators are 2-alkyl- or 2-aryl- (4H) -3,1-benzoxain-4-ones, as for example in EP-B-332 294 and EP-B-502 013. In particular, 2-phenyl- (4H) -3,1-benzoxain-4-one and 2-methyl- (4H) -3,1-benzoxain-4-one can be used.

In addition, bleach activators from the N or O-acyl compounds, for example multi-acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular Tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, Hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, also carboxylic anhydrides, especially phthalic anhydride, Carboxylic acid esters, especially sodium nonanoyloxy-benzenesulfonate, Sodium isononanoyloxy-benzenesulfonate and acylated sugar derivatives, such as Pentaacetyl glucose can be used.

European patent application EP 0 464 880 discloses bleach-boosting cationic nitriles of the general formula R'R ", R""N ⁺ -CR ₁ R ₂ -CNX ^- in which R ₁ and R _{2 are} hydrogen or a substituent with at least one a C atom, R 'is a C ₁ -C ₂₄ alkyl, alkenyl or alkyl ether group or a group -CR ₁ R ₂ -CN, and R''andR''' each have a C ₁ -C ₂₄ alkyl - or hydroxyalkyl group and the counter anion X ^{- is} an organic sulfonate, or a carboxylate.

In addition, connections can be used, as in the DE 100 38 844 A1 are described under the general formula I.

However, a preferred bleach activator is a quaternized one Glycine nitrile from the group N-methylmorpholinium acetonitrile methyl sulfate, sulfate and hydrogen sulfate. The preferred activator can as the only bleach activator in the detergent composition be used, or in combination with one of the aforementioned Bleach activators.

In a preferred embodiment, a combination of one quaternized glycine nitrile with TAED. In one particularly preferred embodiment is a quaternized glycine nitrile TAED used in a ratio of 4: 1 to 1: 4. In particular preferred embodiments use a ratio of TAED to Glycine nitrile of 4: 1, 3: 1 and 3: 2, the latter ratio is particularly suitable for textile detergents.

It has been shown that it is of particular advantage and that Washing and cleaning performance of the agent according to the invention clearly can improve if for use at low temperatures (below 45 ° C) a TAED is used in a processing form that has a delayed release of peracetic acid. This means that preferably a TAED assembled in this way is used that does not immediately in contact with water in combination with percarbonate Peracetic acid releases, but only with a certain delay. The delayed release of peracetic acid increases the washing performance other ingredients, especially at a washing temperature from 30 ° C. Without wishing to be bound by the following explanation assumed that the improved washing performance is due to the fact that At the beginning of the washing process, the bleach activator used Effect comes from the rapid release of peracetic acid performance seems to be disturbed by the TAED. This means, that the bleach activator shows a significantly better effect if too No very high peracetic acid concentration at the beginning of the washing process is present. The same applies to the performance of Properase. After the Bleach activator has its effect, it is beneficial for that Washing result if the Peracetic acid concentration increased. Such a "delayed" occurrence a high peracetic acid concentration improves in particular Bleaching action of the washing or cleaning agent according to the invention low temperatures.

a) die Auflösegeschwindigkeit des TAED Coatings

b) die Dicke des TAED Coatings

c) die Dichte des TAED Granulats

The peracetic acid kinetics are determined by:

a) the dissolution rate of the TAED coating

b) the thickness of the TAED coating

c) the density of the TAED granules

Regarding a): A TAED with a protective cover is preferably used coated (coated), which dissolves only slowly in the wash liquor, and thus the TAED comes into effect only after a delay, namely if that Coating is removed.

To b) the thickness of the coating also influences the speed with that the TAED can come into effect. The thicker the coating, the more it takes longer until the coating in the wash liquor is so far away is that the TAED can be effective.

To c) a highly compressed TAED granulate must first in the wash liquor be decompacted before the TAED releases its effect on peracetic acid can unfold. Therefore, the compacting of the used granules the peracetic acid release kinetics.

According to the definitions of the present description, under a "low peracetic acid concentration" a concentration of less than 100 mg / l are understood to mean a "high Peracetic acid concentration "a concentration of more than 300 mg / l.

"Delayed release" means that a Concentration of more than 100 mg / l peracetic acid in the wash liquor only after a few minutes, preferably after at least 5 minutes and especially preferably occurs after at least 8 min. After that time is then a rapid increase in the concentration of peracetic acid in the wash liquor he wishes.

TAED's with a delayed or slow peracetic acid release kinetics are commercially available.

In addition to the bleach activator, the detergent composition suitable bleaching agents are added, which are customary, generally known Can be bleach for detergent compositions.

Suitable peroxygen compounds for use in agents according to the invention are, in particular, hydrogen peroxide and inorganic salts which give off hydrogen peroxide under the washing conditions, to which alkali metal perborates such as, for. B. sodium perborate tetrahydrate and sodium perborate monohydrate, further include alkali metal carbonate perhydrates such as sodium carbonate perhydrate ("sodium percarbonate") and -persilicates and / or -persulfates such as caroate. Mostly in addition to these inorganic peroxo compounds, the bleaching system of the detergent formulation can contain inorganic or organic peracids, especially percarboxylic acids, e.g. B. C ₁ -C ₁₂ percarboxylic acids, C ₈ -C ₁₆ dipercarboxylic acids, imidopercaproic acids or aryldipercaproic acids. Preferred examples of usable acids are peracetic acid, perbenzoic acid, linear or branched octanoic, nonanoic, decanoic or dodecane monoperacids, decanoic and dodecane diper acid, mono- and diperphthalic acids, isophthalic acids and terephthalic acids, phthalimidopercaproic acid, terephthaloyl diamide peroxapaponic acid (PAP). These percarboxylic acids can be used as free acids or as salts of the acids, preferably alkali or alkaline earth metal salts. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be coated in a manner known in principle. A particularly preferred peracid used is the peracid available under the trade name Eureco® (Ausimont, Italy). Peroxygen compounds are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight and particularly preferably from 8% by weight to 25% by weight. The addition of smaller amounts of known bleach stabilizers, such as, for example, phosphonates, borates or metaborates and metasilicates, and magnesium salts, such as magnesium sulfate, can be expedient.

In one embodiment of the present invention, at least a bleach activator and an effective peracid as raw materials side by side in the detergent or cleaning agent formulation, your Effect is time shifted against each other by the peracid delayed effect. The peracid is preferably in granular form Form before. This embodiment has the advantage that regardless of that pH set in the wash liquor and the wash temperature in each If there is a bleaching effect. At low pH (pH 8.5 to 9) occurs especially the effect of peracid in the foreground without Activation develops a bleaching effect. At higher pH (pH> 9) the bleach activator unfolds its full effect, so that here too there is an increased bleaching effect.

Also various bleach activators, namely those that work unfold at low temperatures (below 45 ° C) and those that their Can have an effect at higher temperatures (from 40 ° C) side by side as a mixture in the washing or cleaning composition available. In this way, the temperature range in which the Detergent can be used to be significantly broadened.

Quaternized imines or are usually used as bleaching catalysts Sulfonimines used, as described for example in US-A-5,360,568, US-A-5,360,569 and EP-A-453 003 are described, as well as manganese complexes, as described for example in WO-A 94/21777. Further Metal-containing bleaching catalysts which can be used are described in EP-A-458 397, EP-A-458 398 and EP-A-549 272. Bleaching catalysts are used in generally in amounts of up to 1% by weight, in particular 0.01 to 0.5% by weight, based on the detergent formulation.

Bleach stabilizers are additives that interfere with bleaching Traces of heavy metals can adsorb, bind or complex. In particular, common complexing agents such as Ethylenediaminetetraacetate, nitrilotriacetic acid, methylglycinediacetic acid, β-alaninediacetic acid, ethylenediamine-N, N'-disuccinate and phosphonates such as ethylenediaminetetramethylenephosphonate, diethylenetriaminepentamethylenephosphonate or hydroxyethylidene-1,1-diphosphonic acid in the form of Acids or as partially or fully neutralized Alkali metal salts in amounts of up to 1% by weight, in particular 0.01 to 0.5% by weight, based on the detergent formulation.

A washing or cleaning agent according to the invention preferably contains 0.001 mg to 0.5 mg, in particular 0.02 mg to 0.3 mg of enzymatic active protein per gram of total agent. The protein concentration can be made using known methods, e.g. B. the bicinchonic acid process (BCA method, Pierce Chemical Co., Rockford, IL) or the biuret method (A.G. Gornall, C.S. Bardawill and M.M. David, J. Biol. Chem. 177, 751-766, 1948).

A protease is used as at least one wash-active enzyme at temperatures below 45 ° C an essential part of their activity developed. An example of such a protease is the enzyme Properase® 4000 E, distributed by Genencor International becomes.

The other enzymes used can also be those which are a Have maximum activity at low temperatures. The used Enzymes should, however, at least at temperatures below 45 ° C Develop activity, even if the maximum does not have to be there.

In addition to these proteins, which are specialized in low temperatures further enzymes commonly used in previous detergents are used, such as proteases, lipases, amylases, Cellulases and peroxidases. Preferably for detergents optimized enzymes effective in the alkaline medium in the usual amounts (about 0.1 to 3 wt .-%) used.

Proteases that can be used include those from microorganisms, especially bacteria or fungi, extractable enzymes with a pH optimum in the alkaline range, for example those from the international patent applications WO 92/07067, WO 91/02792, WO 88/03947 or WO 88/03946 or the European patent applications EP 471 265, EP 416 967 or EP 394 352 known proteases.

Protease is preferably in such amounts in the agent according to the invention used that the finished agent 100 PE / g (protease units per Gram, determined according to that described in Tenside 7, 125 (1970) Method), in particular 125 PE / g to 5,000 PE / g and particularly preferred 150 PE / g to 4,500 PE / g. Suitable proteases are commercially available available, for example under the names Alcalase®, Alkolase®, BLAP®, Durazym®, Esperase®, Everlase (RE), FN-Base®, Maxatase®, Maxaclean®, Maxacal®, Maxapem®, Optimase®, Optimax®, Opticlean®, Ovozyme®, Properase® Purafect®, Purafect®OxP or Savinase®. Of the above The use of Properase® is particularly preferred for proteases.

The amylases which can be used in agents according to the invention which preferably in combination with at least one further enzyme Are used include those that can be obtained from bacteria or fungi Enzymes that have a pH optimum, preferably in the alkaline range have about pH 10. Useful commercial products are, for example Amylase-LT, Aquazym®, Duramyl®, Maxamyl®, Purastar®, Purafect® OxAm or Termamyl®. Amylase is preferably in the agent according to the invention in such amounts that the finished agent 0.01 KNU / g to 2 KNU / g ("Kilo Novo Units" per gram according to the company's standard method Novo, where 1 KNU is the amount of enzyme, the 5.26 g starch at pH 5.6 and 37 ° C, based on that of P. Bernfeld in S.P. Colowick and N.D. Kaplan, Methods in Enzymology, Volume 1, 1955, page 149 described method), in particular 0.015 KNU / g to 1.8 KNU / g and particularly preferably 0.03 KNU / g to 1.6 KNU / g. If that means according to the invention contains an amylase, this is preferred selected from the genetically modified amylases. genetically modified amylases are, for example, from the international Patent applications WO 94/18314 or WO 95/21247 known.

In the case of the lipase optionally contained in the agent according to the invention is one of microorganisms, in particular bacteria or Mushrooms, extractable enzyme. Such is for example from the European patent applications EP 0 204 208, EP 0 214 761, EP 0 258 068, EP 0 385 401, EP 0 407 225, EP 0 571 982 or the international Patent applications WO 87/00859 or WO 90/10695 known. Lipase is used in Agents according to the invention preferably used in such amounts that the finished agent has a lipolytic activity in the range of 10 LU / g up to 10,000 LU / g ("lipase activity units" per gram, determined via the enzymatic hydrolysis of tributyrin at 30 ° C and pH 7 after the in Method mentioned in EP 258 068), in particular 80 LU / g to 5,000 LU / g and particularly preferably 100 LU / g to 1,000 LU / g. commercial Lipases are, for example, Lipex®, Lipolase®, Lipolase Ultra®, Lipomax®, Lipoprime®, Lipozym® and Lumafast®,

The cellulase usable according to the invention also belongs to the group Bacteria or fungi are extractable enzymes, which have a pH optimum preferably in the almost neutral to weakly alkaline pH range of 6 up to 9.5. Such cellulases are for example from the German published documents DE 31 17 250, DE 32 07 825, DE 32 07 847, DE 33 22 950, the European patent applications EP 265 832, EP 269 977, EP 270 974, EP 0273 125 and EP 339 550 or international patent applications WO 96/34108 and WO 97/34005 known. They are preferably used in the agent according to the invention in such Amounts used that the finished agent are cellulolytic Activity from 0.05 IU / g to 1.5 IU / g ("International Units" per gram, based on the enzymatic hydrolysis of Na-carboxymethyl cellulose at pH 9.0 and 40 ° C, as in Agric, Biol. Chem. 53, 1275 (1989) by S.Ito et al. described), in particular 0.07 IU / g to 1.4 IU / g and particularly preferably 0.1 IU / G to 1.3 IU / g. Suitable commercial products are for example Carezyme®, Celluzyme®, Ecostase®, and Novozym® des Manufacturer Novo Nordisk or KAC® from Kao. Among the preferred Cellulases also include those from Melanocarpus sp. or Myriococcum sp. Available 20K cellulase from the international patent application WO 97/14804 is known. It has one as described there Molecular weight of about 20 kDa and shows at 50 ° C in the pH range of 4 to 9 at least 80% of their maximum activity, with almost 50 % of maximum activity is maintained at pH 10. You can like also described there, can be isolated from Melanocarpus albomyces and in genetically engineered Trichoderma reseei transformants to be produced.

Enzymes that can also be used in the compositions come from Class of cutinases, pullulanases, hemicellulases, oxidases, laccases and peroxidases and mixtures thereof. Are particularly suitable from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, Pseudomonas cepacia or Coprinus cinereus obtained enzymatic Agents. The enzymes can, e.g. B. in the European Patent EP 0 564 476 or in the international patent application WO 94/23005 described, adsorbed on carriers and / or in Enveloping substances can be embedded to prevent them from premature inactivation to protect. They are in the washing or Detergents preferably in amounts up to 5 wt .-%, in particular from 0.2% by weight to 4% by weight.

If several enzymes are used in the agent according to the invention this can be done by incorporating the two or more separate ones or in a known manner separately assembled enzymes or made up of two or more together in one granulate Enzymes such as B. from international patent applications WO 96/00772 or WO 96/00773 known.

In a particularly preferred embodiment, the washing or cleaning agents according to the invention a mixture of two Proteases, one of which is Properase®, may be used in addition to other enzymes (amylase, lipase, cellulase). The use of Properase® along with another protease improves washing and Cleaning property of the washing and cleaning agent according to the invention clearly, while at the same time less total amount of protease must be used, both with regard to the used absolute amount, as well as with regard to the international used Enzyme units of the enzymes. This also leads to a Cost reduction in the production of the manufactured product.

Another benefit of reducing the total amount of protease is that a textile detergent produced in this way is particularly gentle on Woolen laundry works.

As further common detergent ingredients, surfactants can be and detergent composition may be included, in particular nonionic and / or anionic surfactants or mixtures are preferred thereof.

Suitable anionic surfactants are, for example, fatty alcohol sulfates of fatty alcohols having 8 to 22, preferably 10 to 18, carbon atoms, e.g. B. C ₉ -C ₁₁ alcohol sulfates, C ₁₂ -C ₁₃ alcohol sulfates, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate.

Other suitable anionic surfactants are sulfated ethoxylated C ₈ -C ₂₂ alcohols (alkyl ether sulfates) or their soluble salts. Compounds of this type are prepared, for example, by firstly using a C ₈ -C ₂₂ , preferably a C ₁₀ -C ₁₈ alcohol, e.g. B. a fatty alcohol, alkoxylated and the alkoxylation product then sulfated. Ethylene oxide is preferably used for the alkoxylation, 2 to 50, preferably 3 to 20, moles of ethylene oxide being used per mole of fatty alcohol. However, the alkoxylation of the alcohols can also be carried out using propylene oxide alone and, if appropriate, butylene oxide. Also suitable are those alkoxylated C ₈ -C ₂₂ alcohols which contain ethylene oxide and propylene oxide or ethylene oxide and butylene oxide. The alkoxylated C ₈ -C ₂₂ alcohols can contain the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or in statistical distribution.

Other suitable anionic surfactants are alkanesulfonates such as C ₈ -C ₂₄ , preferably C ₁₀ -C ₁₈ alkanesulfonates, and soaps such as the salts of C ₈ -C ₂₄ carboxylic acids.

Other suitable anionic surfactants are C ₉ -C ₂₀ linear alkylbenzenesulfonates (LAS).

Further suitable anionic surfactants are N-acyl sarcosinates with aliphatic saturated or unsaturated C ₈ -C ₂₅ acyl radicals, preferably C ₁₀ -C ₂₀ acyl radicals, e.g. B. N-oleoyl sarcosinate.

The anionic surfactants are preferred to the detergent formulation added 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 z. B. Hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium ions.

Of the anionic surfactants mentioned are linear alkylbenzenesulfonates and fatty alcohol sulfates of particular interest.

Examples of suitable nonionic surfactants are alkoxylated C ₈ -C ₂₂ 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. All alkoxylated alcohols which contain at least two molecules of an alkylene oxide mentioned above can be used as the surfactant. Here too, block polymers of ethylene oxide, propylene oxide and / or butylene oxide come into consideration or addition products which contain the alkylene oxides mentioned in a statistical distribution. As a rule, 2 to 50, preferably 3 to 20, mol of at least one alkylene oxide are used per mol of alcohol. Preferably used as the alkylene oxide is ethylene oxide. The alcohols preferably have 10 to 18 carbon atoms.

Another class of suitable nonionic surfactants are alkylphenol ethoxylates with C ₆ -C ₁₄ alkyl chains and 5 to 30 moles of ethylene oxide units.

Another class of nonionic surfactants are alkyl polyglucosides with 8 to 22, preferably 10 to 18 carbon atoms in the alkyl chain. These compounds usually contain 1 to 20, preferably 1.1 to 5 Glucoside.

Wobei R⁶ C₆-C₂₂-Alkyl, R⁷ H oder C₁-C₄-Alkyl und R⁸ ein Polyhydroxyalkylrest mit 5 bis 12 C-Atomen und mindestens 3 Hydroxygruppen ist. Vorzugsweise ist R⁶ C₁₀-C₁₈-Alkyl, R⁷ Methyl und R⁸ ein C₅-C₆-Rest. Beispielsweise erhält man derartige Verbindungen durch die Acylierung von reduzierend aminierten Zuckern mit Säurechloriden von C₁₀-C₁₈-Carbonsäuren.Another class of nonionic surfactants are N-alkyl glucamides of general structure II or III

Where R ^{6 is} C ₆ -C ₂₂ alkyl, R ⁷ H or C ₁ -C ₄ alkyl and R ^{8 is} a polyhydroxyalkyl radical having 5 to 12 carbon atoms and at least 3 hydroxy groups. R ⁶ is preferably C ₁₀ -C ₁₈ alkyl, R ^{7 is} methyl and R ^{8 is} a C ₅ -C ₆ radical. For example, such compounds are obtained by the acylation of reducing aminated sugars with acid chlorides of C ₁₀ -C ₁₈ carboxylic acids.

The textile detergent formulation according to the invention preferably contains, as nonionic surfactants, ethoxylated C ₁₀ -C ₁₆ alcohols with 3 to 12 moles of ethylene oxide, in particular ethoxylated fatty alcohols and / or ethoxylated oxo alcohols.

As substances with primarily builder or cobuilder function preferably representatives from the group of zeolites, silicates, Alkali metal phosphates, polycarboxylates and aminopolycarboxylates individually or used in mixtures.

In principle, zeolites and silicates can be used as inorganic Ion exchangers are called. Suitable zeolites (alumosilicates) are in particular those of the types A, P, X, B, HS and MAP in their Sodium form or in forms in which sodium is partially against others Cations such as Li, K, Ca, Mg or ammonium are exchanged. such Zeolites are described, for example, in EP-A 0 038 591, EP-A 0 087 035, US-A 4,604,224, GB-A 2 013 259, EP-A 0 522 726, EP-A 0 384 070 and WO-A 94/24251.

Suitable amorphous or crystalline silicates, in particular Layered silicates are primarily amorphous disilicates and crystalline ones Disilicates such as the layered silicate SKS-6 (manufacturer Hoechst). The Silicates can be in the form of their alkali metal, alkaline earth metal or Ammonium salts are used. Na, Li and Mg silicates are preferred used.

Trisodium polyphosphate is particularly suitable as the alkali metal phosphate Consideration, which is also regarded as an inorganic ion exchanger can be.

• C₄-C₂₀-Di-, -Tri- und -Tetracarbonsäuren wie z. B. Bernsteinsäure, Propantricarbonsäure, Butantetracarbonsäure, Cyclopentantetracarbonsäure und Alkyl- und Alkenylbernsteinsäuren mit C₂-C₁₆-Alkyl- bzw. Alkenylresten.
• C₄-C₂₀-Hydroxycarbonsäuren wie z. B. Apfelsäure, Weinsäure, Gluconsäure, Glucarsäure, Citronensäure, Lactobionsäure und Saccharosemono-, -di- und tricarbonsäure;
• komplexbildend wirkende Aminopolycarboxylate wie z. B. Nitrilotriessigsäure, Methylglycindiessigsäure, β-Alanindiessigsäure, Ethylendiamintetraessigsäure, Serindiessigsäure oder Ethylendiamin-N,N'-disuccinat, vorzugsweise in Form ihrer teilweise oder vollständig neutralisierten Alkalimetall-(insbesondere Natrium)-salze.

Suitable low molecular weight polycarboxylates and aminopolycarboxylates are in particular:

• C ₄ -C ₂₀ di, tri and tetracarboxylic acids such as. B. succinic acid, propane tricarboxylic acid, butane tetracarboxylic acid, cyclopentane tetracarboxylic acid and alkyl and alkenyl succinic acids with C ₂ -C ₁₆ alkyl or alkenyl radicals.
• C ₄ -C ₂₀ hydroxycarboxylic acids such. B. malic acid, tartaric acid, gluconic acid, glucaric acid, citric acid, lactobionic acid and sucrose mono-, di- and tricarboxylic acid;
• complexing aminopolycarboxylates such. B. nitrilotriacetic acid, methylglycinediacetic acid, β-alaninediacetic acid, ethylenediaminetetraacetic acid, serinediacetic acid or ethylenediamine-N, N'-disuccinate, preferably in the form of their partially or completely neutralized alkali metal (especially sodium) salts.

• Oligomaleinsäuren, wie sie beispielsweise in EP-A 0 451 508 und EP-A 0 396 303 beschrieben sind;
• Co- und Terpolymere ungesättigter C₄-C₈-Dicarbonsäuren, wobei als Comonomere monoethylenisch ungesättigte Monomere
• - aus der Gruppe (i) in Mengen von bis zu 95 Gew.-%,
• - aus der Gruppe (ii) in Mengen von bis zu 60 Gew.-%,
• - aus der Gruppe (iii) in Mengen von bis zu 20 Gew.-% einpolymerisiert enthalten sein können.

Suitable oligomeric or polymeric polycarboxylates and aminopolycarboxylates are in particular:

• Oligomaleic acids as described, for example, in EP-A 0 451 508 and EP-A 0 396 303;
• Copolymers and terpolymers of unsaturated C ₄ -C ₈ dicarboxylic acids, with monoethylenically unsaturated monomers as comonomers
• from group (i) in amounts of up to 95% by weight,
• from group (ii) in amounts of up to 60% by weight,
• - From group (iii) in amounts of up to 20 wt .-% can be copolymerized.

Examples of suitable unsaturated C ₄ -C ₈ dicarboxylic acids here are maleic acid, fumaric acid, itaconic acid and citraconic acid. Maleic acid is preferred.

Group (i) includes monoethylenically unsaturated C ₃ -C ₈ monocarboxylic acids such as. As acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid. From group (i), preference is given to using acrylic acid and methacrylic acid.

Group (ii) includes monoethylenically unsaturated C ₂ -C ₂₂ olefins, vinyl alkyl ethers with C ₁ -C ₈ alkyl groups, styrene, vinyl esters of C ₁ -C ₈ carboxylic acids, (meth) acrylamide and vinyl pyrrolidone. From group (ii), preference is given to using C ₂ -C ₆ -olefins, vinyl alkyl ether with C ₁ -C ₄ -alkyl groups, vinyl acetate and vinyl propionate.

Group (iii) includes (meth) acrylic esters of C ₁ -C ₈ alcohols, (meth) acrylonitrile, (meth) acrylamides of C ₁ -C ₈ amines, N-vinylformamide and vinylimidazole.

If the polymers of group (ii) polymerize vinyl esters contain, they can also partially or completely to vinyl alcohol structural units be hydrolyzed. Suitable copolymers and terpolymers are known for example from US-A 3,887,806 and DE-A 43 13 909.

• Copolymere von Maleinsäure und Acrylsäure im Gewichtsverhältnis 10:90 bis 95:5, insbesondere solche im Gewichtsverhältnis 30:70 bis 90:10, insbesondere mit Molmassen von 1.000 bis 150.000;
• Terpolymere aus Maleinsäure, Acrylsäure und einem Vinylester einer C₁-C₃-Carbonsäure im Gewichtsverhältnis 10 (Maleinsäure) : 90 (Acrylsäure + Vinylester) bis 95 (Maleinsäure) : 5 (Acrylsäure + Vinylester), wobei das Gewichtsverhältnis von Acrylsäure zu Vinylester im Bereich von 20:80 bis 80:20 variieren kann;
• Terpolymere aus Maleinsäure, Acrylsäure und Vinylacetat oder Vinylpropionat im Gewichtsverhältnis 20 (Maleinsäure) : 80 (Acrylsäure + Vinylester) bis 90 (Maleinsäure) : 10 (Acrylsäure + Vinylester), wobei das Gewichtsverhältnis von Acrylsäure zum Vinylester im Bereich von 30:70 bis 70:30 variieren kann.
• Copolymere von Maleinsäure mit C₂-C₈-Olefinen im Molverhältnis 40:60 bis 80:20, wobei Copolymere von Maleinsäure mit Ethylen, Propylen oder Isobutan im Molverhältnis von ca. 50:50 besonders bevorzugt sind.

The following are particularly suitable as copolymers of dicarboxylic acids:

• Copolymers of maleic acid and acrylic acid in a weight ratio of 10:90 to 95: 5, in particular those in a weight ratio of 30:70 to 90:10, in particular with molecular weights of 1,000 to 150,000;
• Terpolymers of maleic acid, acrylic acid and a vinyl ester of a C ₁ -C ₃ carboxylic acid in a weight ratio of 10 (maleic acid): 90 (acrylic acid + vinyl ester) to 95 (maleic acid): 5 (acrylic acid + vinyl ester), the weight ratio of acrylic acid to vinyl ester in Range can vary from 20:80 to 80:20;
• Terpolymers of maleic acid, acrylic acid and vinyl acetate or vinyl propionate in a weight ratio of 20 (maleic acid): 80 (acrylic acid + vinyl ester) to 90 (maleic acid): 10 (acrylic acid + vinyl ester), the weight ratio of acrylic acid to vinyl ester in the range from 30:70 to 70 : 30 may vary.
• Copolymers of maleic acid with C ₂ -C ₈ olefins in a molar ratio of 40:60 to 80:20, copolymers of maleic acid with ethylene, propylene or isobutane in a molar ratio of about 50:50 being particularly preferred.

Graft polymers of unsaturated carboxylic acids on low molecular weight Carbohydrates or hydrogenated carbohydrates, cf. US-A 5,227,446, DE-A 44 15 623 and DE-A 43 13 909 are also suitable. suitable unsaturated carboxylic acids include maleic acid, Fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, Crotonic acid and vinyl acetic acid as well as mixtures of acrylic acid and Maleic acid in amounts of 40 to 95 wt .-%, based on the grafting component to be grafted on.

Up to 30% by weight, based on the addition, can also be used for the modification grafting component, further monoethylenically unsaturated monomers are present in polymerized form. Suitable modifying monomers are above-mentioned monomers of groups (ii) and (iii).

Degraded polysaccharides such as e.g. B. acidic or enzymatically degraded starches, inulins or cellulose, reduced (hydrogenated or hydrogenated aminated) degraded polysaccharides such. B. mannitol, sorbitol, aminosorbitol and glucamine and polyalkylene glycols with molecular weights up to M _w = 5,000 such as. B. polyethylene glycols, ethylene oxide / propylene oxide or ethylene oxide / butylene oxide block copolymers, statistical ethylene oxide / propylene oxide or ethylene oxide / butylene oxide copolymers or alkoxylated mono- or polybasic C ₁ -C ₂₂ alcohols, cf. US-A 4,746,456.

Grafted mined or mined from this group are preferred reduced starches and grafted polyethylene oxides, 20 up to 80% by weight of monomers based on the graft component in the Graft polymerization can be used. For grafting is preferred a mixture of maleic acid and acrylic acid in a weight ratio of 90:10 used until 10:90.

Polyglyoxylic acids are described, for example, in EP-B 0 001 004, US-A 5,399,286, DE-A 41 06 355 and EP-A 0 656 914. The end groups of Polyglyoxylic acids can have different structures.

Are polyamidocarboxylic acids and modified polyamidocarboxylic acids for example known from EP-A 0 454 126, EP-B 0 511 037, WO-A 94/01486 and EP-A 0 581 452.

The aminopolycarboxylates used are preferably also polyaspartic acid or cocondensates of aspartic acid with further amino acids, C ₄ -C ₂₅ mono- or dicarboxylic acids and / or C ₄ -C ₂₅ mono- or diamines. Are particularly preferred in phosphorus-containing acids used prepared with C ₆ -C ₂₂ -mono- or -dicarboxylic acids or with C ₆ -C ₂₂ -mono- or -diamines.

Condensation products of citric acid with hydroxycarboxylic acids or Polyhydroxy compounds are e.g. B. known from WO-A 93/22362 and WO-A 92/16493. Such condensates containing carboxyl groups usually molecular weights up to 10,000, preferably up to 5,000.

Particular preference is given to the textile detergent formulation according to the invention of the substance classes mentioned zeolite A, zeolite P, zeolite X, layered silicates such as SKS-6, trisodium polyphosphate, Acrylic acid / maleic acid copolymers (especially those of molecular weight 10,000 to 100,000), polyaspartic acid, citric acid, nitrilotriacetic acid, Methylglycinediacetic acid and mixtures thereof used.

Of particular interest as mixtures are those of zeolites and Polyaspartic acid, zeolites and oligomaleic acids, zeolites and Acrylic acid / maleic acid copolymers, trisodium polyphosphate and layered silicates, Trisodium polyphosphate and acrylic acid / maleic copolymers, Zeolites and trisodium polyphosphate as well as from zeolites, layered silicates and acrylic acid / maleic acid copolymers.

The textile detergent according to the invention can be used as an additional component formulation usual graying inhibitors and / or soil release polymers in the usual amounts for this (about 0.1 to 2% by weight) contain.

• Polyester aus Polyethylenoxiden mit Ethylenglycol und/oder Propylenglycol und aromatischen Dicarbonsäuren oder aromatischen und aliphatischen Dicarbonsäuren;
• Polyester aus einseitig endgruppenverschlossenen Polyethylenoxiden mit zwei- und/oder mehrwertigen Alkoholen und Dicarbonsäure.

Suitable soil release polymers and / or graying inhibitors for detergents are, for example:

• Polyesters of polyethylene oxides with ethylene glycol and / or propylene glycol and aromatic dicarboxylic acids or aromatic and aliphatic dicarboxylic acids;
• Polyester made of polyethylene oxides which are end group-capped with di- and / or polyhydric alcohols and dicarboxylic acid.

Such polyesters are known, for example from US-A 3,557,039, GB-A 1 154 730, EP-A-185 427, EP-A-421 984, EP-A-241 985, EP-A-272 033 and US-A 5,142,020.

Other suitable soil release polymers are amphiphilic graft or Copolymers of vinyl and / or acrylic esters on polyalkylene oxides (cf. US-A 4,746,456, US-A 4,846,995, DE-A 37 11 299, US-A 4,904,408, US-A 4,846,994 and US-A 4,849,126) or modified celluloses such as e.g. B. Methyl cellulose, hydroxypropyl cellulose or carboxymethyl cellulose.

To increase the cleaning performance, the detergents according to the invention can in particular contain soiling-releasing polymers, so-called soil-release polymers, which are generally composed of carboxylic acid units and, if appropriate, polymeric diol units and, for. B. contain ethylene terephthalate and polyoxyethylene terephthalate groups. Other monomer units, for example propylene glycol, polypropylene glycol, alkylene or alkenylene dicarboxylic acids, isophthalic acid, carboxy- or sulfo-substituted phthalic acid isomers can be contained in the soil release polymer. End-capped derivatives, ie polymers which have neither free hydroxyl groups nor free carboxyl groups but instead carry, for example, C ₁ -C ₄ -alkyl groups or are terminally esterified with monobasic carboxylic acids, for example benzoic acid or sulfobenzoic acid, can be used. Also suitable are the polyesters known from European patent application EP 0 241 985, which contain, in addition to oxyethylene groups and terephthalic acid units, 1,2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene groups and glycerol units and with C ₁ -C ₄ alkyl groups are end group-capped, the soil release polymers of ethylene terephthalate and polyethylene oxide terephthalate used in the agents of European patent application EP 0 253 567 with a molecular weight of 900 to 9,000, the polyethylene glycol units having molecular weights of 300 to 3,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 0.6 to 0.95, the polyesters with polypropylene terephthalate and polyoxyethylene terephthalate units which are end-capped at least partly by C ₁ -C ₄ -alkyl or acyl radicals and which are known from European patent application EP 0 272 033 and which in the European patent application EP 0 274 907 called sulfoethylene end groups closed terephthalate-containing soil-release polyester, the soil-release polyester produced by sulfonation of unsaturated end groups with terephthalate, alkylene glycol and poly-C ₂ -C ₄ -glycol units of European patent application EP 0 357 280, which is derived from European patent application EP 0 398 133 known cationic soil release polyesters with amine, ammonium and / or amine oxide groups and the cationic soil release polyesters with ethoxylated, quaternized morpholine units of European patent application EP 0 398 137. Polymers made from ethylene terephthalate and polyethylene oxide terephthalate are also suitable which the polyethylene glycol units have molecular weights from 750 to 5,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10 and their use in detergents is described in German patent DE 28 57 292, and polymers with a molecular weight of 15,000 to 50,000 from ethylene terephthalate and po is polyethylene oxide terephthalate to polyethylene oxide terephthalate 2: 1 to 6: 1, which can be used in detergents according to German patent application DE 33 24 258.

As a further additional component, the invention Textile detergent formulation usual color transfer inhibitors in the amounts usual for this (about 0.1 to 2 wt .-%) contain.

Color transfer inhibitors are, for example, homo- and Copolymers of vinyl pyrrolidone, vinyl imidazole, vinyl oxazolidone and 4-vinylpyridine-N-oxide with molecular weights from 15,000 to 100,000 and cross-linked, finely divided polymers based on these monomers used. The use of such polymers mentioned here is known see. DE-B 22 32 353, DE-A 28 14 287, DE-A 28 14 329 and DE-A 43 16 023.

As a further additional component, the invention Textile detergent formulation usual optical brighteners in the for this usual quantities included.

Are suitable for. B. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed Compounds that have a diethanolamino group instead of the morpholino group, a methylamino group, an anilino group or a 1-methoxyethylamino group wear. Brighteners of the type of substituted Diphenylstyryle be present, e.g. B. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Also Mixtures of the aforementioned optical brighteners can be used.

Dinatrium-4,4'-bis(2-dethanolamino-4-anilino-s-triazin-6-yl-amino)-stilben-2,2'-disulfonat,

Dinatrium-4,4'-bis(2-morpholino-4-anilino-s-triazin-6-yl-amino)stilben-2,2'-disulfonat,

Dinatrium-4,4'-bis(2,4-dianilino-s-triazin-6-yl-amino)stilben-2,2'-disulfonat.

Mononatrium-4',4''-bis(2,4-dianilino-s-triazin-6-yl-amino)stilben-2-sulfonat,

Dinatrium-4,4'-bis(2-anilino-4(N-methyl-N-2-hydroxyethylamino)s-triazin-6-yl-amino)stilben-2,2'-sulfonat,

Dinatrium-4,4'-bis(4-phenyl-2,1,3-triazol-2-yl)stilben-2,2'-disulfonat,

Dinatrium-4,4'-bis(2-anilino-4(1-methyl-2-hydroxyethylamino)s-triazin-6-yl-amino)stilben-2,2'-disulfonat und

Natrium-2(stilbyl-4''(naphtho-1',2',4,5)-1,2,3-triazol)-2-sulfonat.

Examples of common anionic optical brighteners are:

Disodium 4,4'-bis (2-dethanolamino-4-anilino-s-triazin-6-yl-amino) stilbene-2,2'-disulfonate,

Disodium 4,4'-bis (2-morpholino-4-anilino-s-triazin-6-ylamino) stilbene-2,2'-disulfonate,

Disodium 4,4'-bis stilbene-2,2'-disulfonate (2,4-dianilino-s-triazin-6-yl-amino).

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-ylamino) stilbene-2,2'-sulfonate,

Disodium 4,4'-bis (4-phenyl-2,1,3-triazol-2-yl) stilbene-2,2'-disulfonate,

Disodium 4,4'-bis (2-anilino-4 (1-methyl-2-hydroxyethylamino) s-triazin-6-yl-amino) stilbene-2,2'-disulfonate and

Sodium-2 (stilbyl-4 '' (naphtho-1 ', 2', 4,5) -1,2,3-triazol) -2-sulfonate.

Graying inhibitors have the task of that of the textile fiber to keep detached dirt suspended in the fleet. For this are water-soluble colloids mostly of an organic nature, for example Starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids the starch or the cellulose or salts of acidic Sulfuric acid esters of cellulose or starch. Also water soluble, polyamides containing acidic groups are suitable for this purpose. Furthermore, starch derivatives other than those mentioned above can be used use, e.g. B. aldehyde starches. Cellulose ethers such as Carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methylhydroxyethyl cellulose, methyl hydroxypropyl cellulose, Methyl carboxymethyl cellulose and mixtures thereof, for example in amounts of 0.1 to 5% by weight, based on the composition, used.

Furthermore, the textile detergent formulation according to the invention alkaline additives, especially sodium carbonate and / or Sodium bicarbonate, in amounts of up to 40% by weight, especially 1 up to 25 wt .-%, and adjusting agents, in particular alkali metal sulfates such as Sodium sulfate, in amounts of up to 60% by weight, in particular 1 to 30% by weight.

To those in the agents according to the invention, especially when they are in present in liquid or pasty form, usable in addition to water organic solvents include alcohols with 1 to 4 carbon atoms, especially methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms, especially ethylene glycol and propylene glycol, and their mixtures and those derived from the compound classes mentioned Ether. Such water-miscible solvents are in the agents according to the invention preferably in amounts not exceeding 30% by weight, in particular from 6% by weight to 20% by weight.

In particular when used in machine processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bisfatty acid alkyl diamides. Mixtures of different foam inhibitors are also used with advantages, e.g. B. from silicone, paraffins or waxes. The foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamide are particularly preferred.

To set a desired one by mixing the rest Components that do not have a self-determined pH value agents according to the invention systemic and environmentally compatible acids, especially citric acid, acetic acid, tartaric acid, malic acid, Lactic acid, glycolic acid, succinic acid, glutaric acid and / or Adipic acid, but also mineral acids, especially sulfuric acid or Contain bases, especially ammonium or alkali hydroxides. such In the agents according to the invention, pH regulators are present in amounts of preferably not more than 20% by weight, in particular from 1.2% by weight to 17 % By weight.

The agents can also be used in detergents and cleaning agents Contain common ingredients. On these optional components include in particular enzyme stabilizers as well as dyes and fragrances, Corrosion inhibitors, clays, bactericides, phosphonates and abrasives contain.

The detergent or cleaning agent formulation according to the invention can Bleach activators, especially the quaternized glycine nitriles incorporated that they as pure components or as with suitable additives pre-assembled components in powder or Granules of detergent are included, or so that they are distributed as pure components or as pre-assembled with suitable additives Components as from the other detergent ingredients separated powder or granules are present. Incorporation of quaternized glycine nitriles as separated powder or granules, in particular as a product pre-assembled with suitable additives, allows the gentle production of detergents with a special good stability of the bleach activator.

Uncompacted powder or granular detergents and cleaning agents usually have a low bulk density, usually from 200 to 600 g / l. You can also build a system based on Contain phosphate, be reduced in phosphate or be free of phosphate.

The washing and cleaning agent formulation according to the invention lies preferably in powder or granule form with a bulk density of 200 up to 1,100 g / l. However, liquid formulations are also possible.

The compositions according to the invention are not for use in Textile detergents limited, but can also be used for dishwashers, Stain removers (stain remover formulations), abrasives and descaling agents can be used.

1. schonende Bedingungen für Textilwaschgut aufgrund

• niedriger Waschtemperatur
• niedrigem pH-Wert im Vergleich zu herkömmlichen Waschmitteln

2. verbesserte Waschleistung bei geringerem Materialeinsatz (insbesondere Enzyme)

3. verbesserte Bleichwirkung bei schonenden Waschbedingungen.

The advantages of the detergent and cleaning agent compositions according to the invention can be summarized as follows:

1. gentle conditions for textile laundry due

• low washing temperature
• low pH compared to conventional detergents

2. Improved washing performance with less use of materials (especially enzymes)

3. Improved bleaching effect in gentle washing conditions.

Examples example 1

Peracetic acid release of different assembled TAED types

This method can be used to determine the peracetic acid kinetics in raw materials and full products can be used.

Principle:

TAED reacts to peracetic acid in the presence of hydrogen peroxide, which can be determined iodometrically. Thereby, through the titration on ice exploited the effect that only peracetic acid at low In contrast to temperatures, iodide is able to oxidize to iodine Hydrogen peroxide.

reagents:

Ice (distilled water)

Percarbonate (13.7% active)

Na ₂ S ₂ O ₃ standard solution (0.01 mol / l)

AI solution approx. 8%

Starch solution 3%

Acetic acid 20%

Equipment:

analytical balance

IKA RCT basic heating agitator, 250 ° C and level 6 (agitator)

IKA ETS-D4 fuzzy digital control thermometer, 40 ° C

Beaker 1000 ml wide shape

Dosimat with exchange unit

Full pipette 10 ml

Magnetic stirrer core 40x7 mm round shape

stopwatch

Mortar and pestle

Thermostat, 20 ° c

The analysis of the peracetic acid kinetics is carried out as follows:

1 g TAED are mixed with 4 g percarbonate in 1000 ml dist. Water (20 ° C) dissolved, analogously to 10 g of full product. From the time the samples were added to the water, the stopwatch was started and 10 ml was taken from the reacting mixture every 3 minutes. These 10 ml are pipetted onto approx. 50-100 g of ground ice. The sample / ice mixture is mixed with 10 ml of 8% KI solution and titrated rapidly with 0.1 Na thiosulfate solution to pale yellow. After adding a few drops of starch solution, titration is continued until it is colorless. The entire titration must run extremely quickly so that no distortion by hydrogen peroxide occurs. In addition, the temperature must be recorded when the sample is removed from the reaction vessel.
After 10 pairs of values have been recorded, the values are shown graphically in a diagram.

Evaluation:

V =

Verbrauch in ml

0,38 =

1 ml Na-Thiosulfatlösung (0,01 mol/l) zeigt 0,38 mg Peressigsäure an.

1000 =

Einwaage wurde in 1000 ml Wasser gelöst

10 =

10 ml wurden zur Titration abpipettiert

The calculation is based on the following formula: mg peracetic acid / 1 = V x 0.38 x 1000 10

V =

Consumption in ml

0.38 =

1 ml Na thiosulfate solution (0.01 mol / l) indicates 0.38 mg peracetic acid.

1000 =

Weigh-in was dissolved in 1000 ml of water

10 =

10 ml were pipetted off for titration

The results for three differently coated TAEDs are shown in Diagram 1. It is easy to see that the release of peracetic acid by the individual TAED types occurs at different speeds, depending on the packaging of the TAED.

Example 2

Washing performance of the detergent compositions according to the invention different temperatures (30 ° C and 40 ° C)

Detergent composition:

(Wt .-%) system Builder Sodium aluminum silicate 33 polycarboxylates 2 sodium 15 surfactant alkylbenzenesulfonate 2 Fatty alcohol sulfate 6 Nonionic 9 bleaching system Sodium percarbonate 15 Tetraacetylethylenediamine (TAED) 5 Cationic bleach activator (KB) 1 enzyme system protease <1 Properase.RTM 0.2 amylase <0.5 cellulase <0.1 lipase <0.5

additives

Oil release polymer, sodium sulfate, anti-foaming agent, brightener, phosphonate, Speckels, perfume ad 100

Stain removal on natural stains Test conditions: Prewash:

50 cmPer test product Cotton (BW) 50 X 50 cm for 5 washes Polyester / cotton (PES / BW) 50 X 20 cm Polyester (PES) 50 X 20 cm

50 cm

Each product is individually with 2/3 dosage without ballast at the prewashed later washing temperature.

Stain preparation:

Natural stains, e.g. Spinach, cocoa, gravy, fries fat

Storage:

1 week at room temperature (dark), then cool at approx. 7 ° C.

Washing:

With each product, 5 washes with the monitor and strong dirty household laundry (3.7 kg) at the desired temperature carried out.

color matching:

The monitors are first cut and labeled.
The sampling takes place according to the school grade principle, for this purpose the 5 replicas of all test products are spread out on the table and then divided into groups. Afterwards there is a reasonable grade.

Evaluation:

The average of 5 replicas is calculated and a duplicate Analysis of variance performed to provide statistical coverage receive.

The results of the washing tests are shown in diagrams 2a and 2b.

Example 3

Washing test evaluation of various TAED: bleach activator (BA) ratios at 30 ° C
A conventional heavy duty detergent (VWM) composition as described in Example 2 is used as the detergent. A combination of TAED and a bleach activator, here a quaternized glycine nitrile, is used in the detergent as the bleaching system. Spots BW VWM / 4.5% TAED VWM / 3% TAED / 2% BA VWM / 3% TAED / 1% BA VWM / 4% TAED / 1% BA lipstick 4 3.5 4.2 3.3 red wine 4 2.9 3.3 3.1 tea 3.8 2.8 3.3 3 PES / BW lipstick 4.2 4.2 3.5 4.2 Engine oil 4.6 4.6 4.0 4.6

1 = völlig entfernt

5 = sehr stark sichtbar

The washing results are evaluated according to the school grade system, i.e.:

1 = completely removed

5 = very visible

The results show that the addition of a bleach activator is additional to the previously used TAED to a significant improvement in Results in washing. In particular, a ratio of TAED: 3: 2 bleach activator, especially for bleach-sensitive stains (Red wine, tea) for very good washing results.

Example 4 Different enzyme ratios, use of Properase (Linite tests, 2nd Tables) wanted test Carrying out a linite test

Linitest uses four different fabrics, namely cotton, polyester, polyester / cotton and crude nettle. The four types of fabric are each cut to a size of 10 cm x 15 cm, with the crude nettle being pre-washed in the washing machine with 170 ml of surfactant solution.
For each series, a lobule with the same full whiteness is now sought from each fabric, whereby this may fluctuate up or down by 1 whiteness. The values are noted and then the initial Ry value is determined from each lobe.
A 10 cm x 15 cm WFK 10C soiling is added to each laundry for loading dirt.

Amount of washing powder for 1 wash liquor g wash liquor Dosage quantity for HB II in g 16 (fleet ratio)

Amount of wash liquor = weight of the 5 tissues x 16 (liquor ratio)

The beakers of the Linite test are filled with the calculated amount of wash liquor, the tissues are introduced and the beakers are closed. After insertion, a certain heating output (here 30 ° C and 40 ° C) and the duration are set.
After the set time, the lobules are taken out, rinsed and the whole process repeated accordingly.

Evaluation:

After the corresponding washes, the lobules are dried, measured and the Ry values or whiteness values are noted. The results are shown in diagrams 4a and 4b. Recipe 1 Recipe 2 Recipe 3 system Builder Active content in% by weight Sodium aluminum silicate 33 33 33 polycarboxylates 2 2 2 sodium 15 15 15 surfactant alkylbenzenesulfonate 2 2 2 Fatty alcohol sulfate 6 6 6 Nonionic 9 9 9 bleaching system Sodium percarbonate 15 15 15 Tetraacetylethylenediamine (TAED) 4 4 4 Cationic bleach activator (KB) 1 1 1 enzyme system Everlase® 0.67 0.42 1.54 Properase.RTM 0.20 0.20 amylase <0.50 <0.50 <0.50 cellulase <0.10 <0.10 <0.10 lipase <0.50 <0.50 <0.50 additives: ad 100 each Oil release polymer sodium sulphate Anti-foaming agents brighteners phosphonate Speckels Perfume

Claims (7)

Detergent or cleaning agent containing at least one Bleach activator and at least one TAED with a slow one Peracetic acid release kinetics. Detergent or cleaning agent according to claim 1, characterized in that it additionally contains a protease which develops maximum enzymatic activity at temperatures below 45 ° C. Detergent or cleaning agent according to claim 1 or 2, wherein as at least one bleach activator is a quaternized glycine nitrile is used. Detergent or cleaning agent according to one of claims 1 to 3, containing a combination of one at low temperatures (below 45 ° C) effective bleach activator with a Temperatures above 45 ° C effective bleach activator. Detergent or cleaning agent according to one of claims 1 to 4, a combination of low temperature (below 45 ° C) effective protease with at least one further protease is used. Detergent or cleaning agent according to one of claims 1 to 5, where the TAED is selected from such assembled TAEDs, that a peracetic acid concentration in the wash liquor of more than 100 mg / l is only reached after at least 5 min. Use of a cleaning agent according to one of claims 1 up to 6 for use as or in a textile detergent, Dish detergent, stain remover (stain remover), Descaling agents, abrasives.

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