EP1433839B2 - 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

Optimized detergent and cleaner system for improved bleaching action at low temperatures

The present invention relates to a composition for detergents or cleaners which have a bleaching effect at low temperatures.

Fabric detergent formulations as powders and as pressed molded articles usually contain a bleach system which consists mostly of active oxygen-supplying peroxo compounds, peracids or mixtures thereof and bleach activators. The most commonly used bleach activator is tetraacetylethylenediamine ("TAED"). The effect of TAED starts above 40 ° C, so TAED does not show sufficient effect in detergent liquors where the temperature is set below 40 ° C to protect clothing.

Other bleach activators are also known in the art. So describes z. For example, DE 100 38 844 A1 discloses a washing and cleaning agent containing a cationic bleach activator, this cationic bleach activator being an acetonitrile derivative with the anion of cumene sulfonic acid. By adding this bleach activator, the bleach effect of aqueous peroxide liquors can be increased to such an extent in this application that substantially the same effect as with the peroxide liquor alone at 95 ° C. can be achieved even at temperatures below 60 ° C. The application also describes the simultaneous use of the acetonitrile derivative with an enzyme to increase the cleaning performance of the washing and cleaning agent, especially against proteinaceous, starchy and / or colored stains, for use in aqueous washing and cleaning solutions, the contain a peroxygen compound. Enzymes which are particularly described are enzymes which have a pH optimum, preferably in the alkaline range, up to about pH 10. A particular bleaching effect at low temperatures is not considered in this application.

EP 0 941 299 describes a laundry detergent formulation which contains quaternized glycine nitriles as bleach activators, bleaches, surfactants and a calcium- and / or magnesium sequestering compound having a builder or co-builder function in specific proportions to one another. With this detergent composition an improved bleaching effect is achieved at low washing temperatures (from 20 ° C to 60 ° C), especially when using this detergent formulation in hard water.

EP 0 778 832 is concerned with a process for preparing such quaternized glycine nitriles which can be used as a bleach activator in detergent compositions.

Another bleach activator, namely an n-alkylammonium acetonitrile salt and its preparation are proposed in WO 00/58273. German Offenlegungsschriften DE 100 38 832 and DE 100 38 845 describe various formulations of bleach activators of the quaternized aminoalkyl nitrile type or the acetonitrile derivatives for use in detergents.

Further documents are DE 19740669 and DE 19914353.
However, none of the latter documents addresses the issue of increasing wash performance at low temperatures.

WO 02/083829 relates to mixed bleach activator compositions.

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

This object is achieved by a detergent composition containing at least one bleach activator and at least one TAED characterized in that the TAED is in a processing form which effects a peracetic acid release kinetics delayed to the bleach activator effect such that a peracetic acid concentration in the wash liquor of greater than 100 mg / l is reached only after at least 5 minutes, wherein as at least one bleach activator a quaternized glycine nitrile is used.

According to the invention, at least one bleach activator is a quaternized glycinonitrile. As a further bleach activators all bleach activators may be used, show at temperatures below 45 ° C an activating for the bleaching action in washing liquors, these are, for example, compounds of the substance classes of polyacyliertem sugars or sugar derivatives with C ₁ -C ₁₀ acyl radicals, preferably acetyl , Propionyl, octanoyl, nonanoyl or benzoyl radicals, in particular acetyl radicals. 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.

Also useful as additional bleach activators are O-acyl oxime esters such as e.g. O-acetylactone oxime, O-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 additional bleach activators are N-acyl caprolactams, such as N-acetyl caprolactam, N-benzoyl caprolactam, N-octanoyl caprolactam, N-octanoyl caprolactam, or carbonyl biscaprolactam, which patented uses at least one bleach activator, a quaternized glycine nitrile.

• N-diacylierte und N,N'-tetracylierte Amine, z. B. N,N,N',N'-Tetra-acetylmethyldiamin 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-mesylacetamid 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-succinylhydroxylamin 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.

Further useful as bleach activators besides the patented use of quaternized glycine nitrile as at least one bleach activator

• N-diacylated and N, N'-tetracyclized amines, e.g. N, N, N ', N'-tetra-acetylmethyldiamine 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-carboxamides, eg. N-methyl-N-mesylacetamide or N-methyl-N-mexylbenzamide;
• N-acylated cyclic hydrazides, acylated triazoles or urazoles, e.g. Monoacetyl-maleic hydrazide;
• O, N, N-trisubstituted hydroxylamines, e.g. B. ON, N-trisubstituted hydroxylamines, eg. O-benzoyl-N, N-succinylhydroxylamine, O-acetyl-N, N-succinylhydroxylamine or O, N, N-triacetalhydroxylamine;
• N, N'-diacyl-sulfurylamides, e.g. N, N'-dimethyl-N, N'-diacetylsulfurylamide or N, N'-diethyl-N, N'-dipropionyl-sulfurylamide;
• Triacylcyanurates, e.g. Triacetyl cyanurate or tribenzoyl cyanurate;
• Carboxylic anhydrides, eg. 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. For example, 1,4-diacetyl-2,5-diketopiperazine;
• Acylation products of propylene diurea and 2,2-dimethylpropylenediurea, e.g. B. tetraacetylpropylenediurea,
• α-acyloxy-polyacyl malonamides, e.g. For example, α-acetoxy-N, N'-diacetylmalonamide;
• Diacyl-dioxohexahydro-1,3,5-triazines, e.g. For example, 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine.

Also usable as bleach activators in addition to the patented use of quaternized glycine nitrile as at least one bleach activator are 2-alkyl- or 2-aryl- (4H) -3,1-benzoxain-4-ones, as described, for example, in EP-B-332 294 and EP-B-502 013 are described. In particular, 2-phenyl- (4H) -3,1-benzoxain-4-one and 2-methyl- (4H) -3,1-benzoxain-4-one can be used in addition to the patented use of quaternized glycine nitrile as at least one bleach activator ,

In addition, bleach activators from the classes of N- or O-acyl compounds, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, also carboxylic acid anhydrides , in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyloxybenzenesulfonate, sodium isononanoyloxy-benzenesulfonate and acylated sugar derivatives, such as pentaacetylglucose are used, wherein a quaternized glycinenitrile is used according to the patent as at least one bleach activator.

European Patent Application EP 0 464 880 discloses bleach-enhancing 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 having at least one 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 "and R"' are each a C ₁ -C ₂₄ alkyl or hydroxyalkyl group and the counteranion X ^{- is} an organic sulfonate, or a carboxylate.

In addition, it is also possible to use compounds as described in DE 100 38 844 A1 under the general formula I, wherein a quaternized glycinonitrile is used according to the patent as at least one bleach activator.

However, at least one bleach activator is a quaternized glycine nitrile from the group consisting of N-methylmorpholinium acetonitrile methylsulfate, sulfate and hydrogen sulfate. The activator can act as the sole bleach activator in the detergent composition are used, or in combination with one of the aforementioned bleach activators.

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

It has been shown that it is of particular advantage and the washing and cleaning performance of the composition according to the invention can be significantly improved if, for use at low temperatures (below 45 ° C.), a TAED is used in a processing form which contains a delayed peracetic acid Release causes. This means that it is preferable to use a ready-made TAED which does not release peracetic acid immediately upon contact with water in combination with percarbonate, but only with a certain delay. Delayed peracetic acid release enhances the washing performance of other ingredients, especially at a wash temperature of 30 ° C. Without wishing to be bound by the following explanation, it is assumed that the improved washing performance is based on the fact that, at the beginning of the washing process, the bleach activator used, which is at least one quaternized glycine nitrile, is activated by too-rapid release of peracetic acid the TAED seems to be disturbed in its performance. This means that the bleach activator shows a significantly better effect, if at the beginning of the washing process, no very high peracetic acid concentration is present. The same applies to the performance of Properase. After the bleach activator has exerted its effect, it is advantageous for the washing result if the peracetic acid concentration increases in the course of the washing process. Such a "delayed" occurrence of a high peracetic acid concentration improves in particular the bleaching action of the washing or cleaning agent according to the invention at low temperatures.

1. a) die Auflösegeschwindigkeit des TAED Coatings
2. b) die Dicke des TAED Coatings
3. c) die Dichte des TAED Granulats

The peracetic acid kinetics is determined by:

1. a) the dissolution rate of the TAED coating
2. b) the thickness of the TAED coating
3. c) the density of the TAED granules

On a): it is preferred to use a TAED coated with a protective coating which dissolves only slowly in the wash liquor, and thus the TAED only takes effect with a delay, namely when the coating is removed.

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

On c) a highly compressed TAED granules must first be decompressed in the wash liquor before the TAED can develop its action for peracetic acid release. Therefore, the compacting of the granules used also influences the peracetic acid release kinetics.

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

By a "delayed release" is meant that a concentration of more than 100 mg / l peracetic acid in the wash liquor occurs only after a few minutes, according to the patent after at least 5 min and preferably after at least 8 min. After this time, however, a rapid increase in the peracetic acid concentration in the wash liquor is desired.

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

In addition to the bleach activator, which is at least one quaternized glycine nitrile, suitable bleaching agents, which may be common, commonly known bleaches for detergent compositions, are added to the detergent composition.

As for the use in agents according to the invention suitable peroxygen compounds are in particular hydrogen peroxide and under the washing conditions hydrogen peroxide donating inorganic salts to which alkali metal perborates such. As sodium perborate tetrahydrate and sodium perborate monohydrate, further alkali metal carbonate perhydrates such as sodium carbonate perhydrate ("sodium percarbonate") and persilicates and / or - persulfates such as caroate include. In most cases, in addition to these inorganic peroxy compounds, the bleach system of the detergent formulation may contain inorganic or organic peracids, especially percarboxylic acids, e.g. B. C ₁ -C ₁₂ -Percarbonsäuren, C ₈ -C ₁₆ -Dipercarbonsäuren, Imidopercapronsäuren or Aryldipercapronsäuren. preferred Examples of acids which can be used are peracetic acid, perbenzoic acid, linear or branched octane, nonane, decane or dodecane monoperacids, decane and dodecane diperacid, mono- and diperphthalic acids, isophthalic acids and terephthalic acids, phthalimidopercaproic acid, terephthaloyldiamidopercaproic acid and e-phthalimido peroxohexanoic 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 enveloped in a manner known in principle. A particularly preferably used peracid is the peracid available under the trade name Eureco® (Ausimont, Italy). Peroxygen compounds are present in amounts of preferably up to 50% by weight, more preferably from 5% to 30% and most preferably from 8% to 25% by weight. The addition of minor amounts of known bleach stabilizers such as phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful.

In one embodiment of the present invention, at least one bleach activator, which is a quaternized glycine nitrile, and an effective peracid are present as raw materials side by side in the detergent formulation, however, their effect is offset in time by the sustained release of the peracid. Preferably, the peracid is in granular form. This embodiment has the advantage that, regardless of the pH and washing temperature set in the wash liquor, a bleaching effect is achieved in each case entry. At low pH (pH 8.5 to 9), especially the effect of the peracid, which develops a bleaching effect without activation, comes to the fore. At higher pH (pH> 9) the bleach activator unfolds its full effect, so that here too an increased bleaching effect occurs.

Also, various bleach activators, namely those which exert their action at low temperatures (below 45 ° C) and those which exert their action at higher temperatures (from 40 ° C), may coexist as a mixture in the washing or cleaning composition. In this way, the temperature range in which the detergent can be used, be significantly widened.

The bleach catalysts used are usually quaternized imines or sulfonimines, as described, for example, in US Pat. No. 5,360,568, US Pat. No. 5,360,569 and EP-A-453,003, as well as manganese complexes, as described, for example, in WO-A 94/21777 are. Other useful metal-containing bleach catalysts are described in EP-A-458,397, EP-A-458,398 and EP-A-549,272. Bleach catalysts are generally used in amounts of up to 1 wt .-%, in particular 0.01 to 0.5 wt .-%, based on the detergent formulation.

Bleach stabilizers are additives which can adsorb, bind or complex interfering heavy metal traces during bleaching. In particular, customary complexing agents such as ethylenediaminetetraacetate, nitrilotriacetic acid, methylglycinediacetic acid, .beta.-alaninediacetic acid, ethylenediamine-N, N'-disuccinate and phosphonates such as ethylenediamine tetramethylenephosphonate, diethylenetriaminepentamethylenephosphonate or Hydroxyethylidene-1,1-diphosphonic acid in the form of acids or as partially or completely neutralized alkali metal salts in amounts of up to 1 wt .-%, in particular 0.01 to 0.5 wt .-%, based on the detergent formulation used.

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 enzymatically active protein per gram of the total composition. The protein concentration can be determined by known methods, e.g. The bicinchonic acid method (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).

As at least one washing-active enzyme, a protease is used which develops a substantial part of its activity at temperatures below 45 ° C. An example of such a protease is the enzyme Properase.RTM ^® 4000 E, which is marketed by Genencor International.

The other enzymes used may also be those which have an activity maximum at low temperatures. However, the enzymes used should develop a certain activity, at least at temperatures below 45 ° C, even though their maximum does not have to be there.

In addition to these proteins which are specialized at low temperatures, it is possible to use further enzymes conventionally used in previous detergents, for example proteases, lipases, amylases, cellulases and peroxidases. Preference is given to using detergents which are optimized in the alkaline medium and which are active in the alkaline medium in amounts customary for this purpose (about 0.1 to 3% by weight).

Suitable proteases include the enzymes obtainable from microorganisms, in particular bacteria or fungi, having a pH optimum in the alkaline range, for example those from international patent applications WO 92/07067, WO 91/02792, WO 88/03947 or WO 88/03946 or European patent applications EP 471 265,
EP 416 967 or EP 394 352 known proteases.

Protease is preferably used in the composition according to the invention in amounts such that the finished composition contains 100 PE / g (protease units per gram, determined by the method described in Tenside 7, 125 (1970)), in particular 125 PE / g to 5,000 PE / g and more preferably 150 PE / g to 4500 PE / g. Suitable proteases are commercially 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 proteases mentioned, the use of Properase® is particularly preferred.

The amylases which can be used in the compositions according to the invention, which are preferably used in combination with at least one further enzyme, include the enzymes which can be obtained from bacteria or fungi and which have a pH optimum preferably in the alkaline range up to about pH 10. Useful commercial products are, for example, amylase LT, Aquazym®. Duramyl®, Maxamyl®, Purastar®, Purafect® 0xAm or Termamyl®. Amylase is preferably used in the composition according to the invention in amounts such that the finished product is from 0.01 KNU / g to 2 KNU / g ("kilo-novo units" per gram according to the standard method of the Company Novo, where 1 KNU is the amount of enzyme which builds 5.26 g of starch at pH 5.6 and 37 ° C, based on that of P. Bernfeld in SP Colowick and ND Kaplan, Methods in Enzymology, Volume 1, 1955, Page 149), in particular 0.015 KNU / g to 1.8 KNU / g and more preferably 0.03 KNU / g to 1.6 KNU / g. If the agent according to the invention contains an amylase, it is preferably selected from the genetically modified amylases. Genetically modified amylases are known, for example, from international patent applications WO 94/18314 or WO 95/21247.

The lipase optionally contained in the agent according to the invention is an enzyme which can be obtained from microorganisms, in particular bacteria or fungi. 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 preferably used in the composition of the invention in amounts such that the finished composition has a lipolytic activity in the range of 10 LU / g to 10,000 LU / g ("Lipase Activity Units" per gram as determined by the enzymatic hydrolysis of tributyrin at 30 ° C and pH 7 according to the 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. Commercially available lipases are, for example, Lipex®, Lipolase®, Lipolase Ultra®, Lipomax®, Lipoprime®, Lipozym® and Lumafast®,

Likewise, the cellulase useful in the invention belongs to the enzymes obtainable from bacteria or fungi, which have a pH optimum preferably in the almost neutral to slightly alkaline pH range of 6 to 9.5. such Cellulases are known, for example, from German laid-open applications DE 31 17 250, DE 32 07 825, DE 32 07 847, DE 33 22 950, 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. They are preferably used in the composition according to the invention in amounts such that the finished composition has a cellulolytic activity of from 0.05 IU / g to 1.5 IU / g ("International Units" per gram, based on the enzymatic hydrolysis of Na-carboxymethylcellulose) pH 9.0 and 40 ° C, as described in Agric, Biol. Chem. 53, 1275 (1989) by S.Ito et al.), in particular 0.07 IU / g to 1.4 IU / g and particularly preferred 0.1 IU / G to 1.3 IU / g. Suitable commercial products include, for example, Carezyme®, Celluzyme®, Ecostase®, and Novozym® from Novo Nordisk or KAC® from Kao. The preferred cellulases include those from Melanocarpus sp. or Myriococcum sp. Available 20K cellulase known from international patent application WO 97/14804. It has as described there a molecular weight of about 20 kDa and has at 50 ° C in the pH range of 4 to 9 at least 80% of their maximum activity, while still maintaining almost 50% of the maximum activity at pH 10. It can, as also described there, be isolated from Melanocarpus albomyces and be produced in genetically engineered Trichoderma reseei transformants.

Suitable enzymes which can additionally be used in the compositions are those from the class of cutinases, pullulanases, hemicellulases, oxidases, laccases and peroxidases and mixtures thereof. Particularly suitable are fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, Pseudomonas cepacia or Coprinus cinereus derived enzymatic agents. The enzymes can, such as. As described in European patent EP 0 564 476 or in the international patent application WO 94/23005, adsorbed on carriers and / or embedded in encapsulants to protect against premature inactivation. They are preferably present in the detergents or cleaners according to the invention in amounts of up to 5% by weight, in particular from 0.2% by weight to 4% by weight.

If several enzymes are to be used in the composition according to the invention, this can be achieved by incorporation of the two or more separate or in a known manner separately prepared enzymes or by two or more together in a granule ready-made enzymes, such as. From international patent applications WO 96/00772 or WO 96/00773.

In a particularly preferred embodiment, a mixture of two proteases, of which one is Properase®, is used in the washing or cleaning agent according to the invention, optionally together with other enzymes (amylase, lipase, cellulase). The use of Properase® in addition to another protease significantly improves the washing and cleaning properties of the washing and cleaning agent according to the invention, while at the same time less total amount of protease must be used, both in terms of the absolute amount used, as well as in terms of the international enzyme units used the enzymes. This additionally leads to a cost reduction in the production of the product produced.

Another advantage of reducing the total amount of protease is that a textile detergent produced in this way acts particularly gently on wool laundry.

Surfactants may be present in the detergent and cleaner composition as further customary detergent ingredients; nonionic and / or anionic surfactants or mixtures thereof are particularly preferred.

Suitable anionic surfactants are, for example, fatty alcohol sulfates of fatty alcohols having 8 to 22, preferably 10 to 18 carbon atoms, for. 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 first preparing a C ₈ -C ₂₂ -, preferably a C ₁₀ -C ₁₈ -alcohol, for. As a fatty alcohol, alkoxylated and then sulfating the alkoxylation product. 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 with propylene oxide alone and optionally 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 may contain the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or in random distribution.

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

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

Further suitable anionic surfactants are N-acylsarcosinates with aliphatic saturated or unsaturated C ₈ -C ₂₅ -acyl radicals, preferably C ₁₀ -C ₂₀ -acyl radicals, eg. B. N-Oleoylsarcosinate.

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. B. hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium ions.

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

Suitable nonionic surfactants are, for example, alkoxylated C ₈ -C ₂₂ -alcohols, such as fatty alcohol alkoxylates or oxo alcohol alkoxylates. The alkoxylation can be carried out with ethylene oxide, propylene oxide and / or butylene oxide. Suitable surfactants are all alkoxylated alcohols which contain at least two molecules of an abovementioned alkylene oxide added. Also suitable here are block polymers of ethylene oxide, propylene oxide and / or butylene oxide or adducts which contain the abovementioned alkylene oxides in random distribution. Per mole of alcohol As a rule, 2 to 50, preferably 3 to 20, moles of at least one alkylene oxide are used. Preferably used as alkylene oxide ethylene oxide. The alcohols preferably have 10 to 18 carbon atoms.

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

Another class of nonionic surfactants are alkyl polyglucosides of 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 units.

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-alkylglucamides of general structure II or III

Wherein R ^{6 is} C ₆ -C ₂₂ -alkyl, R ^{7 is} H or C ₁ -C ₄ -alkyl and R ^{8 is} a polyhydroxyalkyl radical having 5 to 12 C-atoms and at least 3 hydroxy groups. Preferably, R ^{6 is} 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 acylation of reductively aminated sugars with acid chlorides of C ₁₀ -C ₁₈ carboxylic acids.

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

As substances with primarily builder or cobuilder function, preference is given to using representatives from the group of zeolites, silicates, alkali metal phosphates, polycarboxylates and aminopolycarboxylates individually or in mixtures.

Zeolites and silicates can be referred to in principle as inorganic ion exchangers. Suitable zeolites (aluminosilicates) are especially those of the type A, P, X, B, HS and MAP in their sodium form or in forms in which sodium is partially exchanged for other cations such as Li, K, Ca, Mg or ammonium. Such zeolites are described, for example, in EP-A 0 038 591, EP-A 0 087 035, US Pat. No. 4,604,224, GB-A 2 013 259, EP-A 0 522 726, EP-A 0 384 070 and WO-A 94 / 24,251th

Suitable amorphous or crystalline silicates, in particular phyllosilicates, are above all amorphous disilicates and crystalline disilicates, such as the phyllosilicate SKS-6 (manufacturer: Hoechst). The silicates can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Preferably, Na, Li and Mg silicates are used.

Particularly suitable alkali metal phosphate is trisodium polyphosphate, which may also be considered as an inorganic ion exchanger.

• 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 -Tetracarbonsäuren such. Succinic acid, propane tricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid and alkyl and alkenyl succinic acids with C ₂ -C ₁₆ alkyl or alkenyl radicals.
• C ₄ -C ₂₀ -hydroxycarboxylic acids such as. Malic acid, tartaric acid, gluconic acid, glucaric acid, citric acid, lactobionic acid and sucrose mono-, di- and tricarboxylic acid;
• complexing acting Aminopolycarboxylate such. Nitrilotriacetic acid, methylglycinediacetic acid, β-alaninediacetic acid, ethylenediaminetetraacetic acid, serinediacetic acid or ethylenediamine-N, N'-disuccinate, preferably in the form of their partially or fully 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.
  Als ungesättigte C₄-C₈-Dicarbonsäuren sind hierbei beispielsweise Maleinsäure, Fumarsäure, Itaconsäure und Citraconsäure geeignet. Bevorzugt wird Maleinsäure.

Suitable oligomeric or polymeric polycarboxylates and aminopolycarboxylates are in particular:

• Oligomaleeinsäuren, as described for example in EP-A 0 451 508 and EP-A 0396303;
• Co- and terpolymers of unsaturated C ₄ -C ₈ -dicarboxylic acids, wherein as comonomers monoethylenically unsaturated monomers
  • from the group (i) in amounts of up to 95% by weight,
  • from the group (ii) in amounts of up to 60% by weight,
  • from the group (iii) in amounts of up to 20 wt .-% may be included in copolymerized form.
  Examples of suitable unsaturated C ₄ -C ₈ -dicarboxylic acids are maleic acid, fumaric acid, itaconic acid and citraconic acid. Preference is given to maleic acid.

The group (i) comprises monoethylenically unsaturated C ₃ -C ₈ monocarboxylic acids such as. For example, acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid. Preferably, from group (i), acrylic acid and methacrylic acid are used.

Group (ii) comprises monoethylenically unsaturated C ₂ -C ₂₂ -olefins, vinylalkyl ethers having C ₁ -C ₈ -alkyl groups, styrene, vinyl esters of C ₁ -C ₈ -carboxylic acids, (meth) acrylamide and vinylpyrrolidone. C ₂ -C ₆ -olefins, vinyl alkyl ethers having C ₁ -C ₄ -alkyl groups, vinyl acetate and vinyl propionate are preferably used from group (ii).

Group (iii) comprises (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) contain copolymerized vinyl esters, these can also be partially or completely hydrolyzed to vinyl alcohol structural units. Suitable copolymers and terpolymers are known, for example, from US Pat. No. 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.

Suitable copolymers of dicarboxylic acids are, in particular:

• Copolymers of maleic acid and acrylic acid in a weight ratio of 10:90 to 95: 5, in particular those in the weight ratio 30:70 to 90:10, in particular having molecular weights of from 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 10 (maleic acid): 90 (acrylic acid + vinyl ester) to 95 (maleic acid): 5 (acrylic acid + vinyl ester), wherein the weight ratio of acrylic acid to vinyl ester may vary in the range of 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), wherein the weight ratio of acrylic acid to vinyl ester may vary in the range of 30:70 to 70:30.
• 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 the molar ratio of about 50:50 are 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 contemplated. Examples of suitable unsaturated carboxylic acids are maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid and also mixtures of acrylic acid and maleic acid which are grafted in amounts of from 40 to 95% by weight, based on the component to be grafted.

For modification, in addition up to 30% by weight, based on the component to be grafted, of further monoethylenically unsaturated monomers can be present in copolymerized form. Suitable modifying monomers are the above-mentioned monomers of groups (ii) and (iii).

As a graft are degraded polysaccharides such. B. acidic or enzymatically degraded starches, inulins or cellulose, reduced (hydrogenated or hydrogenated aminated) degraded polysaccharides such. As mannitol, sorbitol, aminosorbitol and glucamine suitable as well as polyalkylene glycols having molecular weights up to M _w = 5,000 such. B. polyethylene glycols, ethylene oxide / propylene oxide or ethylene oxide / butylene oxide block copolymers, random 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 degraded or degraded reduced starches and grafted polyethylene oxides are preferably used from this group, with from 20 to 80% by weight of monomers, based on the grafting component, being used in the graft polymerization. For grafting, preference is given to using a mixture of maleic acid and acrylic acid in a weight ratio of 90:10 to 10:90.

Polyglyoxylic acids are described, for example, in EP-B 0 001 004, US Pat. No. 5,399,286, DE-A 41 06 355 and EP-A 0 656 914. The end groups of the polyglyoxylic acids may have different structures.

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

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 preferably also used as aminopolycarboxylates. Particularly preferred are in phosphorus-containing Acids produced, with C ₆ -C ₂₂ mono- or dicarboxylic acids or with C ₆ -C ₂₂ mono- or diamines modified polyaspartic acids used.

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

Particularly preferred in 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 copolymers (especially those of molecular weight 10,000 to 100,000), polyaspartic acid, citric acid, nitrilotriacetic acid, methylglycinediacetic and mixtures used therefrom.

As mixtures of particular interest 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 and zeolites, layered silicates and acrylic acid / maleic acid copolymers ,

As an additional constituent, the textile detergent formulation according to the invention may contain customary grayness inhibitors and / or soil-release polymers in the amounts customary for this purpose (about 0.1 to 2% by weight).

• 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 grayness 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;
• Polyesters of unilaterally end-capped polyethylene oxides with dihydric 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.

Further suitable soil-release polymers are amphiphilic graft 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. Methylcellulose, hydroxypropylcellulose or carboxymethylcellulose.

In order to enhance the cleaning performance, in particular the detergents according to the invention may comprise soil release polymers, so-called soil release polymers, which are generally composed of carboxylic acid units and optionally polymeric diol units and z. As 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 may be included in the soil release polymer. Also end-capped derivatives, ie polymers which have neither free hydroxyl groups nor free carboxyl groups, but carry, for example, C ₁ -C ₄ -alkyl groups or terminally esterified with monobasic carboxylic acids, for example benzoic acid or sulfobenzoic acid, can be used. Also suitable are the polyesters disclosed in 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 also glycerol units C ₁ -C ₄ alkyl groups are end-capped, used in the agents of European Patent Application EP 0253567 soil release polymers of ethylene terephthalate and polyethylene oxide terephthalate having a molecular weight of 900 to 9,000, wherein the polyethylene glycol units have molecular weights from 300 to 3,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 0.6 to 0.95, the polyesters disclosed in European Patent Application EP 0 272 033, at least partially terminated by C ₁ -C ₄ alkyl or acyl groups, with polypropylene terephthalate and polyoxyethylene terephthalate units disclosed in US Pat the European Patent Application EP 0 274 907 sulfoethylendgruppenve terephthalate-containing soil-release polyester, the soil release polyester prepared 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 are described in European Patent Application EP 0 398 133 known cationic soil-release polyester having amine, ammonium and / or amine oxide groups and the cationic soil release polyesters with ethoxylated, quaternized morpholine units of the European patent application EP 0 398 137. Also suitable are polymers of ethylene terephthalate and polyethylene oxide, in in which the polyethylene glycol units have molecular weights of from 750 to 5,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is from 50:50 to 90:10 and their use in detergents is described in German Patent DE 28 57 292, and polymers having a molecular weight of from 15,000 to 50,000 of ethylene terephthalate and Polyethylene oxide terephthalate to polyethylene oxide terephthalate 2: 1 to 6: 1, which can be used according to the German patent application DE 33 24 258 in detergents.

As a further additional constituent, the textile detergent formulation according to the invention may comprise customary color transfer inhibitors in the quantities customary for this purpose (about 0.1 to 2% by weight).

As color transfer inhibitors, for example, homopolymers and copolymers of vinylpyrrolidone, of vinylimidazole, of vinyl oxazolidone and of 4-vinylpyridine N-oxide having molecular weights of from 15,000 to 100,000 and crosslinked finely divided polymers based on these monomers are used. The use of such polymers mentioned here is known, cf. 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 constituent, the textile detergent formulation according to the invention may contain customary optical brighteners in the quantities customary for this purpose.

Suitable z. B. salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure, instead of the morpholino group a diethanolamino group, a methylamino group, an anilino group or a 1-methoxyethylamino group wear. Furthermore, brighteners of the type of substituted Diphenylstyryle be present, for. 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). Mixtures of the aforementioned optical brightener 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 (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-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 keeping suspended from the textile fiber dirt suspended in the fleet. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids starch or 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, other than the above-mentioned starch derivatives can be used, for. B. aldehyde levels. Preference is given to using cellulose ethers, such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the compositions.

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

Among the solvents according to the invention, in particular when they are in liquid or pasty form, organic solvents which can be used in addition to water include alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C -Atomen, in particular ethylene glycol and propylene glycol, and mixtures thereof and derived from the classes of compounds mentioned ether. Such water-miscible solvents are preferably present in the compositions according to the invention in amounts of not more than 30% by weight, in particular from 6% by weight to 20% by weight.

In particular, when used in mechanical processes, it may be advantageous to add conventional foam inhibitors to the compositions. As 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 foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silicic acid or bis-fatty acid alkylenediamides. With advantages, mixtures of different foam inhibitors are used, for. As those of silicones, 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. In particular, mixtures of paraffins and bistearylethylenediamide are preferred.

To establish a desired, by the mixture of the other components not automatically resulting pH value, the compositions of the invention system and environmentally acceptable acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid or bases, in particular ammonium or alkali hydroxides. Such pH regulators are present in the compositions according to the invention in amounts of preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.

In addition, the agents may contain other ingredients customary in detergents and cleaners. These optional ingredients include in particular Enzyme stabilizers and colorants and fragrances, corrosion inhibitors, clays, bactericides, phosphonates and scouring agents.

The washing or cleaning agent formulation according to the invention may contain the bleach activators, which comprise at least one quaternized glycinonitrile incorporated in such a way that they are distributed as pure components or as prefabricated components with suitable additives in the powder or granules of the detergent, or in such a way that they pure components or as prefabricated with suitable additives components as separated from the other detergent ingredients powder or granules. The incorporation of quaternized glycine nitriles as separated powder or granules, in particular as a product prefabricated with suitable additives, allows the gentle production of detergents with a particularly good stability of the bleach activator.

Non-compacted powdered or granular detergents and cleaners usually have a low bulk density, usually from 200 to 600 g / l. They may also contain a phosphate-based builder system, phosphate-reduced or phosphate-free.

The detergent and cleaner formulation according to the invention is preferably in powder or granule form with a bulk density of 200 to 1100 g / l. However, liquid formulations are also possible.

The compositions of the invention are not limited to use in laundry detergents but can also be used for dishwashing detergents, stain removers (Stain salt formulations), scouring agents and descaling agents.

1. 1. schonende Bedingungen für Textilwaschgut aufgrund
   • niedriger Waschtemperatur
   • niedrigem pH-Wert im Vergleich zu herkömmlichen Waschmitteln
2. 2. verbesserte Waschleistung bei geringerem Materialeinsatz (insbesondere Enzyme)
3. 3. verbesserte Bleichwirkung bei schonenden Waschbedingungen.

In summary, the advantages of the detergent and cleaner compositions according to the invention can be represented as follows:

1. 1. Gentle conditions for textile laundry due to
   • low washing temperature
   • low pH compared to conventional detergents
2. 2. improved washing performance with lower material usage (especially enzymes)
3. 3. improved bleaching effect with gentle washing conditions.

Examples example 1 Peracetic acid release of various types of TAED types

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

Principle:

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

reagents:

Ice (distilled water)
Percarbonate (13.7% active)
Na ₂ S ₂ O ₃ mass solution (0.01 mol / l)
AI solution approx. 8%
Starch solution 3%
Acetic acid 20%

Equipment:

analytical balance
IKA RCT basic stirrer, 250 ° C and stage 6 (stirrer)
IKA ETS-D4 fuzzy digital thermostat, 40 ° C
Beaker 1000 ml wide form
Dosimat with exchange unit
Full pipette 10 ml
Magnetic stirrer 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 of TAED are distilled with 4 g of percarbonate in 1000 ml.
• Dissolved water (20 ° C), analogous to 10 g of full product. From the time the samples are added to the water, the stopwatch is started and every 3 minutes 10 ml are removed from the reacting mixture. These 10 ml are pipetted to about 50-100 g of crushed ice. The sample / ice mixture is mixed with 10 ml of 8% KI solution and quickly titrated with 0.1 Na thiosulfate solution to pale yellow. After adding a few drops of starch solution, titration is continued until colorless. The entire titration must be extreme run smoothly, so that no distortion by hydrogen peroxide occurs. In addition, when removing the sample from the reaction vessel, the temperature must be detected. After 10 pairs of values have been recorded, the values are graphically displayed 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 abpipettiertThe calculation is made according to the following formula: $$\mathrm{mg\; peracetic\; acid}/\mathrm{l}=\frac{\mathrm{V\; x}\mathrm{0}.\mathrm{38}\mathrm{x}\mathrm{1000}}{\mathrm{10}}$$

V = consumption in ml
0.38 = 1 ml of sodium thiosulfate solution (0.01 mol / l) shows 0.38 mg
Peracetic acid on.
1000 = weight was dissolved in 1000 ml of water
10 = 10 ml were pipetted off for titration

The results for three differently coated TAED are shown in diagram 1. It is good to see that the release of peracetic acid by the individual TAED types takes place at different rates, depending on the preparation of the TAED.

Example 2 Washing performance of the invention

Detergent compositions at various 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 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-soluble polymer, sodium sulfate, antifoaming agent, brightener, phosphonate, speckle, perfume
ad 100
Stain removal on natural stains

Test conditions:

50 cmPrewash: Per 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 prewashed at 2/3 dosage without ballast at the later washing temperature.

• Natürliche Verfleckungen, z.B. Spinat, Kakao, Bratensauce, Frittenfett

Stain preparation:

• Natural stains, eg spinach, cocoa, gravy, frying fat

• 1 Woche bei Raumtemperatur (dunkel), danach kühl bei ca. 7 °C.

Storage:

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

• Bei jedem Produkt werden 5 Wäschen mit dem Monitor und stark verschmutzter Haushaltswäsche (3,7 kg) bei gewünschter Temperatur durchgeführt.

Washing:

• For each product, 5 washes are performed with the monitor and heavily soiled household linen (3.7 kg) at the desired temperature.

• Die Monitore werden zunächst zerschnitten und beschriftet. Die Abmusterung erfolgt nach dem Schulnotenprinzip, dazu werden die 5 Replikate aller Testprodukte auf dem Tisch ausgebreitet und dann in Gruppen eingeteilt. Anschließend erfolgt eine sinnvolle Benotung.

color matching:

• The monitors are first cut and labeled. The matching takes place according to the school grading principle, in addition the 5 replicates of all test products are spread out on the table and then divided into groups. Subsequently, a meaningful grading takes place.

• Von 5 Replikaten wird der Durchschnitt errechnet und eine doppelte Varianz-Analyse durchgeführt, um eine statistische Absicherung zu erhalten.

Evaluation:

• From 5 replicates, the average is calculated and a double variance analysis is performed to obtain a statistical hedge.

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

Example 3

Washing test evaluation of various TAED: bleach activator (BA) ratios at 30 ° C
The detergent used is a conventional heavy-duty detergent (VWM) composition, as described in Example 2. As bleaching system according to the invention a combination of TAED with the bleach activator quaternized glycine nitrile is used in the detergent. Patch 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 evaluation of the washing results takes place according to the school grading system, thus:

• 1 = completely removed
• 5 = very visible

The results show that the addition of the bleach activator quaternized glycine nitrile in addition to the previously used TAED leads to a significant improvement in the washing result. In particular, a ratio of TAED: bleach activator of 3: 2 leads to very good washing results, especially in the case of bleach-sensitive stains (red wine, tea).

Example 4 Different enzyme ratios, use Properase (Linitests, 2 tables) Wolltest Carrying out a linitest

The Linitest uses four different fabrics: cotton, polyester, polyester / cotton and raw armchair. The four fabric types are each cut to a size of 10 cm x 15 cm, wherein the raw bean is previously prewashed in the washing machine with 170 ml of surfactant solution.

For each series, each fabric is now searched for a lobe with the same whiteness, which may fluctuate up or down by 1 whiteness. The values are noted and then from each lobule the output Ry value is determined.

For dirt loading, a 10 cm x 15 cm WFK 10C soiling is added to each wash.

Menge an Waschlauge = Gewicht der 5 Gewebe x 16(Flottenverhältnis)Amount of washing powder for 1 wash $$\mathrm{g\; of\; washing\; liquor}\frac{\mathrm{Dosing\; quantity\; for\; HB\; II\; in\; g}}{16\left(\mathrm{liquor\; ratio}\right)}$$

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

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

Evaluation:

After the appropriate washes, the lobes are dried, measured and the Ry values or Whole Whiteness values noted. The results are shown in the 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 carbonate 15 15 15 surfactant Alkylbenzenesulfonate 2 2 2 Fatty alcohol sulphate 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 1.54 0.67 0.42 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: each ad 100 Oil release polymer sodium sulphate Anti-foaming agents brighteners phosphonate Speckels Perfume

Claims (6)

1. Detergent or cleaning agent containing at least one bleach activator and at least one TAED, characterised in that the TAED is in a processing form which brings about a delayed peracetic acid release kinetic in the effect of the bleach activator so that a peracetic acid concentration in the detergent solution of more than 100 mg/l is achieved only after at least 5 minutes, wherein a quaternised glycine nitrile is used as at least one bleach activator.
2. Detergent according to claim 1 containing the TAED in coated and/or compacted form.
3. Detergent or cleaning agent according to claim 1 or 2, characterised in that it also contains a protease which develops maximum enzymatic activity at temperatures below 45°C.
4. Detergent or cleaning agent according to one of claims 1 to 3, containing a combination of a bleach activator that is effective at low temperatures (below 45°C) and a bleach activator that is effective at temperatures above 45°C.
5. Detergent or cleaning agent according to one of claims 1 to 4, wherein a combination of the protease that is effective at low temperature (below 45°C) with at least one other protease is used.
6. Use of a cleaning agent according to at least one of claims 1 to 5 for use as or in a textile detergent, dishwashing agent, stain remover (stain removal powder), decalcifier or scouring agent.