DE102007040326A1 - Laundry pre-treatment agent and method - Google Patents

Abstract

The present invention relates to a process for improving the cleaning performance of detergents, in which soils on the laundry to be cleaned are pretreated with a pretreatment agent before carrying out the washing process, containing hydrogen peroxide-producing oxidoreductase and preferably a bleach activator and / or a substrate for a perhydrolase.

Description

The The present invention relates to a method for improving the Cleaning performance of detergents in which stains on the laundry to be cleaned with a pretreatment agent be pretreated before carrying out the washing process, wherein the pretreatment agent is a substrate for a hydrogen peroxide producing oxidoreductase, and preferably a bleach activator and / or a substrate for a perhydrolase.

At the Washing textiles are occasionally used to improve the washing performance Bleach used. In the bleach used can it is about directly to hydrogen peroxide or about peracids act.

alternative this or as a further auxiliary component is the use of bleach catalysts and bleach activators, their addition to detergents in situ during the washing process, the formation of bleach-active Enables or facilitates connections. As alternative The use of bleach activators is also the use of perhydrolases described that bleach active while reacting a suitable substrate Compounds can form in situ.

Except The aforementioned bleaching agents and bleaching aids are used in Some publications also use enzymes for their production of hydrogen peroxide described in situ. These enzymes are oxidoreductases, especially glucose oxidase. The catalyzed Reaction is the transfer of electrons from the organic substrate, about the glucose, to oxygen as an electron acceptor under training the desired hydrogen peroxide.

In spite of the use of said bleaching agents, bleaching agents and cleaning-active enzymes is related to the cleaning performance some stubborn soiling still not satisfied stellend.

task The present invention was therefore a method with improved To provide cleaning performance.

Surprisingly has now been found that the removal of stubborn Staining of textiles can be improved if the stains pretreated with an agent that is a substrate for contains a hydrogen peroxide-producing oxidoreductase. Another significant improvement can be achieved when in the agent next to the substrate for a hydrogen peroxide producing oxidoreductase additionally a bleach activator is included.

in the Individual it was found out that one at application a mixture of enzyme substrate and bleach activator on the textile achieves more than fourteen times better cleaning performance than when the enzyme substrate and the bleach activator in the same amount in the detergent, if in the detergent, which subsequently used for the washing process, an enzyme substrate containing enzyme to form hydrogen peroxide is. Above all, it was surprising that even Stains on other textiles that are in the same wash liquor like the textile with the pre-treated soiling, clearly are better removed, even if they are not pretreated were. So could not pretreated even for this Soiling almost five times better cleaning performance be achieved.

It can therefore be assumed that, independently of which position and / or on which textile of the wash liquor the pretreatment agent is applied, the textile and / or the Wash liquor as a whole is cleaned much better than without Use of the pretreatment agent according to the invention instead, add the same amount of components to the detergent to introduce into the wash liquor. The cleaning effects could hereby be further improved if the laundry pre-treatment agent is allowed to act for a while before washing.

Farther it was surprisingly found that even if no reacting the enzyme substrate to form hydrogen peroxide Enzyme is contained in the detergent, with the after pretreatment the washing process is carried out, even then the treatment with the enzyme substrate and optionally bleach activator containing pretreatment agent significantly improved cleaning performance could be achieved. If the pretreatment agent is long enough was allowed to so act even without the use of an enzyme a more than 10 times better cleaning performance can be achieved.

One The first object of the present invention is therefore a method for cleaning textile fabrics, characterized that the textile fabrics, and in particular the on it soiling, before washing with be treated with an agent containing at least one substrate for contains a hydrogen peroxide-producing oxidoreductase.

One Another object of the present invention is therefore a method for cleaning textile fabrics, characterized that the textile fabrics, and in particular the on it soiling, before washing with be treated with an agent containing at least one substrate for a hydrogen peroxide producing oxidoreductase and at least contains a bleach activator.

alternative bleach activators can also be perhydrolases in combination be used with a suitable substrate. Using of perhydrolases in combination with a suitable substrate at least the substrate of the perhydrolase in the pretreatment agent, the perhydrolase itself can be used both in the pretreatment agent as well as being contained in the detergent.

One Another object of the present invention is therefore also a Process for cleaning textile fabrics, characterized characterized in that the textile fabrics, and in particular the soiling thereon, before the Washing process should be treated with a means that at least one Substrate for a hydrogen peroxide-producing oxidoreductase and at least one substrate for a perhydrolase as well optionally contains at least one perhydrolase.

• a) ein textiles Flächengebilde, und insbesondere mindestens eine sich darauf befindliche Anschmutzung, wird mit einem Mittel, enthaltend mindestens ein Substrat für eine Wasserstoffperoxid produzierende Oxidoreduktase behandelt,
• b) das textile Flächengebilde gemäß (a) wird einem Waschvorgang unterworfen, wobei während des Waschvorgangs vorzugsweise ein Waschmittel eingesetzt wird, das eine Wasserstoffperoxid produzierende Oxidoreduktase enthält, das das Substrat gemäß (a) unter Ausbildung von Wasserstoffperoxid umsetzen kann.

A further subject of the present invention is therefore also a process for the cleaning of textile fabrics, comprising the following steps:

• a) a textile fabric, and in particular at least one soiling thereon, is treated with an agent containing at least one substrate for a hydrogen peroxide-producing oxidoreductase,
• b) the fabric according to (a) is subjected to a washing process, wherein during the washing process preferably a detergent is used which contains a hydrogen peroxide-producing oxidoreductase, which can implement the substrate according to (a) to form hydrogen peroxide.

• a) ein textiles Flächengebilde, und insbesondere mindestens eine sich darauf befindliche Anschmutzung, wird mit einem Mittel, enthaltend mindestens ein Substrat für eine Wasserstoffperoxid produzierende Oxidoreduktase und mindestens einen Bleichaktivator behandelt,
• b) das textile Flächengebilde gemäß (a) wird einem Waschvorgang unterworfen, wobei während des Waschvorgangs vorzugsweise ein Waschmittel eingesetzt wird, das eine Wasserstoffperoxid produzierende Oxidoreduktase enthält, das das Substrat gemäß (a) unter Ausbildung von Wasserstoffperoxid umsetzen kann.

A further subject of the present invention is therefore also a process for the cleaning of textile fabrics, comprising the following steps:

• a) a textile fabric, and in particular at least one soiling thereon, is treated with an agent containing at least one substrate for a hydrogen peroxide-producing oxidoreductase and at least one bleach activator,
• b) the fabric according to (a) is subjected to a washing process, wherein during the washing process preferably a detergent is used which contains a hydrogen peroxide-producing oxidoreductase, which can implement the substrate according to (a) to form hydrogen peroxide.

• a) ein textiles Flächengebilde, und insbesondere mindestens eine sich darauf befindliche Anschmutzung, wird mit einem Mittel, enthaltend mindestens (a1) ein Substrat für eine Wasserstoffperoxid produzierende Oxidoreduktase und mindestens (a2) ein Substrat für eine Perhydrolase behandelt,
• b) das textile Flächengebilde gemäß (a) wird einem Waschvorgang unterworfen, wobei während des Waschvorgangs vorzugsweise ein Waschmittel eingesetzt wird, das mindestens eine Wasserstoffperoxid produzierende Oxidoreduktase enthält, die das Substrat gemäß (a1) unter Ausbildung von Wasserstoffperoxid umsetzen kann, sowie mindestens eine Perhydrolase enthält, die das Substrat gemäß (a2) unter Umsetzung von Wasserstoffperoxid in eine Persäure umwandeln kann.

A further subject of the present invention is therefore also a process for the cleaning of textile fabrics, comprising the following steps:

• a) a textile fabric, and in particular at least one soiling thereon, is treated with an agent containing at least (a1) a substrate for a hydrogen peroxide-producing oxidoreductase and at least (a2) a substrate for a perhydrolase,
• b) the textile fabric according to (a) is subjected to a washing process, during the washing process preferably a detergent is used which contains at least one hydrogen peroxide-producing oxidoreductase, which can implement the substrate according to (a1) to form hydrogen peroxide, and at least one perhydrolase contains, which can convert the substrate according to (a2) under reaction of hydrogen peroxide into a peracid.

• c) ein textiles Flächengebilde, und insbesondere mindestens eine sich darauf befindliche Anschmutzung, wird mit einem Mittel, enthaltend mindestens (a1) ein Substrat für eine Wasserstoffperoxid produzierende Oxidoreduktase und mindestens (a2) ein Substrat für eine Perhydrolase sowie ferner enthaltend mindestens eine Perhydrolase, die das Substrat gemäß (a2) unter Umsetzung von Wasserstoffperoxid in eine Persäure umwandeln kann, behandelt,
• d) das textile Flächengebilde gemäß (a) wird einem Waschvorgang unterworfen, wobei während des Waschvorgangs vorzugsweise ein Waschmittel eingesetzt wird, das mindestens eine Wasserstoffperoxid produzierende Oxidoreduktase enthält, die das Substrat gemäß (a1) unter Ausbildung von Wasserstoffperoxid umsetzen kann.

A further subject of the present invention is therefore also a process for the cleaning of textile fabrics, comprising the following steps:

• c) a fabric, and in particular at least one soiling thereon, containing an agent containing at least (a1) a substrate for a hydrogen peroxide-producing oxidoreductase and at least (a2) a substrate for a perhydrolase, and further containing at least one perhydrolase, the the substrate according to (a2) can be converted by reaction of hydrogen peroxide in a peracid, treated
• d) the fabric according to (a) is subjected to a washing process, during the washing process preferably a detergent is used which contains at least one hydrogen peroxide-producing oxidoreductase, which can implement the substrate according to (a1) to form hydrogen peroxide.

object The present invention therefore also provides a laundry pre-treatment agent. the at least one substrate for a hydrogen peroxide containing producing oxidoreductase.

object The present invention therefore also provides a laundry pre-treatment agent. the at least one substrate for a hydrogen peroxide producing oxidoreductase and at least one bleach activator contains.

object The present invention therefore also provides a laundry pre-treatment agent. the at least one substrate for a hydrogen peroxide producing oxidoreductase and at least one substrate for one Contains perhydrolase.

object The present invention therefore also provides a laundry pre-treatment agent. the at least one substrate for a hydrogen peroxide producing oxidoreductase, at least one substrate for contains a perhydrolase and at least one perhydrolase.

• a) ein Wäschevorbehandlungsmittel, enthaltend mindestens ein Substrat für eine Wasserstoffperoxid produzierende Oxidoreduktase,
• b) ein Waschmittel, das vorzugsweise eine Wasserstoffperoxid produzierende Oxidoreduktase enthält, die das Substrat gemäß (a) unter Ausbildung von Wasserstoffperoxid umsetzen kann.

The subject of the present invention is therefore likewise a multi-component kit containing

• a) a laundry pre-treatment agent containing at least one substrate for a hydrogen peroxide-producing oxidoreductase,
• b) a detergent, preferably containing a hydrogen peroxide-producing oxidoreductase, which can implement the substrate according to (a) to form hydrogen peroxide.

• c) ein Wäschevorbehandlungsmittel, enthaltend mindestens ein Substrat für eine Wasserstoffperoxid produzierende Oxidoreduktase und mindestens einen Bleichaktivator,
• d) ein Waschmittel, das vorzugsweise eine Wasserstoffperoxid produzierende Oxidoreduktase enthält, die das Substrat gemäß (a) unter Ausbildung von Wasserstoffperoxid umsetzen kann.

The subject of the present invention is therefore likewise a multi-component kit containing

• c) a laundry pretreatment agent comprising at least one substrate for a hydrogen peroxide-producing oxidoreductase and at least one bleach activator,
• d) a detergent which preferably contains a hydrogen peroxide-producing oxidoreductase which can react the substrate according to (a) to form hydrogen peroxide.

• a) ein Wäschevorbehandlungsmittel, enthaltend mindestens (a1) ein Substrat für eine Wasserstoffperoxid produzierende Oxidoreduktase und mindestens (a2) ein Substrat für eine Perhydrolase,
• b) ein Waschmittel, das vorzugsweise mindestens eine Wasserstoffperoxid produzierende Oxidoreduktase enthält, die das Substrat gemäß (a1) unter Ausbildung von Wasserstoffperoxid umsetzen kann, und vorzugsweise mindestens eine Perhydrolase enthält, die das Substrat gemäß (a2) unter Umsetzung von Wasserstoffperoxid in einer Persäure umsetzen kann.

The subject of the present invention is therefore likewise a multi-component kit containing

• a) a laundry pre-treatment composition comprising at least (a1) a substrate for a hydrogen peroxide-producing oxidoreductase and at least (a2) a substrate for a perhydrolase,
• b) a detergent which preferably contains at least one hydrogen peroxide-producing oxidoreductase which can react the substrate according to (a1) to form hydrogen peroxide, and preferably contains at least one perhydrolase, which convert the substrate according to (a2) by reacting hydrogen peroxide in a peracid can.

• a) ein Wäschevorbehandlungsmittel, enthaltend mindestens (a1) ein Substrat für eine Wasserstoffperoxid produzierende Oxidoreduktase und mindestens (a2) ein Substrat für eine Perhydrolase sowie mindestens eine Perhydrolase, die das Substrat gemäß (a1) unter Umsetzung von Wasserstoffperoxid in eine Persäure umsetzen kann,
• b) ein Waschmittel, das vorzugsweise mindestens eine Wasserstoffperoxid produzierende Oxidoreduktase enthält, die das Substrat gemäß (a1) unter Ausbildung von Wasserstoffperoxid umsetzen kann.

The subject of the present invention is therefore likewise a multi-component kit containing

• a) a laundry pre-treatment agent containing at least (a1) a substrate for a hydrogen peroxide-producing oxidoreductase and at least (a2) a substrate for a perhydrolase and at least one perhydrolase, which can convert the substrate according to (a1) by reacting hydrogen peroxide into a peracid,
• b) a detergent, which preferably contains at least one hydrogen peroxide-producing oxidoreductase, which can implement the substrate according to (a1) to form hydrogen peroxide.

at the previously mentioned laundry pretreatment means which at least a substrate for a hydrogen peroxide producing Containing oxidoreductase is the substrate for the hydrogen peroxide producing oxidoreductase in the laundry pre-treatment agent preferably in an amount of at least 5, 10 or 15% by weight, more preferably in an amount of at least 20, 25 or 30 Wt .-% included.

In the aforementioned laundry pretreatment compositions containing at least one bleach activator and at least one substrate for a hydrogen peroxide-producing oxidoreductase, the bleach activator and the substrate for the hydrogen peroxide-producing oxidoreductase in the laundry pretreatment agent are each independently preferably in an amount of at least 5, 10 or 15 wt %, more preferably in an amount of at least 20, 25 or 30 wt .-%, wherein the total amount of bleach activator and substrate for a hydrogen peroxide-producing oxidoreductase preferably at least 10 or 20 wt .-%, more preferably at least 30 or 40 Wt .-%, esp especially at least 50 or 60 wt .-% is.

at the previously mentioned laundry pretreatment means which at least a substrate for a perhydrolase and at least one substrate for a hydrogen peroxide-producing oxidoreductase are the substrate for the perhydrolase and the Substrate for the hydrogen peroxide-producing oxidoreductase in the laundry pretreatment agent independently of each other preferably in an amount of at least 5, 10 or 15% by weight, more preferably in an amount of at least 20, 25 or 30 Wt .-%, wherein the total amount of substrate for a perhydrolase and substrate for a hydrogen peroxide producing oxidoreductase preferably at least 10 or 20 Wt .-%, particularly preferably at least 30 or 40 wt .-%, in particular at least 50 or 60 wt .-% is.

at the previously mentioned laundry pretreatment means which at least a substrate for a perhydrolase, at least one hydrogen peroxide containing oxidoreductase and at least one perhydrolase, are the substrate for the perhydrolase and the substrate for the hydrogen peroxide producing oxidoreductase in the laundry pretreatment agent independently of each other preferably in an amount of at least 5, 10 or 15% by weight, more preferably in an amount of at least 20, 25 or 30 Wt .-%, wherein the total amount of substrate for a perhydrolase and substrate for a hydrogen peroxide producing Oxidoreductase preferably at least 10 or 20 wt .-%, more preferably at least 30 or 40 wt .-%, in particular at least 50 or 60 Wt .-% is.

Especially advantageous laundry pre-treatment agent according to the invention are advantageous used in combination with liquid detergent. Because This can be the complicated integration of bleaching agents in liquid detergents be avoided. Instead, only small quantities taken up in oxidoreductase in the liquid detergent while the others are required for bleaching Components added to the laundry pretreatment can be achieved by targeted dosage and application significantly improved wash performance possible.

Hydrogen peroxide producing oxidoreductases

The hydrogen peroxide-producing oxidoreductase according to the invention is preferably an oxidoreductase which produces hydrogen peroxide by using oxygen as an electron acceptor. In particular, oxidoreductases of EC classes EC 1.1.3 (CH-OH as electron donor), EC 1.2.3 (aldehyde or oxo group as electron donor), EC 1.4.3 (CH-NH ₂ as donor), EC 1.7 are used. 3 (N-containing group as donor) and EC 1.8.3 (S-containing group as donor) into consideration, preference being given to enzymes of the EC class EC 1.1.3.

Preferred enzymes are in particular selected from the group consisting of malate oxidase (EC 1.1.3.3), glucose oxidase (EC 1.1.3.4), hexose oxidase (EC 1.1.3.5), cholesterol oxidase (EC 1.1.3.6), Galactose oxidase (EC 1.1.3.9), pyranose oxidase (EC 1.1.3.10), alcohol oxidase (EC 1.1.3.13), choline oxidase (EC 1.1.3.17, see in particular WO 04/58955 ), Oxidases for long-chain alcohols (EC 1.1.3.20), glycerol-3-phosphate oxidase (EC 1.1.3.21), cellobiose oxidase (EC 1.1.3.25), nucleoside oxidase (EC 1.1.3.39), D-mannitol Oxidase (EC 1.1.3.40), xylitol oxidase (EC 1.1.3.41), alditol oxidase, sorbitol oxidase, sugar alcohol oxidase, glycerol oxidase, aldehyde oxidase (EC 1.2.3.1), pyruvate oxidase (EC 1.2.3.3), oxalate oxidase (EC 1.2.3.4), glyoxylate oxidase (EC 1.2.3.5), indole-3-acetaldehyde oxidase (EC 1.2.3.7), pyridoxal oxidase (EC 1.2.3.8), aryl aldehyde Oxidase (EC 1.2.3.9), retinal oxidase (EC 1.2.3.11), L-amino acid oxidase (EC 1.4.3.2), amine oxidase (EC 1.4.3.4, EC 1.4.3.6), L-glutamate Oxidase (EC 1.4.3.11), L-lysine oxidase (EC 1.4.3.14), L-aspartate oxidase (EC 1.4.3.16), tryptophan-alpha, beta-oxidase (EC 1.4.3.17), glycine oxidase EC 1.4.3.19), urea oxidase (EC 1.7.3.3), thiol oxidase (EC 1.8.3.2) and glutathione oxidase (EC 1.8.3.3) as well as variants of these enzymes.

at the hydrogen peroxide producing oxidoreductase is in a preferred embodiment, one that used a sugar as an electron donor. The hydrogen peroxide producing and sugar oxidizing oxidoreductase is according to the invention preferably selected from glucose oxidase (EC 1.1.3.4), hexose oxidase (EC 1.1.3.5), galactose oxidase (EC 1.1.3.9) and pyranose oxidase (EC 1.1.3.10). Particularly preferred according to the invention is the Glucose oxidase (EC 1.1.3.4) and variants of this enzyme.

Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes, in order to enhance the activity of the relevant oxidoreductases (enhancers) or, in the case of greatly differing redox potentials, between the oxidizing Enzymes and soiling to ensure the flow of electrons (mediators).

The Hydrogen peroxide-producing oxidoreductase is used in the inventive Detergents and cleaners are preferably used in an amount that the whole agent has an oxidoreductase-related enzyme activity from 30 U / g to 20,000 U / g, especially from 60 U / g to 15,000 U / g having. The unit 1 U (unit) corresponds to the activity the amount of enzyme containing 1 μmol of its substrate at pH 7 and 25 ° C in one minute.

substrates for the hydrogen peroxide producing oxidoreductase As a substrate for the hydrogen peroxide-producing oxidoreductase can be used depending on the used Enzyme, in particular malate, glucose, hexoses, cholesterol, galactose, Pyranoses, alcohols, choline, glycerol-3-phosphate, cellobiose, nucleosides, D-mannitol, xylitol, sugar alcohols, alditol, sorbitol, glycerol, Aldehydes, pyruvate, oxalate, glyoxylate, indole-3-acetaldehyde, pyridoxal, Aryl aldehydes, retinal, L-amino acids, amines, L-glutamate, L-lysine, L-aspartate, tryptophan, glycine, urea, thiols or Glutathione can be used.

In a particularly preferred embodiment is used as a substrate Used glucose.

perhydrolases

at the perhydrolase is preferably an enzyme selected from the group of lipases, esterases and proteases, which is capable of starting from carboxylic acids and Hydrogen peroxide to form peracids. In a preferred Embodiment is in the reaction center of perhydrolase contain the catalytic triad Ser-His-Asp.

With regard to perhydrolases which can be used according to the invention, reference may be made in particular to the applications DE 10260903 . DE 102004029475 . WO 98/45398 . WO 04/58961 . WO 05/56782 , PCT / EP 05/06178 and US 2007105740 directed. Furthermore, in particular variants of these enzymes can be used.

The Perhydrolase is preferably used according to the invention, in particular as an enzyme concentrate or as a solid perhydrolase preparation, in amounts of 0.1 to 5.0 wt .-%, particularly preferably from 0.2 to 3.0 wt .-%, each based on the total agent used.

Perhydrolase substrates

Carboxylic acid esters, carboxylic acids and / or their salts and / or derivatives thereof can be used as substrate for the perhydrolase. Examples which may be mentioned in general are compounds of the formula R ¹ - (R ² ) _m -OR ³ , where
R ^{1 is} R ⁴ C (O) - or R ⁴ C (NR ⁵ ) -,
R ^{3 is} hydrogen or optionally substituted, in particular substituted by optionally substituted amino groups, alkyl, alkenyl, alkynyl, aryl, alkylaryl, heteroaryl or alkylheteroaryl or a group -XO- (R ^2b ) _n -R ^1b ,
R ^{4 is} hydrogen or optionally substituted alkyl, alkenyl, alkynyl, aryl, alkylaryl, heteroaryl or alkylheteroaryl or a group -YR ^1a - (R ^2a ) _o -OR ^3a ,
X and Y are optionally substituted alkyl, alkenyl, alkynyl, aryl, alkylaryl, heteroaryl or alkylheteroaryl,
R ² , R ^2a and R ^{2b represent} an alkoxy group,
R ^{1a represents} -C (O) - or -C (NR ⁵ ) -,
R ^{1b is} R ⁶ C (O) - or R ⁶ C (NR ⁵ ) -,
R ^3a and R ^{6 are} hydrogen or optionally substituted alkyl, alkenyl, alkynyl, aryl, alkylaryl, heteroaryl or alkylheteroaryl,
R ^{5 is} hydrogen or alkyl,
m, n and o independently assume a value from 0 to 12.

When Examples of as perhydrolase substrate optionally Carboxylic acids which can be used in the form of their esters and / or salts are in particular acetic acid, propionic acid, butyric acid, Valeric acid, hexanoic acid, heptanoic acid, Octanoic acid, decanoic acid, maleic acid, Oxalic acid, benzoic acid, citric acid, Lactic acid, fruit acids and phthalic acid called.

Bleach activators

As bleach activators it is possible, in particular, to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular 1,3,4,6 Tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), acylated hydroxycarboxylic acids, such as triethyl-O-acetylcitrate (TEOC), Carboxylic acid anhydrides, in particular phthalic anhydride, isatoic anhydride and / or succinic anhydride, carboxylic acid amides such as N-methyldiacetamide, glycolide, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, isopropenyl acetate, 2,5-diacetoxy-2,5-dihydrofuran and those from the German patent applications DE 196 16 693 and DE 196 16 767 known enol esters and acetylated sorbitol and mannitol or their in the European patent application EP 0 525 239 mixtures described (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine or gluconolactone, triazole or triazole derivatives and / or particulate caprolactams and / or caprolactam derivatives, preferably N-acylated lactams, for example, N-benzoylcaprolactam and N-acetylcaprolactam. Hydrophilic substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used. Likewise, nitrile derivatives such as cyanopyridines, nitrile quats, for example N-alkylammonium acetonitriles, and / or cyanamide derivatives can be used. Preferred bleach activators are sodium 4- (octanoyloxy) benzenesulfonate, n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), undecenoyloxybenzenesulfonate (UDOBS), sodium dodecanoyloxybenzenesulfonate (DOBS), decanoyloxybenzoic acid (DORA, OBC 10) and / or dodecanoyloxybenzenesulfonate (OBS 12), as well as N-methylmorpholinum acetonitrile (MMA).

in der R¹ für -H, -CH₃, einen C_2-24-Alkyl- oder -Alkenylest, einen substituierten C_2-24-Alkyl- oder -Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN, einen Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe und mindestens einem weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -CH₂-CN, -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, -CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, -(CH₂CH₂-O)_nH mit n = 1, 2, 3, 4, 5 oder 6 und X ein Anion ist.Other bleach activators which can be used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitriles of the formula

in the R ^{1 is} -H, -CH ₃ , a C _2-24 alkyl or alkenyl radical, a substituted C _2-24 alkyl or alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical having a C _1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C _1-24 -alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ - OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) - CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H where n = 1, 2, 3, 4, 5 or 6 and X is an anion.

in der R⁴, R⁵ und R⁶ unabhängig voneinander ausgewählt sind aus -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, wobei R⁴ zusätzlich auch -H sein kann und X ein Anion ist, wobei vorzugsweise R⁵ = R⁶ = -CH₃ und insbesondere R⁴ = R⁵ = R⁶ = -CH₃ gilt und Verbindungen der Formeln (CH₃)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH₂)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH₂CH₂)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH(CH₃))₃N⁽⁺⁾CH₂-CN X^–, oder (HO-CH₂-CH₂)₃N⁽⁺⁾CH₂-CN X^– besonders bevorzugt sind, wobei aus der Gruppe dieser Substanzen wiederum das kationische Nitril der Formel (CH₃)₃N⁽⁺⁾CH₂-CN X^–, in welcher X^– für ein Anion steht, das aus der Gruppe Chlorid, Bromid, Iodid, Hydrogensulfat, Methosulfat, p-Toluolsulfonat (Tosylat) oder Xylolsulfonat ausgewählt ist, besonders bevorzugt wird.Particularly preferred is a cationic nitrile of the formula

in which R ⁴ , R ⁵ and R ^{6 are} independently selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , wherein R ⁴ additionally also -H may be and X is an anion, preferably R ⁵ = R ⁶ = -CH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = -CH ₃ and compounds of the formulas (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ( CH ₃ )) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , or (HO-CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^{- are} particularly preferred, wherein from the group of these substances turn the cationic Nitrile of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- in which X ^{- represents} an anion selected from the group consisting of chloride, bromide, iodide, hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate is particularly preferred.

at the bleach activator is a particularly preferred Embodiment to TAED.

Of the Bleach activator is in the compositions of the invention, especially in detergents and cleaners, preferably in one Amount of 0.01 to 20 wt .-%, preferably in an amount of 0.1 up to 15% by weight, in particular in an amount of 1 to 10% by weight, especially in an amount of 2 to 5 wt .-%, based on the total Composition, included.

The Inventive laundry pre-treatment agent and laundry detergents may contain other ingredients, as usual for detergents and cleaners are.

bleach

Under A bleaching agent is hydrogen peroxide itself as well as water To understand hydrogen peroxide-yielding compounds. The use bleaching agents are not required according to the invention, since the hydrogen peroxide producing oxidoreductase is the hydrogen peroxide generated in situ. In a preferred invention Embodiment is therefore directed to the use of bleaching agents waived. Nevertheless, bleach can of course be used used to enhance the bleaching effect according to the invention so that in another invention Embodiment bleach either in the laundry pre-treatment or may be included in the laundry detergent or in both. If present, the bleaching agents are preferably in the laundry pre-treatment agent used.

Among the compounds serving as bleaches in water H ₂ O ₂ , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, peroxopyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as persulfates or persulfuric acid. Also useful is the urea peroxohydrate percarbamide, which can be described by the formula H ₂ N-CO-NH ₂ .H ₂ O ₂ . In particular, when using the means for cleaning hard surfaces, for example in automatic dishwashing, they may, if desired, also contain bleaching agents from the group of organic bleaches, although their use is also possible in principle for laundry detergents. Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid (Phthalimidoperoxyhexanoic acid, PAP and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4 diacid, N, N-terephthaloyl-di (6-aminopercaproic acid).

When Bleaching agents can also chlorine or bromine releasing substances be used. Among the suitable chlorine or bromine releasing Materials include, for example, heterocyclic N-bromo- and N-chloroamides, for example, trichloroisocyanuric acid, tribromoisocyanuric acid, Dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICH) and / or their salts with cations such as potassium and sodium into consideration. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

According to the invention Compositions, in particular detergents or cleaners, before all automatic dishwashing detergent, preferably, the bis at 45% by weight, especially 1 to 35% by weight, preferably 2.5 to 30 wt .-%, particularly preferably 3.5 to 20 wt .-% and in particular 5 to 15 wt .-% bleach, preferably sodium percarbonate.

Of the Active oxygen content of the compositions according to the invention, especially the washing or cleaning agents, especially the machine Dishwashing detergent, is, in each case based on the total weight of the agent, preferably between 0.4 and 10 Wt .-%, more preferably between 0.5 and 8 wt .-% and in particular between 0.6 and 5 wt .-%. Particularly preferred agents have one Active oxygen content above 0.3% by weight, preferably above 0.7 Wt .-%, more preferably above 0.8 wt .-% and in particular above 1.0% by weight.

bleach catalysts

Of Further, both in the laundry pre-treatment agent as well as in the detergent used for the textile cleaning be contained about bleach catalysts.

at These substances may generally be any bleach-enhancing transition metal salt or act any transition metal complex. As transition metals in particular Mn, Fe, Co, Ru, Mo, Ti, V or Cu come in here different oxidation states into consideration. As possible Complexing ligands come in particular, as in the literature guanidines, aminophenols, amine oxides, salene, sodimines, Lactams, monocyclic and cross-bridged polycyclic Polyazaalkanes, terpyridines, dendrimers, tetraamido ligands, bis- and tetrakis (pyridylmethyl) alkylamines, secondary amines and polyoxometalates.

Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or Cobalt salts and / or complexes, more preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the Chlorides of cobalt or manganese, manganese sulfate are used in common Quantities, preferably in an amount up to 5 wt .-%, in particular from 0.0025 wt.% to 1 wt.%, and more preferably from 0.01 Wt .-% to 0.25 wt .-%, each based on the total weight of bleach activator-containing agent used. In special cases however, more bleach activator can also be used.

It is particularly preferred to use complexes of manganese in the oxidation state II, III, IV or IV, which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S. Preferably, ligands are used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononan (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and or 2-methyl-1,4,7-triazacyclononane (Me / TACN). Suitable manganese complexes are, for example, [Mn ^III ₂ (μ-O) ₁ (μ-OAc) ₂ (TACN) ₂ ] (ClO ₄ ) ₂ , [Mn ^III Mn ^IV (μ-O) ₂ (μ-OAc) ₁ (TACN ) ₂ ] (BPh ₄ ) ₂ , [Mn ^IV ₄ (μ-O) ₆ (TACN) ₄ ] (ClO ₄ ) ₄ , [Mn ^III ₂ (μ-O) ₁ (μ-OAc) ₂ (Me-TACN ) ₂ ] (ClO ₄ ) ₂ , [Mn ^III Mn ^IV (μ-O) ₁ (μ-OAc) ₂ (Me-TACN) ₂ ] (ClO ₄ ) ₃ , [Mn ^IV ₂ (μ-O) ₃ ( Me-TACN) ₂ ] (PF ₆ ) ₂ and [Mn ^IV ₂ (μ-O) ₃ (Me / Me-TACN) ₂ ] (PF ₆ ) ₂ (OAc = OC (O) CH ₃ ).

bleach catalysts can in usual amounts, preferably in one Amount up to 5% by weight, in particular from 0.0025% by weight to 1% by weight and more preferably from 0.01% to 0.25% by weight, respectively based on the total weight of the composition, in particular a washing or cleaning agent used. In special However, it is also possible to use more bleach catalyst in cases become.

Furthermore can both in the laundry pretreatment as well as being included in the laundry detergent components, usually be used in detergents and cleaners.

embodiments The present invention includes all of the prior art established and / or all appropriate dosage forms the laundry pre-treatment agent according to the invention and the textile detergent according to the invention. These include liquid, gel and pasty dosage forms for the laundry pre-treatment agent and solid, powdered, liquid, gelatinous and pasty dosage forms for the laundry detergent, optionally also from several phases, compressed or not compressed. Furthermore, the laundry pre-treatment agent sprayed in the form of a spray on the textile to be treated become. For the laundry detergent also come Extrudates, granules, tablets or pouches in question, both in Large packs as well as portionwise packed. Especially advantageous is the combination of laundry pre-treatment agent and liquid laundry detergent, as in liquid Textile detergents so far only insufficient bleaching activities could be achieved.

The Laundry pre-treatment agent according to the invention is preferably largely anhydrous.

Either the laundry pre-treatment agent as well as the laundry detergent may contain surfactant (s) where anionic, nonionic, zwitterionic and / or amphoteric surfactants can be used. Preference is given to mixtures of anionic and nonionic surfactants The total surfactant content of the liquid detergent or cleaner is preferably below 40 wt .-% and particularly preferred below 35 wt .-%, based on the total liquid Laundry detergent.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture, as they usually in oxoal koholresten present. In particular, however, alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO, 4 EO or 7 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 7 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention. Here, block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers. Of course, it is also possible to use mixed alkoxylated nonionic surfactants in which EO and PO units are not distributed in blocks, but randomly. Such products are available by the simultaneous action of ethylene and propylene oxide on fatty alcohols.

In addition, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) _x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4. Alkyl glycosides are known, mild surfactants.

A another class of preferred nonionic surfactants, the either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl ester.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamide may be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated Fatty alcohols, especially not more than half of them.

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R1 für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Further suitable surfactants are polyhydroxy fatty acid amides of the formula (I)

in which RCO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C _1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.

[Z] is preferably obtained by reductive amination of a sugar, for example, glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxyfatty acid amides are transferred.

Of the The content of nonionic surfactants in the washing or cleaning agent preferably 5 to 30 wt .-%, preferably 7 to 20 wt .-% and in particular 9 to 15 wt .-%, each based on the washing or cleaning agent.

In addition to the nonionic surfactants, the washing or cleaning agent may also contain anionic surfactants. As anionic surfactants, for example, those of the sulfonate type and sulfates are used. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C _12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise suitable are the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Further Suitable anionic surfactants are sulfated fatty acid glycerol esters. Among fatty acid glycerol esters are the mono-, di- and triesters As well as their mixtures to understand, as in the production through Esterification of a monoglycerine with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol to be obtained. Preferred sulfated fatty acid glycerol esters are the sulfonation of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, Caprylic acid, capric acid, myristic acid, Lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. Also 2,3-alkyl sulfates, which can be obtained as commercial products of Shell Oil Company under the name DAN ^® , are suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C _7-21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11- alcohols having on average 3.5 mol of ethylene oxide (EO) or C _12-18 . Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Especially preferred anionic surfactants are soaps. Suitable are saturated and unsaturated fatty acid soaps, such as the salts lauric, myristic, palmitic, Stearic acid, (hydrogenated) erucic acid and behenic acid and in particular from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids, derived soap mixtures.

The anionic surfactants, including the soaps, may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. In front Preferably, the anionic surfactants are in the form of their sodium or potassium salts, especially in the form of the sodium salts.

Of the Content of an inventive agent of anionic Surfactants can be from 0.01 to 30% by weight, based on the total washing or detergents. However, it is preferred that the Amount of anionic surfactants relatively is low to possibly interactions of anionic surfactants contained color transfer inhibitor, the effect of this minimize, minimize. In a preferred embodiment contains an agent according to the invention therefore anionic surfactants in amounts up to 5 wt .-%. In a special Embodiment contains an inventive Means no anionic surfactants.

In of the present invention may consist, inter alia, of stability and / or aesthetic reasons extremely be preferred that the textile detergent exclusively contains nonionic surfactants.

Either the laundry pre-treatment agent as well as the laundry detergent may contain other ingredients that are the application-related and / or aesthetic properties of the means concerned improve further. In the context of the present invention contains the pretreatment agent and / or the laundry detergent preferably additionally one or more substances from the group of Builders, other enzymes, electrolytes, non-aqueous Solvents, pH adjusters, perfumes, perfume carriers, Fluorescers, dyes, hydrotopes, foam inhibitors, silicone oils, Anti redeposition agents, grayness inhibitors, anti-shrinkage agents, Anti-crease agents, color transfer inhibitors, antimicrobial Active ingredients, germicides, fungicides, antioxidants, preservatives, Corrosion inhibitors, antistatic agents, bittering agents, ironing aids, phobizers and impregnating agents, swelling and anti-seizing agents, neutral Filling salts, softening components and UV absorbers, these additional components, if used, in a preferred embodiment only in the laundry detergent, not included in the laundry pre-treatment agent. The laundry pre-treatment agent according to the invention is particularly preferred free from builders or other water softening agents Substances.

in the The following applies, provided that the textile detergent and the laundry pre-treatment agent Reference is made, generally the term "detergent" second hand.

When Color transfer inhibitors are especially nitrogen-containing Color transfer inhibitors into consideration. It is here especially preferred that the color transfer inhibitor a polymer or copolymer of cyclic amines such as vinylpyrrolidone and / or vinylimidazole. As a color transfer inhibitor suitable polymers include polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI), copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI), Polyvinylpyridine N-oxide, poly-N-carboxymethyl-4-vinylpyridium chloride and mixtures thereof. Particularly preferred are polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI) or copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI) as a color transfer inhibitor used.

The polyvinylpyrrolidone (PVP) preferably have an average molecular weight of from 2,500 to 400,000, and are commercially available from ISP Chemicals as PVP K 15, PVP K 30, PVP K 60 or PVP K 90 or from BASF as Sokalan ^® HP 50 or Sokalan ^® HP 53 available.

The copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI) used preferably have a molecular weight in the range from 5,000 to 100,000. A commercially available PVP / PVI copolymer is, for example, by BASF under the name Sokalan ^® HP 56th

Furthermore, it is also possible to use fatty alkyl dialkylhydroxyethylammonium salts as color transfer inhibitors, in particular in admixture with the abovementioned nitrogenous dye transfer inhibitors. The fatty alkyl dialkylhydroxyethylammonium salt is preferably a fatty alkyldimethylhydroxyethylammonium salt, more preferably a C ₁₂ -C ₁₈ fatty alkyldimethylhydroxyethylammonium salt. It is particularly preferred that the fatty alkyl dimethyl hydroxyethyl ammonium salt is C ₁₂ -C ₁₄ fatty alkyl dimethyl hydroxyethyl ammonium chloride.

The Amount of second color transfer inhibitor, if any, based on the total amount of detergent is preferred in the range from 0.01 to 2% by weight, preferably from 0.05 to 1% by weight and more preferably from 0.1 to 0.5% by weight.

As builders, which may be included in a cleaning agent according to the invention are esp special silicates, aluminum silicates (especially zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.

Suitable crystalline layered sodium silicates have the general formula NaMSi _x O _{2x + 1} H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays which have a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of up to a maximum of 50 nm and in particular up to a maximum of 20 nm being preferred. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. Also suitable, however, are zeolite X and mixtures of A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) which is sold by SASOL under the brand name VEGOBOND AX ^® and by the formula), nNa ₂ O · (1-n) K ₂ O · Al ₂ O ₃ · (2 - 2.5) SiO ₂ · (3.5 - 5.5) H ₂ O n = 0.90 - 1.0 can be described. The zeolite can be used as a spray-dried powder or else as undried, still moist, stabilized suspension of its preparation. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols having 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Of course it is also possible to use the generally known phosphates as builders, if such use is not for environmental reasons should be avoided. Particularly suitable are the sodium salts the orthophosphates, the pyrophosphates and in particular the tripolyphosphates.

organic Builders present in the detergent may be, for example, in the form of their sodium salts usable polycarboxylic acids, wherein among polycarboxylic acids Such carboxylic acids are understood to be more than one Wear acidity. For example, these are citric acid, adipic acid, Succinic acid, glutaric acid, malic acid, Tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA) and its derivatives as well as mixtures of these. Preferred salts are the salts of Polycarboxylic acids such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, Sugar acids and mixtures of these.

The acids themselves can also be used. In addition to their builder effect, the acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these are in particular call. Further useable acidulants are known pH regulators, such as sodium bicarbonate and sodium hydrogen sulfate.

When Builders are further suitable polymeric polycarboxylates. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

suitable Polymers are in particular polyacrylates, which preferably have a molecular weight from 2,000 to 20,000 g / mol. Because of their superior Solubility can turn out of this group the short-chain polyacrylates, the molecular weights of 2,000 to 10,000 g / mol, and more preferably from 3,000 to 5,000 g / mol, be preferred.

suitable Polymers may also include substances that partially or entirely from units of vinyl alcohol or its Derivatives exist.

Suitable are furthermore copolymeric polycarboxylates, especially those of Acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As special suitable copolymers of acrylic acid with maleic acid proven, the 50 to 90 wt .-% acrylic acid and 50 to 10 Wt .-% maleic acid. Your molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol. The (co) polymeric polycarboxylates can be either as an aqueous solution or preferably used as a powder.

to The water solubility can be improved Polymers also allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.

Especially Biodegradable polymers of more than two are also preferred various monomer units, for example, those as monomers Salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers, salts of acrylic acid and the 2-Alkylallylsulfonsäure and sugar derivatives.

Further preferred copolymers are those which are preferably used as monomers Acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

As well as further preferred builders are polymeric aminodicarboxylic acids, to mention their salts or their precursors. Especially preference is given to polyaspartic acids or their salts and derivatives, in addition to builder properties also a bleach-stabilizing Have effect.

Further Suitable builders are polyacetals, which by reaction of dialdehydes with polyolcarboxylic acids, which are 5 to 7 C atoms and at least 3 hydroxyl groups can be obtained. Preferred polyacetals are selected from dialdehydes such as glyoxal, glutaraldehyde, Terephthalaldehyde and mixtures thereof and from Polyolcarbonsäuren such as gluconic acid and / or glucoheptonic acid.

Other suitable organic builders are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500 000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dex trine and white dextrins with higher molecular weights in the range of 2,000 to 30,000 g / mol

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Also suitable is an oxidized oligosaccharide. A product oxidized to C _{6 of} the saccharide ring may be particularly advantageous. Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are also other suitable builders. In this case, ethylenediamine-N, N'-disuccinate (EDDS), preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates.

Further useful organic builders are, for example acetylated hydroxycarboxylic acids or their salts, which optionally also be present in Lactonform and which at least 4 carbon atoms and at least one hydroxy group and contain a maximum of two acid groups.

It may also be preferred that the cleaning agent is a softening Detergent ("2in1") is included for this purpose the cleaning agent next to the color transfer inhibitor and the surfactants also have a softening component.

The softening component includes, for example, quaternary Ammonium compounds such as monoalk (en) yltrimethylammonium compounds, Dialk (en) yldimethylammonium compounds, mono-, di- or triesters of fatty acids with alkanolamines.

wobei in (III) R für einen acyclischen Alkylrest mit 12 bis 24 Kohlenstoffatomen, R¹ für einen gesättigten C₁-C₄ Alkyl- oder Hydroxyalkylrest steht, R² und R³ entweder gleich R oder R¹ sind oder für einen aromatischen Rest stehen. X^– steht entweder für ein Halogenid-, Methosulfat-, Methophosphat- oder Phosphation sowie Mischungen aus diesen. Beispiele für kationische Verbindungen der Formel (III) sind Monotalgtrimethylammoniumchlorid, Monostearyltrimethylammoniumchlorid, Didecyldimethylammoniumchlorid, Ditalgdimethylammoniumchlorid oder Dihexadecylammoniumchlorid.Suitable examples of quaternary ammonium compounds are shown, for example, in formulas (III) and (IV):

wherein in (III) R is an acyclic alkyl radical having 12 to 24 carbon atoms, R ^{1 is} a saturated C ₁ -C ₄ alkyl or hydroxyalkyl radical, R ² and R ^{3 are} either R or R ¹ or are an aromatic radical , X ^- is either a halide, methosulfate, methophosphate or phosphate ion and mixtures thereof. Examples of cationic compounds of the formula (III) are monotaltrimethylammonium chloride, monostearyltrimethylammonium chloride, didecyldimethylammonium chloride, ditallowdimethylammonium chloride or dihexadecylammonium chloride.

Compounds of the formula (IV), (V) and (VI) are so-called ester quats. Esterquats are characterized by excellent biodegradability. In formula (IV) R ^{4 is} an aliphatic alk (en) yl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds and / or optionally with substituents; R ⁵ is H, OH or O (CO) R ⁷ , R ⁶ is, independently of R ^5, H, OH or O (CO) R ⁸ , where R ⁷ and R ⁸ are each independently an aliphatic alk (ene) ylrest having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds. m, n and p can each independently be 1, 2 or 3. X ^- may be either a halide, methosulfate, methophosphate or phosphate ion as well as mixtures of these anions. Preference is given to compounds in which R ^{5 represents} the group O (CO) R ⁷ . Particular preference is given to compounds in which R ^{5 is} the group O (CO) R ⁷ and R ⁴ and R ^{7 are} alk (en) yl radicals having 16 to 18 carbon atoms. Particularly preferred are compounds in which R ^{6 is} also OH. Examples of compounds of the formula (IV) are methyl N- (2-hydroxyethyl) -N, N-di (tallow acyloxyethyl) ammonium methosulfate, bis (palmitoyloxyethyl) hydroxyethyl methyl ammonium methosulfate, 1,2-bis - [tallowloxy] -3-trimethylammonium propane chloride or methyl N, N-bis (stearoyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulphate.

If quaternized compounds of the formula (IV) are used which have unsaturated alkyl chains, the acyl groups are preferred whose corresponding fatty acids have an iodine number between 1 and 100, preferably between 5 and 80, more preferably between 10 and 60 and in particular between 15 and 45 and which have a cis / trans isomer ratio (in% by weight) of greater than 30:70, preferably greater than 50:50 and in particular equal to or greater than 60:40. Commercial examples are sold by Stepan under the tradename Stepantex ^® methylhydroxyalkyldialkoyloxyalkylammonium or those known under Dehyquart ^® Cognis products, known under Rewoquat ^® products from Degussa or those known under Tetranyl ^® products of Kao. Other preferred compounds are the dies terquats of formula (V) which are obtainable under the name Rewoquat ^® 3099 W 222 LM or CR.

R ²¹ and R ²² are each independently an aliphatic radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds.

Instead of the ester group O (CO) R, where R is a long chain Alk (en) ylrest can, softening compounds can be used, which have the following groups: RO (CO), N (CO) R or RN (CO), of which N (CO) R groups are preferred are.

wobei R⁹ für H oder einen gesättigten Alkylrest mit 1 bis 4 Kohlenstoffatomen, R¹⁰ und R¹¹ unabhängig voneinander jeweils für einen aliphatischen, gesättigten oder ungesättigten Alkylrest mit 12 bis 18 Kohlenstoffatomen, R¹⁰ alternativ auch für O(CO)R²⁰ stehen kann, wobei R²⁰ einen aliphatischen, gesättigten oder ungesättigten Alkylrest mit 12 bis 18 Kohlenstoffatomen bedeutet, und Z eine NH-Gruppe oder Sauerstoff bedeutet und X^– ein Anion ist. q kann ganzzahlige Werte zwischen 1 und 4 annehmen.In addition to the quaternary compounds described above, it is also possible to use other compounds as the softening component, for example quaternary imidazolinium compounds of the formula (VI)

where R ^{9 is} H or a saturated alkyl radical having 1 to 4 carbon atoms, R ¹⁰ and R ¹¹ are each independently an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms, R ^{10 may} alternatively be O (CO) R ²⁰ wherein R ^{20 is} an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms, and Z is an NH group or oxygen and X ^{- is} an anion. q can take integer values between 1 and 4.

wobei R¹², R¹³ und R¹⁴ unabhängig voneinander für eine C_1-4-Alkyl-, Alkenyl- oder Hydroxyalkylgruppe steht, R¹⁵ und R¹⁶ jeweils unabhängig ausgewählt eine C_8-28-Alkylgruppe darstellt, X^– ein Anion ist und r eine Zahl zwischen 0 und 5 ist. Ein bevorzugtes Beispiel einer kationischen Abscheidungshilfe gemäß Formel (VII) ist 2,3-Bis[talgacyloxy]-3-trimethylammoniumpropanchlorid.Further particularly preferred plasticizing compounds are described by formula (VII),

wherein R ¹² , R ¹³ and R ¹⁴ independently represent a C _1-4 alkyl, alkenyl or hydroxyalkyl group, each of R ¹⁵ and R ¹⁶ independently represents a C _8-28 alkyl group, X ^{- is} an anion and r is a number between 0 and 5. A preferred example of a cationic deposition aid according to formula (VII) is 2,3-bis [tallowacyloxy] -3-trimethylammoniumpropane chloride.

Further Softening components which can be used according to the invention represent quaternized protein hydrolysates or protonated amines represents.

Furthermore, cationic polymers are also suitable softening component. Suitable cationic polymers include the polyquaternium polymers as described in the CTFA Cosmetic Ingredient Dictionary (The Cosmetic, Toiletry and Fragrance, Inc., 1997), in particular the Polyquaternium-6, Polyquaternium-7, Polyquaternium, also referred to as Merquats. 10 polymers (Polymer JR, LR and KG series from Amerchol), polyquaternium-4 copolymers such as graft copolymers having a cellulose backbone and quaternary ammonium groups attached via allyldimethylammonium chloride, cationic cellulose derivatives such as cationic guar such as guar hydroxypropyltriammonium chloride, and similar quaternized guar Derivatives (eg Cosmedia Guar from Cognis or the Jaguar series from Rhodia), cationic quaternary sugar derivatives (cationic alkyl polyglucosides), e.g. , The commercial product Glucquat ^® 100, according to CTFA nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride", copolymers of PVP and dimethylaminomethacrylate, copolymers of vinylimidazole and vinylpyrrolidone, and copolymers Aminosiliconpolymere.

Polyquaternized polymers (for example Luviquat ^® Care from BASF.), And cationic biopolymers based on chitin and derivatives thereof, for example, under the trade designation chitosan ^® (manufacturer: Cognis) polymer obtainable.

Some said cationic polymers additionally have skin and / or textile care properties.

R¹⁷ kann ein aliphatischer Alk(en)ylrest mit 12 bis 22 Kohlenstoffatomen mit 0, 1, 2 oder 3 Doppelbindungen sein. s kann Werte zwischen 0 und 5 annehmen. R¹⁸ und R¹⁹ stehen unabhängig voneinander jeweils für H, C_1-4-Alkyl oder Hydroxyalkyl und X^– ist ein Anion.It is likewise possible to use compounds of the formula (VIII)

R ¹⁷ can be an aliphatic alk (en) yl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds. s can take values between 0 and 5. R ¹⁸ and R ¹⁹ are each independently H, C _1-4 alkyl or hydroxyalkyl and X ^- is an anion.

Further Suitable softening components include protonated or quaternized Polyamines.

alternative the detergent may also have a textile softening clay, such as bentonite, as softening component included.

Especially preferred plasticizing components are alkylated quaternary Ammonium compounds, of which at least one alkyl chain an ester group and / or amido group is interrupted. Most notably preferred are N-methyl-N- (2-hydroxyethyl) -N, N- (ditalgacyloxyethyl) ammonium methosulfate or bis (palmitoyloxyethyl) hydroxyethyl methyl ammonium methosulfate.

The Detergent may contain a thickener. The thickener For example, a polyacrylate thickener, xanthan gum, gellan Gum, guar gum, alginate, carrageenan, carboxymethylcellulose, Bentonite, Wellan gum, locust bean gum, agar-agar, tragacanth, Gum arabic, pectins, polyoses, starch, dextrins, gelatin and casein. But also modified natural substances such as modified Starches and celluloses, examples being carboxymethylcellulose and other cellulose ethers, hydroxyethyl and propylcellulose as well Called Kernmehlether, can be used as a thickener become.

Examples of polyacrylic and polymethacrylic thickeners include the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI name according to the International Dictionary of Cosmetic Ingredients of The Cosmetic, Toiletry and Fragrance Association (CTFA) ": carbomer), also referred to as carboxyvinyl polymers. Such polyacrylic acids are inter alia from the company. 3 V Sigma under the trade name Polygel ^® , z. B. Polygel DA, and from the company. BF Goodrich under the trade name Carbopol ^® available, z. Carbopol 940 (molecular weight about 4,000,000), Carbopol 941 (molecular weight about 1 250,000) or Carbopol 934 (molecular weight about 3,000,000). Furthermore, the following acrylic acid copolymers are included: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple ester, preferably formed with C _1-4 -alkanols (INCI acrylates copolymer), such as the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS name according to Chemical Abstracts service: 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) and, for example, by the company Rohm & Haas under the trade names Aculyn ^®. and Acusol ^®, and from Degussa (Goldschmidt) under the trade name Tego ^® polymer, z. The anionic non-associative polymers Aculyn 22, Aculyn 28, Aculyn 33 (crosslinked), Acusol 810, Acusol 820, Acusol 823 and Acusol 830 (CAS 25852-37-3); (ii) crosslinked high molecular weight acrylic acid copolymers, such as those crosslinked with an allyl ether of sucrose or pentaerythritol copolymers of C _10-30 alkyl acrylates with one or more monomers selected from the group of acrylic acid, methacrylic acid and their simple, preferably with C _1-4 Alkanols formed, esters (INCI acrylates / C _10-30 alkyl acrylate crosspolymer) and which are available, for example, from the company. BF Goodrich under the trade name Carbopol ^® , z. B. the hydrophobic Carbopol ETD 2623 and Carbopol 1382 (INCI Acrylates / C _10-30 alkyl acrylate crosspolymer) and Carbopol Aqua 30 (formerly Carbopol EX 473).

Another preferred polymeric thickener is xanthan gum, a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions and having a molecular weight of from 2 to 15 million daltons. Xanthan is formed from a chain of β-1,4-linked glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyru vat units determines the viscosity of the xanthan gum.

As thickening agent, a fatty alcohol is also suitable. Fatty alcohols may be branched or unbranched, of native origin or of petrochemical origin. Preferred fatty alcohols have a C chain length of 10 to 20 C atoms, preferably 12 to 18. Preference is given to using mixtures of different C chain lengths, such as tallow fatty alcohol or coconut oil fatty alcohol. Examples are Lorol ^® Special (C _12-14 -ROH) or Lorol ^® Technical (C _12-18 -ROH) (both ex Cognis).

The Detergent may be 0.01 to 3 wt%, and preferably 0.1 to 1 wt .-% thickener included. The amount of inserted Thickener is dependent on the type of thickener and the desired degree of thickening.

Agents according to the invention may comprise further enzymes in addition to the abovementioned oxidoreductases in order to increase the washing or cleaning performance, it being possible in principle to use all enzymes established for this purpose in the prior art. These include in particular proteases, amylases, amadoriases, lipases, hemicellulases or cellulases, and preferably mixtures thereof. These enzymes are usually of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly. Agents of the invention preferably contain enzymes in total amounts of from 1 × 10 ^-6 to 5 weight percent based on active protein.

Among the proteases, those of the subtilisin type are preferable. Examples thereof are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg in a developed form under the trade names Alcalase ^® from Novozymes A / S, Bagsvaerd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase ^®, or Savinase ^® from Novozymes. From the protease from Bacillus lentus DSM 5483 ( WO 91/02792 ) derive from the name under the name BLAP ^® variants, which in particular in WO 92/21760 . WO 95/23221 . WO 02/088340 and WO 03/038082 to be discribed. Other useful proteases from various Bacillus sp. And B. gibsonii strains are found in the patent applications WO 03/054185 . WO 03/056017 . WO 03/055974 and WO 03/054184 out.

Other usable proteases are, for example, under the trade names Durazym ^®, relase ^®, Everlase® ^®, Nafizym, Natalase ^®, Kannase® ^® and Ovozymes ^® from Novozymes, under the trade names Purafect ^®, Purafect ^® OxP, Purafect Prime ^® and Properase.RTM ^® from Genencor, that under the trade name Protosol® ^® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi ^® from Wuxi Snyder Bioproducts Ltd., China, the P under the trade names Proleather® ^® and protease ^® from Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzymes available under the name proteinase K-16 from Kao Corp., Tokyo, Japan.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, B. amyloliquefaciens or B. stearothermophilus and also their further developments improved for use in detergents and cleaners. The enzyme from B. licheniformis is available from Novozymes under the name Termamyl ^® and from Genencor under the name Purastar® ^® ST. Development products of this α-amylase are available from Novozymes under the trade names Duramyl ^® and Termamyl ^® ultra, from Genencor under the name Purastar® ^® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ^®. The α-amylase from B. amyloliquefaciens is marketed by Novozymes under the name BAN ^®, and variants derived from the α-amylase from B. stearothermophilus under the names BSG ^® and Novamyl ^®, likewise from Novozymes. Further commercial products are for example the Amylase-LT ^{®, ®} and Stainzyme® Stainzyme® Ultra ^®, the latter also from the Novozymes.

Furthermore, for this purpose in the application WO 02/10356 disclosed α-amylase from Bacillus sp. A 7-7 (DSM 12368) and in the application WO 02/44350 described cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948). Furthermore, the amylolytic enzymes belonging to the sequence space of α-amylases can be used, which in the application WO 03/002711 is defined, and the ones in the application WO 03/054177 to be discribed. Likewise, fusion products of said molecules can be used, for example those from the application DE 10138753 ,

In addition, the enhancements available under the trade names Fungamyl.RTM ^® by Novozymes of α-amylase from Aspergillus niger and A. oryzae, which are. Another commercial product is, for example, the amylase ^LT® .

Compositions according to the invention may contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ^®, Lipolase Ultra ^®, LipoPrime® ^®, Lipozyme® ^® and Lipex ^®. Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. Likewise useable lipases are available from Amano under the designations Lipase CE ^®, Lipase P ^®, Lipase B ^®, or lipase CES ^®, Lipase AKG ^®, Bacillis sp. ^Lipase® , Lipase ^AP® , Lipase M- ^AP® and Lipase ^{AML® are} available. From the company Genencor, for example, the lipases, or cutinases can be used, the initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. Other important commercial products are the originally marketed by Gist-Brocades preparations M1 Lipase ^® and Lipomax® ^® and the enzymes marketed by Meito Sangyo KK, Japan under the names Lipase MY-30 ^®, Lipase OF ^® and lipase PL ^® to mention also the product Lumafast® ^® from Genencor.

invention Means can, especially if they are for treatment of textiles are thought to contain cellulases, depending on the purpose as pure enzymes, as enzyme preparations or in the form of Mixtures in which the individual components advantageously with regard to their different performance aspects. These performance aspects include, in particular, contributions to the primary washing power, to the secondary washing power of the agent (anti-redeposition effect or graying inhibition) and conditioning (fabric effect), to the exercise of a "stone wash "effect.

A useful fungal, endoglucanase (EG) -rich cellulase preparation, or its further developments are offered by Novozymes under the trade name Celluzyme ^®. The products Endolase® ^® and Carezyme ^®, likewise available from Novozymes, are based on the 50 kD EG and 43 kD EG from H. insolens DSM 1800. Further commercial products of this company are Cellusoft® ^® and Renozyme ^®. The latter is based on the application WO 96/29397 A1 , Performance-enhanced cellulase variants go, for example, from the application WO 98/12307 A1 out. Likewise, those in the application WO 97/14804 A1 disclosed cellulases used; For example, it revealed 20 kD EG Melanocarpus, available from AB Enzymes, Finland, under the trade names Ecostone® ^® and Biotouch ^®. Further commercial products from AB Enzymes are Econase® ^® and ECOPULP ^®. Other suitable cellulases from Bacillus sp. CBS 670.93 and CBS 669.93 are in WO 96/34092 A2 disclosed, the Bacillus sp. CBS 670.93 from the company Genencor under the trade name Puradax ^{® is} available. Further commercial products of the company Genencor are "Genencor detergent cellulase L" and IndiAge ^® Neutra.

Compositions according to the invention may also contain enzymes, which are grouped together under the term hemicellulases, in particular for the removal of certain problem soiling. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases. Suitable mannanases are available, for example under the name Gamanase ^® and Pektinex AR ^® from Novozymes, under the name Rohapec ^® B1 from AB Enzymes and under the name Pyrolase® ^® from Diversa Corp., San Diego, CA, United States. A suitable β-glucanase from a B. alcalophilus, for example, from the application WO 99/06573 A1 out. The obtained from B. subtilis β-glucanase is available under the name Cereflo ^® from Novozymes.

The enzymes used in agents according to the invention are either originally from microorganisms, about genera Bacillus, Streptomyces, Humicola or Pseudomonas, and / or are used according to known biotechnological processes produced by suitable microorganisms, such as transgenic Expression hosts of the genera Bacillus or filamentous Fungi.

The Purification of the enzymes concerned is conveniently carried out over per se established methods, for example about precipitation, Sedimentation, concentration, filtration of the liquid Phases, microfiltration, ultrafiltration, exposure to chemicals, Deodorization or suitable combinations of these steps.

invention The oxidoreductases can be used as well as the optionally additionally used enzymes in each according to the state the technique established form be added. These include, for example those obtained by granulation, extrusion or lyophilization solid preparations or, especially in liquid or gel agents, solutions of enzymes, advantageously as concentrated as possible, low in water and / or mixed with stabilizers. Alternatively, these proteins can for both solid and liquid Dosage form adsorbed on a solid support and / or be encapsulated.

encapsulation For example, by spray drying or extrusion the enzyme solution together with a preferably natural Polymer take place or in the form of capsules in which the enzymes as enclosed in a solidified gel or in such of the core-shell type, in which an enzyme-containing core with a water, Air and / or chemical impermeable protective layer coated is. In superimposed layers may additionally other active ingredients, for example stabilizers, emulsifiers, pigments, Bleaching or dyes are applied. Such capsules are according to methods known per se, for example by pouring or roll granulation or applied in fluid-bed processes. advantageously, are such granules, for example by applying polymeric Film former, low-dust and storage-stable due to the coating.

The encapsulated form lends itself to protecting the enzymes or other ingredients from other ingredients, such as bleaches, or to allow for controlled release. Depending on the size of these capsules, a distinction is made according to milli, micro and nano capsules, with microcapsules for enzymes being particularly preferred. Such capsules are described, for example, in the patent applications WO 97/24177 and DE 19918267 disclosed. Another possible encapsulation method is that the proteins are encapsulated in this substance, starting from a mixture of the protein solution with a solution or suspension of starch or a starch derivative. Such an encapsulation process is with the application WO 01/38471 described.

In a particular embodiment, granulation of the enzymes, in particular of the oxidoreductase to be used according to the invention, as in the application DE 102006018780 described described. In addition to the enzymes, it is also possible to granulate further sensitive detergent or cleaning agent ingredients such as fragrances, optical brighteners or the bleach activators to be used according to the invention in order to protect them from other components, in particular from any bleaching agents present.

In This embodiment is the sensitive detergent or cleaning agent ingredient together with a chemically inert carrier material and granulated a chemically inert binder. The carrier material can in this case be selected from inorganic substances, such as For example, clays, silicates or sulfates, especially talc, Silicas, metal oxides, in particular aluminum oxides and / or titanium dioxide, silicates, in particular phyllosilicates, Sodium aluminum silicates, bentonites and / or aluminosilicates (zeolites). It can also be an organic compound such as Polyvinyl alcohol (PVA), in particular at least partially hydrolyzed PVA act. It is particularly advantageous if these compounds fulfill an additional benefit, for example a builder function when using the detergent or cleaning agent.

By contrast, in this embodiment, a binder is a solid, waxy or liquid material which is solid at room temperature and which is chemically inert to such an extent that it can not be mixed with any of the ingredients of the production, processing and storage conditions of the granules Granules or agent in an affecting the overall efficiency of the granules extent reacts. It is a different material from the substrate. It is or becomes at least so viscous under the conditions of granule production that it virtually sticks the other ingredients together. Of particular importance here is the physico-chemical interaction with the carrier material, which leads to the resulting mass becoming an overall homogeneous phase which can subsequently be converted into individual granulate particles. In this pulp, which is formed predominantly of the carrier material and binder components, the other ingredients and in particular the ingredient to be formulated are included. Suitable binders are inorganic or organic substances which have the properties described, for example non-crosslinked, polymeric compounds selected from the group of polyacrylates, polymethacrylates, methacrylic acid-ethyl acrylate copolymers, polyvinylpyrrolidones, polysaccharides or substituted polysaccharides, in particular cellulose ethers, and / or polyvinyl alcohols (PVA), preferably partially hydrolyzed polyvinyl alcohols and / or ethoxylated polyvinyl alcohols and their copolymers and mixtures. PVA or its derivatives are due to their adsorption properties and their co-existing binding effect both as a carrier material and as a binder component suitable. They can therefore be used as binders, if they are not already used as a carrier material.

Incidentally, with respect to this embodiment, the DE 102006018780 directed.

Farther For example, it is possible to use two or more enzymes, such as one to be used according to the invention Oxidoreductase and another enzyme to assemble together so that a single granule has multiple enzyme activities having.

One contained in a composition according to the invention Protein, in particular the inventive Oxidoreductase, especially against during storage Damage such as inactivation, denaturation or decay by physical influences, oxidation or proteolytic cleavage. In microbial Obtaining the proteins and / or enzymes is inhibiting the Proteolysis particularly preferred, especially if the means Contain proteases. Preferred inventive Means contain stabilizers for this purpose.

A Group of stabilizers are reversible protease inhibitors. Often For this purpose, benzamidine hydrochloride, borax, boric acids, Boronic acids or their salts or esters used, including especially derivatives with aromatic groups, such as ortho-, meta- or para-substituted phenylboronic acids, in particular 4-formylphenyl-boronic acid, or the salts or Esters of the compounds mentioned. Also peptide aldehydes, that is Oligopeptide with reduced C-terminus, especially those from From 2 to 50 monomers are used for this purpose. To the peptidic reversible protease inhibitors include, among others, ovomucoid and Leupeptin. Also specific, reversible peptide inhibitors for the protease subtilisin as well as fusion proteins from proteases and specific peptide inhibitors are suitable for this purpose.

Other enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C ₁₂ , such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Certain organic acids used as builders are additionally capable of stabilizing a contained enzyme.

low aliphatic alcohols, but especially polyols, such as Glycerine, ethylene glycol, propylene glycol or sorbitol are other commonly used enzyme stabilizers. Di-glycerol phosphate also protects against denaturation due to physical influences. As well Calcium and / or magnesium salts are used, such as Calcium acetate or calcium formate.

Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations. Polyamine N-oxide containing polymers act simultaneously as enzyme stabilizers and as dye transfer inhibitors. Other polymeric stabilizers are linear C ₈ -C ₁₈ polyoxyalkylenes. Also, alkylpolyglycosides can stabilize the enzymatic components of the agent according to the invention and are able, preferably, to additionally increase their performance. Crosslinked N-containing compounds preferably perform a dual function as soil release agents and as enzyme stabilizers. Hydrophobic, nonionic polymer stabilizes in particular an optionally contained cellulase.

reducing agent and antioxidants increase the stability of the Enzymes against oxidative decay; are for this For example, sulfur-containing reducing agents familiar. Other examples are sodium sulfite and reducing sugars.

Especially preferably combinations of stabilizers are used, for example from polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing Salt. The effect of peptide-aldehyde stabilizers is favorably by combination with boric acid and / or boric acid derivatives and polyols increased and even further by the extra Effect of divalent cations, such as calcium ions.

In the case of solid compositions, the proteins - polypeptides according to the invention as well as optionally contained further enzymes - can be used, for example, in dried, granulated and / or encapsulated form. They can be used separately, ie as a separate phase, or with other components together the same phase, be added with or without compaction. If microencapsulated enzymes are to be processed in solid form, the water can be removed by methods known from the prior art from the aqueous solutions resulting from the workup, such as spray drying, centrifuging or by solubilization. The particles obtained in this way usually have a particle size between 50 and 200 microns.

liquid, gelatinous or pasty inventive The proteins can be used starting from one after the Prior art protein recovery and preparation in concentrated aqueous or non-aqueous Solution, suspension or emulsion are added, but also in gel form or encapsulated or as a dried powder. such Detergents or cleaning agents according to the invention are usually made by simply mixing the ingredients, in substance or as a solution in an automatic Mixer can be given.

Of the Proportion of enzymes, of the enzyme liquid formulation (s) or the enzyme granules in a detergent can, for example about 0.01 to 5 wt .-%, preferably 0.12 to about 2.5 wt .-% amount.

As electrolytes from the group of inorganic salts, a wide number of different salts can be used. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a production point of view, the use of NaCl or MgCl ₂ in the textile treatment agents is preferred. The proportion of electrolytes in the washing or cleaning agent is usually 0.1 to 5 wt .-%.

non-aqueous Solvents used in the detergent may come, for example, from the group of or polyhydric alcohols, alkanolamines or glycol ethers, if so they are miscible with water in the specified concentration range. Preferably, the solvents are selected from ethanol, n- or i-propanol, butanols, glycol, propane or Butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, Ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, Ethylene glycol monon butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, Propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, di-iso-propylene glycol monomethyl or ethyl ether, Methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, di-n-octyl ether as well as mixtures of these solvents. non-aqueous Solvents may be present in the washing or cleaning agent in amounts of between 0.5 and 15% by weight, but preferably below 12% by weight and in particular be used below 9 wt .-%.

Around the pH of the detergent in the desired range The use of pH adjusters may be indicated. Can be used here all known acids or alkalis, provided that their use is not from application technology or ecological reasons or for reasons consumer protection. Usually exceeds the amount of these adjusting agents is not 10% by weight of the total formulation.

Of the pH of the cleaning agent is preferably between 4 and 10 and preferably between 5.5 and 8.8.

In a preferred embodiment contains the Detergent one or more perfumes in a crowd from usually to 10 wt .-%, preferably 0.01 to 5 wt .-%, in particular 0.3 to 3 wt .-%.

When Perfume oils or fragrances can be individual Fragrance compounds, eg. B. the synthetic products of the type the esters, ethers, aldehydes, ketones, alcohols and hydrocarbons be used. However, mixtures of various are preferred Fragrances are used, which together create an appealing fragrance produce. Such perfume oils can also contain natural fragrance mixtures, such as those from vegetable Sources are accessible.

Around to improve the aesthetic impression of the cleaning agent, they can be colored with suitable dyes become. Preferred dyes, the selection of which the expert no Difficulty, possess a high storage stability and insensitivity to the other ingredients the textile treatment agent and against light and no pronounced Substantivity to textile fibers, not these to stain.

Suitable foam inhibitors which can be used in the detergents or cleaners are, for example, soaps, paraffins or silicone oils, which may be applied to support materials could be brought.

suitable Soil-release polymers, also called "anti-redeposition agents" are, for example, nonionic cellulose ethers such as methylcellulose and methyl hydroxypropylcellulose with a Proportion of methoxy groups from 15 to 30 wt .-% and hydroxypropyl groups from 1 to 15 wt .-%, each based on the nonionic cellulose ether as well as the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular Polymers of ethylene terephthalates and / or polyethylene and / or Polypropylene glycol terephthalates or anionic and / or nonionic modified derivatives of these. Suitable derivatives include the sulfonated derivatives of phthalic and terephthalic acid polymers.

graying have the task, the detached from the fiber dirt to keep suspended in the fleet and so the recovery of the Prevent dirt. These are water-soluble colloids mostly organic nature suitable, for example, glue, gelatin, Salts of ether sulfonic acids of starch or Cellulose or salts of acidic sulfuric acid esters of Cellulose or starch. Also water-soluble, Acidic group-containing polyamides are for this purpose suitable. Furthermore, can be soluble starch preparations and use other than the above starch products, for example degraded starch, aldehyde starches etc. Also, polyvinylpyrrolidone is useful. However, preference is given Cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, Hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, Methylhydroxypropylcellulose, methylcarboxymethylcellulose and their Mixtures in amounts of 0.1 to 5 wt .-%, based on the total amount on washing or cleaning agents used.

There textile fabrics, in particular of rayon, rayon, Cotton and its blends may tend to wrinkle, because the individual fibers against bending, bending, pressing and squeezing transverse to the fiber direction, the washing or detergents containing synthetic crease inhibitors. These include, for example, synthetic products the base of fatty acids, fatty acid esters, fatty acid amides, Alkylolestern, -alkylolamiden or fatty alcohols, usually with Ethylene oxide reacted or products based on lecithin or modified phosphoric acid ester.

to Control of microorganisms can be the cleaners contain antimicrobial agents. Here one differentiates depending on antimicrobial spectrum and mechanism of action between Bacteriostats and bactericides, fungistats and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, Alkylarylsulfonates, halophenols and Phenolmercuriacetat, wherein in the inventive detergents or cleaners also be completely dispensed with these compounds can.

The cleaning agents according to the invention may contain preservatives, it being preferred to use only those which have no or only a slight skin-sensitizing potential. Examples are sorbic acid and its salts, benzoic acid and its salts, salicylic acid and its salts, phenoxyethanol, formic acid and its salts, 3-iodo-2-propynyl butylcarbamate, sodium N- (hydroxymethyl) glycinate, biphenyl-2-ol and mixtures thereof. A suitable preservative provides the solvent-free, aqueous combination of diazolidinyl urea, sodium benzoate and potassium sorbate (available as Euxyl K 500 ^® from Schuelke & Mayr), which can be used in a pH range up. 7

Around undesirable, by oxygen action and other oxidative Processes caused changes to the textile treatment agents and / or to prevent the treated fabrics the detergents or cleaning agents contain antioxidants. To this Class of connection includes, for example, substituted ones Phenols, hydroquinones, catechols and aromatic amines as well organic sulfides, polysulfides, dithiocarbamates, phosphites, phosphonates and vitamin E.

One increased wearing comfort can from the additional Use of antistatic agents that results in detergents or cleansers additionally be attached. Enlarge antistatic agents the surface conductivity and allow thus an improved drainage of formed charges. Outer Antistatic agents are usually substances with at least one hydrophilic Molecule ligands and give on the surfaces a more or less hygroscopic film. These mostly surface-active Antistatic agents can be found in nitrogenous (amines, amides, quaternary Ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. Lauryl (or stearyl) dimethylbenzylammonium chlorides are suitable as antistatics for textile fabrics or as an additive to textile treatment agents, in addition a softening effect is achieved.

to Improvement of the rewettability of the treated textile Fabrics and to facilitate ironing the treated fabrics can used in the textile treatment agents, for example, silicone derivatives become. These additionally improve the rinsing behavior the washing or cleaning agent by its foam-inhibiting Properties. Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups are one to five Have C atoms and are completely or partially fluorinated. preferred Silicones are polydimethylsiloxanes which are optionally derivatized can be and then amino-functional or quaternized or Si-OH, Si-H and / or Si-Cl bonds. The Viscosities of the preferred silicones are 25 ° C in the range between 100 and 100,000 mPas; the silicones being in Amounts between 0.2 and 5% by weight, based on the total amount of washing or cleaning agent can be used.

After all The cleaning agent may also contain UV absorbers on the Treat treated fabrics and the light resistance improve the fibers. Connections that those desired Properties are, for example, those by radiationless Deactivation of effective compounds and derivatives of benzophenone with substituents in the 2- and / or 4-position. Continue to be substituted benzotriazoles, in the 3-position phenyl-substituted Acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural products like umbelliferone and the body's own urocanic acid suitable.

Around the catalyzed by heavy metals decomposition of certain detergent ingredients To avoid substances can be used, the heavy metals complex. Suitable heavy metal complexing agents are, for example the alkali metal salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA), methylglycinediacetic acid trisodium salt (MGDA) and alkali metal salts of anionic polyelectrolytes like polymaleates and polysulfonates.

A preferred class of complexing agents are the phosphonates, which in the washing or cleaning agent in amounts of 0.01 to 2.5 wt .-%, preferably 0.02 to 2 wt .-% and in particular from 0.03 to 1.5 Wt .-% are included. These preferred compounds include in particular organophosphonates such as, for example, 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine-penta (methylenephosphonic acid) (DTPMP or DETPMP) as well as 2-phosphonobutane-1,2,4-tricarboxylic acid (PBS-AM), which are mostly in the form of their ammonium or alkali metal salts be used.

The Cleaning agents according to the invention can for washing and / or cleaning textile fabrics, in particular dyed textile fabrics, be used.

to Preparation of the cleaning agent can initially be a basic formula produced by conventional methods and methods in which, for example, the ingredients of the base recipe are simply mixed in stirred tanks, water, non-aqueous solvents and surfactants suitably be submitted and the other ingredients (if necessary in encapsulated form). A separate one Heating during production is not required. If If desired, the temperature of the mixture should be 80 ° C do not exceed.

EXAMPLES

Example 1: Review the cleaning performance of a detergent with and without pretreatment the laundry by an inventive pretreatment agents

A Pretreatment cream containing a bleach activator (TAED) as well an oxidoreductase substrate (glucose) is put on a laundry soiling applied and either immediately after application or after 30 minutes exposure time, the washing process is carried out. During the subsequent washing process was a commercial Liquid detergent used, which has been extended by that an oxidoreductase (glucose oxidase) was added.

- Preparation of the pretreatment cream

First, a soap is made. For this purpose, 5 g of glycerol and 2 g of fatty acid (Edenor PK 12-18 GA, CAS 67701-05-7, melted at 70 ° C) are mixed together at 70 ° C. Subsequently, NaOH solution is added until the pH is 7-8. The soap is mixed in the liquid state with the other ingredients. 7 g of TAED are mortared and mixed with 7 g of glucose monohydrate. To be this mixture 7 g of liquid soap added. The resulting preparation is mixed and cooled.

- Washing test

It Apply a defined amount of the cream on a smudge lobe (2.5 × 2.5 cm EMPA 167) applied and with the spatula briefly massaged; in this example was dosed so that in the Wash then 0.3 mmol / 300 ml of wash liquor Glucose and 0.26 mmol / 300 ml of TAED. After application of the pretreatment agent was either washed immediately or else allowed to act for 30 minutes before washing. In the piston with The pretreated lobe was also an untreated Läppchen mitgewaschen. For the determination of comparative values was once with commercial liquid detergent washed without oxidoreductase, on the other was liquid detergent used with oxidoreductase, the components of the pre-wash cream (Glucose and TAED) for comparison - in the same amount as applied to the lobules - directly into the wash liquor were given.

The Lappets were dissolved in 300 ml of washing liquor (4.4 g / l liquid detergent, 30 ml 150 mM glycine / NaOH pH 10, 140 ml synthetic tap water, 88 U glucose oxidase for 60 min. at 40 ° C and Washed 150 rpm in 500 ml baffle flask.

The Evaluation took place after drying of the lobules by means of a brightness measurement with the camera Minolta Cm508d. After deduction of the detergent comparison value (no bleach activator, no glucose oxidase, no glucose) the results (ΔL *) are noted.

Production of synthetic tap water:

While stirring
290 mg CaCl2 2H2O
140 mg MgCl2 6H2O and
210 mg NaHCO3
in 1 liter redist. Add water and mix well.

Results

Table 1: Results (ΔL *) of the brightness measurements relative to the result of the reference given in row 1

rehearse 2) and 3) are better bleached than sample 1), so the Pretreatment with the prewash cream according to the invention positive for the washing result in comparison with a one-component detergent which contains the complete bleach system. This benefits surprisingly also the non-treated soiling 2) of the presence Pretreatment 3) in the common wash liquor of the flask No. 1, however, the pretreated soil 2) becomes much stronger bleached as the non-pretreated soiling.

One similar result was also at pretreatment with 30 minutes Pre-incubation achieved (piston no. 2). It was found here be that after 30 minutes preincubation of both the pretreated and untreated dirt (piston 2) again bleached much better than without preincubation (piston 1, Samples 2) and 3)), although the total dosage of TAED and Glucose in the pistons 0, 1 and 2 does not differ on the wash liquor.

piston Figures 3 and 4 show that the pre-wash cream also works without glucose oxidase only on pretreated stains a certain Whitening performance can cause, however, is significantly lower as each with the same length of pretreatment and subsequent Washing with glucose oxidase (sample 7 compared to sample 3 and Sample 9 compared to sample 5)).

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

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Claims (22)

Process for the cleaning of textile fabrics, characterized in that the textile fabrics, and in particular the soils thereon, are treated prior to the washing process with an agent containing at least one substrate for a hydrogen peroxide-producing oxidoreductase. Method according to claim 1, comprising the following steps: a) a textile fabric, and in particular at least a stain on it will come with a remedy containing at least one substrate for a hydrogen peroxide treating producing oxidoreductase, b) the textile fabric according to (a) is subjected to a washing process, during the washing process preferably a detergent is used, which is a hydrogen peroxide-producing oxidoreductase containing the substrate according to (a) below Training hydrogen peroxide can implement. Method according to claim 1, characterized in that that the textile fabrics, and in particular the on it soiling, before washing with be treated with an agent containing at least one substrate for a hydrogen peroxide producing oxidoreductase and at least one Contains bleach activator. Method according to claim 3, comprising the following steps: a) a textile fabric, and in particular at least a stain on it, will be provided with a means containing at least one substrate for a hydrogen peroxide producing oxidoreductase and at least one bleach activator treated b) the textile fabric according to (a) is subjected to a washing process, during which Washing process preferably a detergent is used, the contains a hydrogen peroxide-producing oxidoreductase, which the substrate according to (a) to form Hydrogen peroxide can implement. Method according to claim 1, characterized in that that the textile fabrics, and in particular the on it soiling, before washing with be treated with an agent containing at least one substrate for a hydrogen peroxide producing oxidoreductase and at least one Substrate for a perhydrolase and optionally at least contains a perhydrolase. Method according to claim 5, comprising the following steps: a) a textile fabric, and in particular at least a stain on it, will be provided with a means containing at least (a1) a substrate for a hydrogen peroxide producing oxidoreductase and at least (a2) a substrate for treated a perhydrolase, b) the textile fabric according to (a) is subjected to a washing process, during the washing process preferably a detergent is used, which produces at least one hydrogen peroxide Oxidoreductase containing the substrate according to (a1) with the formation of hydrogen peroxide, as well as at least a perhydrolase containing the substrate according to (a2) by reacting hydrogen peroxide in a peracid can convert. Method according to claim 5 or 6, the following steps full: a) a textile fabric, and in particular at least one soiling thereon, with a An agent containing at least (a1) a substrate for a Perhydrolase and at least (a2) a substrate for one Containing hydrogen peroxide-producing oxidoreductase and further at least one perhydrolase comprising the substrate according to (a1) by reacting hydrogen peroxide in a peracid can handle, treated, b) the textile fabric according to (a) is subjected to a washing process, during the washing process preferably a detergent is used, which produces at least one hydrogen peroxide Containing oxidoreductase containing the substrate according to (a2) can implement with the formation of hydrogen peroxide. Method according to one of the preceding claims, characterized in that producing as hydrogen peroxide Oxidoreductase a glucose oxidase is used. Method according to one of the preceding claims, characterized in that used as a bleach activator TAED becomes. Laundry pre-treatment agent, characterized that there is at least one substrate for a hydrogen peroxide containing producing oxidoreductase. Laundry pre-treatment agent according to claim 10, characterized in that there is at least one substrate for a hydrogen peroxide producing oxidoreductase and at least contains a bleach activator. Laundry pre-treatment agent according to claim 10, characterized in that it has at least one substrate for a hydrogen peroxide producing oxidoreductase and at least contains a substrate for a perhydrolase. Laundry pre-treatment agent according to claim 12, characterized in that it has at least one substrate for a hydrogen peroxide-producing oxidoreductase, at least a substrate for a perhydrolase and at least one Contains perhydrolase. Laundry pre-treatment agent according to one of Claims 10 to 13, characterized in that the substrate for the hydrogen peroxide producing oxidoreductase is contained in an amount of at least 5 wt .-%. Laundry pre-treatment agent according to one of Claims 10 to 14, characterized in that as hydrogen peroxide producing oxidoreductase a glucose oxidase is used. Laundry pre-treatment agent according to one of Claims 10 to 15, characterized in that as bleach activator TAED is used. Containing multi-component kit a) a laundry pre-treatment agent, containing at least one substrate for a hydrogen peroxide producing oxidoreductase, b) a detergent, preferably contains a hydrogen peroxide-producing oxidoreductase, which the substrate according to (a) to form Hydrogen peroxide can implement. A multi-component kit according to claim 17, comprising a) a laundry pre-treatment agent containing at least one Substrate for a hydrogen peroxide-producing oxidoreductase and at least one bleach activator, b) a detergent that preferably a hydrogen peroxide-producing oxidoreductase containing the substrate according to (a) below Training hydrogen peroxide can implement. A multi-component kit according to claim 17, comprising a) a laundry pre-treatment agent containing at least (a1) a substrate for a hydrogen peroxide producing Oxidoreductase and at least (a2) a substrate for one perhydrolase, b) a detergent, preferably at least contains a hydrogen peroxide-producing oxidoreductase, which the substrate according to (a1) to form Hydrogen peroxide can implement, and preferably at least one Containing perhydrolase which is the substrate according to (a2) by reacting hydrogen peroxide in a peracid can implement. A multi-component kit according to claim 19, comprising a) a laundry pre-treatment agent containing at least (a1) a substrate for a hydrogen peroxide producing Oxidoreductase and at least (a2) a substrate for one Perhydrolase and at least one perhydrolase, which is the substrate according to (a2) with the reaction of hydrogen peroxide into a peracid, b) a detergent, which preferably produces at least one hydrogen peroxide Oxidoreductase containing the substrate according to (a1) can implement with the formation of hydrogen peroxide. Multi-component kit according to one of the claims 17 to 20, characterized in that producing as hydrogen peroxide Oxidoreductase a glucose oxidase is used. Multi-component kit according to one of the claims 17 to 21, characterized in that TAED as bleach activator is used.