RU2386670C2 - Composition containing enzyme and toned agent for fabric - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention relates to compositions which contain certain versions of lipase and a toned agent for fabric, and includes use of such compositions for cleaning and/or treating surface areas or fabric.

EFFECT: improved deposition of temporary colourant, reduced activity of the enzyme which leads to bad smell, and improved perception of cleanness.

17 cl, 3 tbl, 16 ex

Description

Technical field

The invention relates to compositions containing lipases and tinting agents for tissues, and methods for producing and using such products.

Prior art

The advent of lipase enzymes suitable for use in detergents creates a new opportunity for the developer to improve the removal of fats. Such enzymes catalyze the hydrolysis of triglycerides, which are the main component of many common fatty contaminants, such as sebaceous secretions, animal fats (e.g. lard, ghee, butter), and vegetable oils (e.g. olive oil, sunflower oil, peanut butter) . However, these enzymes typically have low efficiency in the first wash cycle and typically lead to the formation of an unpleasant odor, which is thought to result from the hydrolysis of fats present in stains from dairy products such as milk drinks, cream, butter and yoghurts. Not limited to theory, it is believed that such contaminants tend to form a lipase-induced odor, since they contain triglycerides functionalized with short-chain (e.g. C ₄ ) fatty acyl units that release unpleasantly smelling volatile fatty acids after lipolysis. Even if the effectiveness of such enzymes improves, the problem of unpleasant odors remains. Therefore, the use of this technology is severely limited.

We found that the combination of a tissue tint agent with certain lipase variants improves the cleaning efficiency, while minimizing an unacceptable unpleasant odor. Not wishing to be bound by theory, we indicate that it is believed that such beneficial effects are probably provided by the following mechanisms: selected lipase variants increase the degree of fat removal, which leads to improved access of the tinting agent to the tissue to the surface of the tissue and, consequently, its improved deposition. The resulting combination of improved removal of oil contaminants and deposition of tint dye leads to improved appearance of the fabric; even in the case of insufficient removal of oil contaminants, hydrolysis of fats to more hydrophilic fatty acids, mono- and diglycerides leads to improved deposition of a tint dye and, thus, a feeling of purity; the presence of dye molecules deposited in the oil contaminants present on the tissue can inhibit the activity of the enzyme, leading to an unpleasant odor.

SUMMARY OF THE INVENTION

This invention relates to compositions containing lipases and tinting agents for tissue, and methods for producing and using such products.

DETAILED DESCRIPTION OF THE INVENTION

Definitions

As used herein, the term “detergent composition” includes, unless otherwise indicated, granular or powdered universal or “heavy-duty” detergents, especially laundry detergents; liquid, gel or paste-like universal detergents, especially the so-called liquid-type detergents for harsh working conditions; liquid detergents for thin lung tissues; manual dishwashing detergents or dishwashing detergents for light modes, especially highly foaming type; means for dishwashers, including various tableted, granular, liquid types and means to reduce the amount of droplets remaining on the dishes for use at home and in catering establishments; liquid detergents and disinfectants, including antibacterials for hand washing, lumpy detergents, mouthwashes, cleaning products for teeth and oral cavity, shampoos for washing machines and carpets, bathroom cleaning products; shampoos and hair rinses; shower gels and shower foams and metal cleaning products; as well as detergent additives, such as bleaching additives and stain pencils or pretreatment agents.

As used herein, the term “fabric tinting agent” means dyes or pigments that, when incorporated into detergent compositions, can be deposited on the fabrics when said fabric is contacted with a cleaning solution containing said detergent compositions, thereby changing the color of said fabric. For the purposes of this application, fluorescent optical brighteners are not considered fabric tinting agents.

As used here, the phrase "independently selected from a group consisting of ..." means that the components or elements selected from the specified Markush group may be the same, may be different, or may be any mixture of elements.

The test methods disclosed in the Test Methods section of this application should be used to determine the corresponding parameter values of the claimed inventions.

Unless otherwise indicated, all levels of components or compositions refer to the active levels of a given component or composition and do not take into account impurities, such as residual solvents or by-products, which may be present in commercially available sources.

All percentages and ratios are calculated by weight unless otherwise indicated. All percentages and ratios are calculated with respect to the entire composition, unless otherwise indicated.

It should be understood that each maximum numerical limit specified in the present description includes each lower numerical limit, as if such lower numerical limits were explicitly indicated here. Each minimum numerical limit specified in the present description will include each upper numerical limit, as if such upper numerical limits were explicitly indicated here. Each numerical range indicated in this description will include each narrower numerical range falling within such a wider numerical range, as if such narrower numerical ranges were all explicitly indicated here.

All cited documents, in the relevant part, are hereby incorporated by reference; reference to any document should not be construed as an assumption that it is a prior art in relation to the present invention.

Songs

The compositions of the present invention typically comprise from about 0.00003% to about 0.1%, from about 0.00008% to about 0.05%, or even from about 0.0001% to about 0.04% of a tissue tint agent and from about 0.0005% to about 0.1%, from about 0.001% to about 0.05%, or even from about 0.002% to about 0.03% lipase.

Such compositions may take any form, for example, the form of a washing composition and / or a composition for processing.

The remainder of the detergent compositions of any one of the aforementioned aspects consists of one or more auxiliary materials.

Suitable lipases

Suitable lipases include lipases selected from the group consisting of lipases belonging to group E.C. 3.1.1 Classification of enzymes, and mixtures thereof. In another aspect, suitable lipases include lipases selected from the group consisting of lipases having classification E.C. 3.1.1.3, as defined in the classification of EC, IUPAC-IUBMB, and mixtures thereof.

Examples of EU lipases 3.1.1.3 include those described in WIPO Publications WO 00/60063, WO 99/42566, WO 02/062973, WO 97/04078, WO 97/04079 and US 5869438. Preferred lipases are produced by Absidia reflexa, Absidia corymbefera, Rhizmucor miehei , Rhizopus delemar, Aspergillus niger, Aspergillus tubigensis, Fusarium oxysporum, Fusarium heterosporum, Aspergillus oryzea, Penicilium camembertii, Aspergillus foetidus, Aspergillus niger, Thermomyces lanoginosus (synonym: humulus penius, lomoginosomus penis, humonosomus penis, lomoginos humus penis Some of the preferred lipases are those sold by Novozymes under the trademarks Lipolase ^® , Lipolase Ultra ^® , Lipoprime ^® and Lipex ^® (registered trademarks of Novozymes), and LIPASE P "AMANO ^® " available from Areario Pharmaceutical Co. Ltd., Nagoya, Japan, AMANO- CES ®, commercially available from Toyo Jozo Co., Tagata, Japan; and other Chromobacter viscosum lipases from US Biochemical Corp., USA and Diosynth Co., Netherlands, and other lipases such as Pseudomonas gladioli. Additional suitable lipases are described in WIPO Publications WO 02062973, WO 2004/101759, WO 2004/101760 and WO 2004/101763. In one embodiment, suitable lipases include “first cycle lipases” described in WO 00/60063 and US Pat. No. 6,939,702 B1, preferably SEQ ID NO: 2, more preferably SEQ ID NO: 2, having at least 90% homology with SEQ ID NO: 2 and containing the substitution of an electrically neutral or negatively charged amino acid by R or K in any of the positions 3, 224, 229, 231 and 233, the most preferred option containing mutations T231R and N233R, and this most preferred option is sold under the trademark Lipex ^® . The above lipases can be used in combination (any mixture of lipases can be used). Suitable lipases can be purchased from Novozymes, Bagsvaerd, Denmark; Areario Pharmaceutical Co. Ltd., Nagoya, Japan; Toyo Jozo Co., Tagata, Japan; Amersham Pharmacia Biotech., Piscataway, New Jersey, USA; Diosynth Co., Oss, Netherlands and / or manufactured in accordance with the examples given in the present invention.

Suitable fabric tinting agents

Fluorescent optical brighteners emit at least some visible light. In contrast, fabric tinting agents can alter the shade of the surface because they absorb at least a portion of the spectrum of visible light. Suitable fabric tinting agents include dyes, dye-clay conjugates and pigments meeting the requirements of Test Method 1 in the Test Methods section of the present description. Suitable dyes include dyes with small molecules and polymer dyes. Suitable dyes with small molecules include dyes with small molecules selected from the group consisting of dyes that fall under the Color Index (CI) classification of direct blue, direct red, direct violet, acid blue, acid red, acid violet, basic blue, basic violet and basic red, or mixtures thereof, for example:

(1) Tris-azo direct blue dyes of the formula

where at least two of the naphthyl rings A, B and C are substituted with a sulfonate group, ring C may be substituted at position 5 with an NH ₂ or NHPh group, X is a benzyl or naphthyl ring substituted with up to 2 sulfonate groups and may be substituted at position 2 an OH group, and may also be substituted with an NH ₂ or NHPh group.

(2) Bis-azo direct violet dyes of the formula:

where Z is H or phenyl, ring A is preferably substituted with methyl and methoxy at the positions indicated by arrows, ring A can also be a naphthyl ring, Y is a benzyl or naphthyl ring which is substituted with a sulfate group and can be mono- or disubstituted methyl in groups.

(3) Blue or red acidic dyes of the formula:

where at least one of X and Y must be an aromatic group. In one aspect, both aromatic groups may be substituted with a benzyl or naphthyl group, which may be substituted with non-water solubilizing groups, such as alkyl or alkyloxy or aryloxy groups, X and Y may not be substituted with water solubilizing groups, such as sulfonates or carboxylates . In another aspect, X is a nitro-substituted benzyl group and Y is a benzyl group.

(4) Red acid structure dyes

или

or

where B is a naphthyl or benzyl group which may be substituted by water-insoluble groups, such as alkyl or alkyloxy or aryloxy groups, B cannot be substituted by water-solubilized groups, such as sulfonates or carboxylates.

(5) Dis-azo dyes structure

or

,

,

where X and Y, independently of each other, are each hydrogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy, R _α is hydrogen or aryl, Z is C ₁ -C ₄ alkyl; C ₁ -C ₄ alkoxy; halogen; hydroxyl or carboxyl, n is 1 or 2, and m is 0, 1 or 2, as well as their corresponding salts and mixtures thereof;

(6) Triphenylmethane dyes of the following structures

и/или

and / or

and mixtures thereof. In another aspect, suitable small molecule dyes include small molecule dyes selected from the group consisting of Color Index (Society of Dyers and Colorists, Bradford, UK) direct violet 9, direct violet 35, direct violet 48, direct violet 51, direct violet 66, direct blue 1, direct blue 71, direct blue 80, direct blue 279, acid red 17, acid red 73, acid red 88, acid red 150, acid violet 15, acid violet 17, acid violet 24, acid violet 43 , acid violet 49, acid blue 15, acid blue 17, acid blue 25, acid blue 29, acid blue 40, acid blue 45, acid blue 75, acid blue 80, acid blue 83, acid blue 90 and acid blue 113, acid black 1, the main violet 1, the main violet 3, the main violet 4, the main violet 10, the main violet 35, the main blue 3, the main blue 16, the main blue 22, the main blue 47, the main blue 66, the main blue 75, the main blue 159, and see them this. In another aspect, suitable small molecule dyes include small molecule dyes selected from the group consisting of Color Index (Society of Dyers and Colorists, Bradford, UK) Acid Purple 17, Acid Purple 43, Acid Red 73, Acid Red 88 , acid red 150, acid blue 25, acid blue 29, acid blue 45, acid blue 113, acid black 1, direct blue 1, direct blue 71, direct violet 51 and mixtures thereof. In another aspect, suitable small molecule dyes include small molecule dyes selected from the group consisting of Color Index (Society of Dyers and Colorists, Bradford, UK) acid violet 17, direct blue 71, direct violet 51, direct blue 1, acid red 88, acid red 150, acid blue 29, acid blue 113, or mixtures thereof.

Suitable polymer dyes include polymer dyes selected from the group consisting of polymers containing conjugated chromogens (dye-polymer conjugates) and polymers with chromogens copolymerized into the polymer backbone, and mixtures thereof.

In another aspect, suitable polymeric dyes include polymeric dyes selected from the group consisting of a substantive dye for fabrics sold under the name of ^{Liquitint ® (Milliken, Spartanburg, South} Carolina, USA), conjugates, dye-polymer formed from at least one reactive dye and a polymer selected from the group consisting of polymers comprising a fragment selected from the group consisting of a hydroxyl group, a primary amino group, a secondary amino group, a thiol group, and mixtures thereof. In still another aspect, suitable polymeric dyes include polymeric dyes selected from the group consisting of ^{Liquitint ® (Milliken, Spartanburg, South} Carolina, USA) Violet CT, carboxymethyl cellulose (CMC), conjugated with a reactive blue, reactive violet or reactive red dye such as CMC, conjugated to CI reactive blue 19, sold by Megazyme, Wicklow, Ireland under the name AZO-CM-CELLULOSE, product code S-ACMS, and mixtures thereof.

Suitable dye-clay conjugates include dye-clay conjugates selected from the group consisting of at least one cationic / basic dye and smectite clay and mixtures thereof. In another aspect, suitable dye-clay conjugates include dye-clay conjugates selected from the group consisting of one cationic / basic dye selected from the group consisting of basic yellow C.I. 1-108, the main orange C.I. 1-69, major reds C.I. 1-118, the main violet C.I. 1-51, the main blue C.I. 1-164, Major Greens C.I. 1-14, basic brown C.I. 1-23, main blacks C.I. 1-11, and clay selected from the group consisting of montmorillonite clay, hectorite clay, saponite clay, and mixtures thereof. In yet another aspect, suitable dye-clay conjugates include dye-clay conjugates selected from the group consisting of montmorillonite-base blue B7 C.I. conjugate. 42595, conjugate montmorillonite-basic blue B9 C.I. 52015, conjugate montmorillonite-base violet V3 C.I. 42555, conjugate montmorillonite-base green G1 C.I. 42040, conjugate montmorillonite-basic red R1 C.I. 45160, conjugate montmorillonite-C.I. primary black 2, conjugate hectorite-primary blue B7 C.I. 42595, conjugate hectorite-base blue B9 C.I. 52015, conjugate hectorite-base violet V3 C.I. 42555, conjugate hectorite-base green GI C.I. 42040, conjugate hectorite-base red R1 C.I. 45160, hectorite-C.I conjugate. primary black 2, conjugate saponite-primary blue B7 C.I. 42595, conjugate saponite-base blue B9 C.I. 52015, conjugate saponite-base violet V3 C.I. 42555, conjugate saponite-base green G1 C.I. 42040, conjugate saponite-base red R1 C.I. 45160, conjugate saponite - C.I. basic black 2, and mixtures thereof.

Suitable pigments include pigments selected from the group consisting of flavantrone, indantrone, chlorinated indantrone containing from 1 to 4 chlorine atoms, pyrantron, dichloropyrantron, monobromodichloropyrantron, dibromodichloropyrantron, tetrabromopyrantron, perylene tetrabronate, 4,9,10 diimide, perylene tetrabronate, 4,4,10 wherein the imide groups may be unsubstituted or substituted by C ₁ -C ₃ -alkyl or a phenyl or heterocyclic radical, and wherein the phenyl and heterocyclic radicals may additionally carry substituents which do not confer tensile Orim in water, amides antrapirimidinkarbonovoy acid violantrona, isoviolanthrone, dioxazine pigments, copper phthalocyanine which may contain up to 2 chlorine atoms per molecule, polihlorftalotsianina polibromhlorftalotsianina copper or copper containing up to 14 bromine atoms per molecule, and mixtures thereof. In another aspect, suitable pigments include pigments selected from the group consisting of ultramarine blue (CI pigment blue 29), ultramarine violet (CI pigment violet 15), and mixtures thereof.

The above fabric tinting agents can be used in combination (any mixture of fabric tinting agents can be used). Suitable fabric tinting agents may be purchased from Aldrich, Milwaukee, Wisconsin, USA; Ciba Specialty Chemicals, Basel, Switzerland; BASF, Ludwigshafen, Germany; Dayglo Color Corporation, Mumbai, India; Organic Dyestuffs Corp., East Providence, Rhode Island, USA; Dystar, Frankfurt, Germany; Lanxess, Leverkusen, Germany; Megazyme, Wicklow, Ireland; Clariant, Muttenz, Switzerland; Avecia, Manchester, UK and / or manufactured in accordance with the examples given in the present invention.

Supporting materials

Although this is not essential for the purposes of the present invention, a non-limiting list of excipients described hereinafter is suitable for use in the compositions of the present invention and may be desirable for inclusion in some embodiments of the invention, for example to provide or increase the cleaning efficiency, for processing the substrate that needs to be cleaned, or to modify the aesthetic characteristics of the detergent, as in the case of fragrances, dyes, dyes, etc. The exact nature of these additional components and their levels of content will depend on the physical form of the composition and the nature of the cleaning operation for which they should be used. Suitable auxiliary materials include, without limitation, surfactants, basic components, chelating agents, dye transfer inhibiting agents, dispersants, additional enzymes and enzyme stabilizers, catalytic materials, bleaching activators, hydrogen peroxide, hydrogen peroxide sources, pre-prepared peracids, polymer dispersants, agents for removing dirt particles and preventing their re-deposition, brighteners, antifoam additives, dyes, perfumes, electric structure astiffifiers, fabric softeners, carriers, hydrotropic substances, processing aids, solvents and / or pigments. In addition to the description below, suitable examples of such other excipients and levels of their use are described in US Pat. Nos. 5,576,282, 6,308,612 B1 and 6,326,348 B1, which are incorporated herein by reference.

As indicated, the auxiliary ingredients are not essential for the claimed compositions. Thus, certain embodiments of the claimed compositions do not contain one or more of the following auxiliary materials: surfactants, basic components, chelating agents, dye transfer inhibiting agents, dispersants, additional enzymes and enzyme stabilizers, catalytic materials, bleaching activators, hydrogen peroxide, sources of hydrogen peroxide, pre-prepared peracids, polymer dispersants, agents for removing dirt particles and preventing Nia their redeposition agents, brighteners, suds suppressors, dyes, perfumes, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids, solvents and / or pigments. However, in the presence of one or more excipients, such one or more excipients may be present, as described below.

Bleaching Agents — The detergent compositions of the present invention may include one or more bleaching agents. Suitable bleaching agents other than bleaching catalysts include photo bleaches, bleaching activators, hydrogen peroxide, sources of hydrogen peroxide, pre-prepared peracids and mixtures thereof. In general, if a whitening agent is used, the compositions of the present invention may comprise from about 0.1% to about 50%, or even from about 0.1% to about 25% of the whitening agent, based on the weight of the detergent composition. Examples of suitable whitening agents include:

(1) photobleaches, for example, sulfonated zinc phthalocyanine, sulfonated aluminum phthalocyanines, xanthene dyes, and mixtures thereof;

(2) pre-prepared peracids: suitable pre-prepared peracids include, without limitation, compounds selected from the group consisting of percarboxylic acids and salts, perugaric acids and salts, perimidic acids and salts, peroxymonosulfuric acids and salts, for example Oxone ^® , and their mixtures. Suitable percarboxylic acids include hydrophobic and hydrophilic peracids having the formula R- (C = O) OO-M, where R is an alkyl group, optionally branched, containing, when the peracid is hydrophobic, from 6 to 14 carbon atoms or from 8 to 12 carbon atoms and, in cases where the peracid is hydrophilic, less than 6 carbon atoms or even less than 4 carbon atoms; M is a counterion, for example sodium, potassium or hydrogen;

(3) sources of hydrogen peroxide, for example, inorganic perhydrate salts, including alkali metal salts, such as sodium perborate salts (usually mono- or tetrahydrate), percarbonate, persulfate, perphosphate, persilicate salts and mixtures thereof. In one aspect of the invention, inorganic perhydrate salts are selected from the group consisting of sodium salts of perborates, percarbonates, and mixtures thereof. In the case of use, inorganic perhydrate salts are typically present in an amount of from 0.05 to 40 wt.% Or from 1 to 30 wt.% Of the total amount of the composition and are typically included in such compositions as a crystalline solid that may be coated. Suitable coatings include inorganic salts, such as silicate, carbonate or borate salts of alkali metals or mixtures thereof, or organic materials, such as water-soluble or dispersible polymers, waxes, oils or fatty soaps;

(4) bleach activators of the formula R- (C = O) -L, where R is an optionally branched alkyl group containing, when the bleach activator is hydrophobic, from 6 to 14 carbon atoms or from 8 to 12 carbon atoms and, in cases where the bleach activator is hydrophilic, less than 6 carbon atoms or even less than 4 carbon atoms; L is a leaving group. Examples of suitable leaving groups are benzoic acid and its derivatives - especially benzenesulfonate. Suitable whitening activators include dodecanoyloxybenzenesulfonate, decanoyloxybenzenesulfonate, decanoyloxybenzoic acid or its salts, 3,5,5-trimethylhexanoyloxybenzenesulfonate, tetraacetylethylenediamine (TAED) and nonanoyloxybenzenesulfonate (NOBS). Suitable whitening activators are also disclosed in WO 98/17767. Although any suitable bleach activator may be used, in one aspect of the invention, the detergent composition of the invention may include NOBS, TAED, or mixtures thereof.

In the case of the presence of peracid and / or bleach activator are usually present in the composition in an amount of from about 0.1 to about 60 wt.%, From about 0.5 to about 40 wt.%; or even from about 0.6 to about 10% by weight of the composition. One or more hydrophobic peracids or its precursors may be used in combination with one or more hydrophilic peracids or its precursor.

The amount of the source of hydrogen peroxide and peracid or bleach activator can be selected so that the molar ratio of available oxygen (from the source of peroxide) to peracid is from 1: 1 to 35: 1 or even from 2: 1 to 10: 1.

Surfactants — The detergent compositions of the present invention may include a surfactant or a surfactant system, where the surfactant may be selected from nonionic surfactants, anionic surfactants, cationic surfactants substances, ampholytic surfactants, zwitterionic surfactants, semi-polar non-ionic surfactants and mixtures thereof. If present, the surfactant is typically present in an amount of from about 0.1% to about 60%, from about 1% to about 50%, or even from about 5% to about 40% by weight, of the composition of the invention.

Main components - detergent compositions of the present invention may include one or more main components of a detergent or system of the main component. In the case of using the main component, the subject composition will typically include at least about 1%, from about 5% to about 60%, or even from about 10% to about 40%, of the main component by weight of the subject composition.

The main components include, without limitation, polyphosphate salts of alkali metals, ammonium and alkanolammonium, alkali metal silicates, alkaline earth and alkali metal carbonates, aluminosilicate basic components and polycarboxylate compounds, ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or 1,3,5 methyl ether. trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxy succinic acid, various salts of alkali metals, ammonium and substituted ammonium polyacetic acids, such such as ethylenediaminetetraacetic acid and nitrilotriacetic acid; and polycarboxylates such as mellitic acid, succinic acid, citric acid, hydroxy succinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxy succinic acid, and their soluble salts.

Chelating Agents — The detergent compositions of the present invention may contain a chelating agent. Suitable chelating agents include copper, iron and / or manganese chelating agents and mixtures thereof. In the case of using a chelating agent, the subject composition may include from about 0.005% to about 15%, or even from about 3.0% to about 10%, a chelating agent based on the weight of the subject composition.

Dye Transfer Inhibiting Agents — Detergent compositions of the present invention may also include one or more dye transfer inhibiting agents. Suitable polymeric dye transfer inhibiting polymers include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyl oxazolidones and polyvinylimidazoles, or mixtures thereof. In the case of the presence in the composition of the invention, dye transfer inhibiting agents may be present in an amount of from about 0.0001% to about 10%, from about 0.01% to about 5%, or even from about 0.1% to about 3% by weight of the composition.

Brighteners — The detergent compositions of the present invention may also contain additional components that can tint laundry items, such as fluorescent brighteners. Suitable levels of fluorescent brightener include from lower levels from about 0.01, from about 0.05, from about 0.1, or even from about 0.2 wt.%, To upper levels of 0.5 or even 0.75 wt.% .

Dispersants — The compositions of the present invention may also contain dispersants. Suitable water-soluble organic materials include homo- or copolymer acids or their salts, in which the polycarboxylic acid comprises at least two carboxy radicals separated from each other by no more than two carbon atoms.

Enzymes — detergent compositions may include one or more enzymes that provide cleaning and / or tissue care effectiveness. Examples of suitable enzymes include, but are not limited to, hemicellulase, peroxidase, protease, cellulase, xylanase, lipase, phospholipase, esterase, cutinase, pectinase, mannanase, pectatliase, keratinase, reductase, oxidase, phenol oxidase, lipoxidase, ligninase, pentanase, malanases, β-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases and amylases, or mixtures thereof. A typical combination is an enzyme shake, which may contain, for example, a protease and lipase in combination with amylase. If present in the detergent composition, the aforementioned additional enzymes may be present in amounts from about 0.00001% to about 2%, from about 0.0001% to about 1%, or even from about 0.001% to about 0.5%, of the enzyme protein by weight of the composition.

Enzyme Stabilizers - Enzymes for use in detergents can be stabilized in many ways. The enzymes used in the present invention can be stabilized by the presence in the finished compositions of water-soluble sources of calcium and / or magnesium ions, which ensure the delivery of such ions to the enzymes. In the case of aqueous compositions containing a protease, a reversible protease inhibitor, such as a boron compound, can be added to further increase stability.

Catalytic metal complexes — The inventive detergent compositions may include catalytic metal complexes. One type of metal-containing bleaching catalyst is a catalyst system comprising a transition metal cation with a specific catalytic bleaching activity, such as copper, iron, titanium, ruthenium, tungsten, molybdenum or manganese cations, an auxiliary metal cation having little or no catalytic bleaching activity, such as zinc or aluminum cations, and a sequestrant having certain stability constants with catalytic and auxiliary metal cations, especially of ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and water- soluble salts thereof. Such catalysts are disclosed in US 4,430,243.

If necessary, the compositions of the present invention can be catalyzed using a manganese compound. Such compounds and their use levels are well known in the art and include, for example, manganese-based catalysts disclosed in US 5,576,282.

Cobalt whitening catalysts suitable for use in this invention are known and described, for example, in US 5597936; US 5595967. Such cobalt catalysts are readily prepared by known methods, such as those described, for example, in US 5597936 and US 5595967.

The compositions of the present invention may also suitably include a transition metal complex with ligands such as bispidones (WO 05/042532 A1) and / or hard macro-polycyclic ligands - abbreviated "MRLs". In practice and without limitation, the compositions and methods of the present invention may be adjusted to provide on the order of at least one part per hundred million of the active MRL particles in the aqueous washing medium, and will typically provide from about 0.005 ^-1 million to about 25 million ^-1 from about 0.05 million to about 10 ^{-1 -1} million or from about 0.1 million ^-1 to about 5 million ^-1 MRL in the wash liquor.

Suitable transition metals in the transition metal bleaching catalyst of the present invention include, for example, manganese, iron and chromium. Suitable MRLs include 5,12-diethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane.

Suitable transition metal MRLs are readily prepared by known methods, such as those described, for example, in WO 00/32601 and US 6225464.

Solvents — Suitable solvents include water and other solvents such as lipophilic liquid media. Examples of suitable lipophilic liquids include siloxanes, other silicones, hydrocarbons, glycol ethers, glycerol derivatives such as glycerol ethers, perfluorinated amines, perfluorinated and hydrofluoroether solvents, low volatile non-fluorinated organic solvents, diol solvents, and other environmentally friendly solvents and mixtures thereof.

Methods for preparing compositions

The compositions of the present invention can be formulated in any suitable form and made by any method selected by the originator, non-limiting examples of which are described in the examples of the application and in US 4990280; US20030087791 A1; US20030087790 A1; US20050003983 A1; US 20040048764 A1; US 4762636; US 6291412; US20050227891 A1; EP 1070115 A2; US 5879584; US 5691297; US 5,574,005; US 5,569,645; US 5565422; US 5516448; US 5,489,392; US 5,486,303, all of which are incorporated herein by reference.

Mode of application

The present invention includes a method for cleaning and / or treating a site, including a surface or fabric. Such a method includes the steps of contacting an embodiment of the inventive detergent composition, undiluted or diluted in a detergent solution, with at least a portion of a surface or fabric, and then optionally rinsing such a surface or fabric. The surface or fabric may be subjected to a washing step before the aforementioned rinsing step. For the purposes of the present invention, washing includes, without limitation, washing and mechanical stirring. As will be understood by those skilled in the art, the detergent compositions of the present invention are ideally suited for use in washing. Accordingly, the present invention includes a method for washing fabrics. The method includes the steps of contacting the fabric to be washed with said detergent for washing, comprising at least one embodiment of the inventive detergent composition, detergent, or a mixture thereof. The fabric may include virtually any fabric suitable for washing under normal conditions of use. The solution preferably has a pH of from about 8 to about 10.5. The compositions may be used in concentrations of from about 500 million to about 15000 ^{-1 -1} million in the solution. The water temperature typically ranges from about 5 ° C to about 90 ° C. The ratio of water: fabric typically ranges from about 1: 1 to about 30: 1.

TEST METHOD 1

The following is a protocol for determining whether a dye or pigment material is a fabric tinting agent for the purposes of the invention:

1) Two tergotometric vessels are filled with 800 ml of water from the city water supply Newcastle upon Tyne, UK (total hardness approx. 12 grains per American gallon - supplied by Northumbrian Water, Pity Me, Durham, Co. Durham, UK).

2) Install the vessels in the thermometer at a given water temperature of 30 ° C and stirring 40 rpm for the duration of the experiment.

3) Add 4.8 g of IEC-B detergent to each vessel (IEC 60456 Reference Basic Detergent for Type B washing machines) - supplied by wfk, Briiggen-Bracht, Germany.

4) After two minutes, 2.0 mg of active dye is added to the first vessel.

5) After one minute, 50 g of unpressed cotton fabric (supplied by Warwick Equest, Consett, County Durham, UK) was added to each vessel, cut into 5 cm × 5 cm samples.

6) After 10 minutes, the liquid is poured from the vessels and again filled with cold water from the Newcastle upon Tyne city water supply (16 ° C).

7) After 2 minutes rinsing, remove the tissue.

8) Repeat steps 3-7 three more times using the same treatment.

9) Gather fabric and dry on a rope in the room for 12 hours.

10) Analyze samples using a Hunter Miniscan spectrometer equipped with a D65 light source and UVA cut-off filter to obtain Hunter (red-green axis) and Hunter b (yellow-green axis) values.

11) Averaging the values of Hunter a and Hunter b for each set of tissues. If the fabrics treated with the test dye show an average shade difference of more than 0.2 units along the a axis or the b axis, then it is considered a fabric tinting agent for the purposes of the invention.

EXAMPLES

Unless otherwise indicated, materials may be obtained from Aldrich, P.O. Box 2060, Milwaukee, WI 53201, USA.

Examples 1-6

Granular detergent compositions for washing intended for hand washing or for top-loading washing machines.

Table 1 1 (wt.%) 2 (wt.%) 3 (wt.%) 4 (wt.%) 5 (wt.%) 6 (wt.%) Linear alkylbenzenesulfonate twenty 22 twenty fifteen twenty twenty C _12-14 dimethylhydroxyethylammonium chloride 0.7 one one 0.6 0,0 0.7 AE3S 0.9 0,0 0.9 0,0 0,0 0.9 AE7 0,0 0.5 0,0 one 3 one Sodium Tripolyphosphate 23 thirty 23 17 12 23 Zeolite A 0,0 0,0 0,0 0,0 10 0,0 1.6R Silicate (SiO ₂ -Na ₂ O in a ratio of 1.6: 1) 7 7 7 7 7 7 Sodium carbonate fifteen fourteen fifteen eighteen fifteen fifteen Polyacrylate MW 4500 one 0,0 one one 1,5 one Carboxymethyl cellulose one one one one one one Savinase ^® 32.89 mg / g 0.1 0,07 0.1 0.1 0.1 0.1 Natalase ^® 8.65 mg / g 0.1 0.1 0.1 0,0 0.1 0.1 Lipex ^® 18 mg / g 0,03 0,07 0.3 0.1 0,07 0.4 Fluorescent brightener 1 0.06 0,0 0.06 0.18 0.06 0.06 Fluorescent brightener 2 0.1 0.06 0.1 0,0 0.1 0.1 Diethylene triamine pentaacetic acid 0.6 0.3 0.6 0.25 0.6 0.6 MgSO ₄ one one one 0.5 one one Sodium percarbonate 0,0 5.2 0.1 0,0 0,0 0,0 Sodium Perborate Monohydrate 4.4 0,0 3.85 2.09 0.78 3.63 NOBS 1.9 0,0 1,66 - 0.33 0.75 TAED 0.58 1,2 0.51 - 0.015 0.28 Sulfated Zinc Phthalocyanine 0.0030 0.0012 0.0030 0.0021 - S-ACMC 0.1 0.06 - - - Straight purple 9 - - 0,0003 0,0005 0,0003 - Acid Blue 29 - - - - - 0,0003 Sulphate / Moisture Up to 100% Up to 100% Up to 100% Up to 100% Up to 100% Up to 100%

Examples 7-10

table 2 Granular detergent detergent compositions for front-loading automatic washing machines. 7 (wt.%) 8 (wt.%) 9 (wt.%) 10 (wt.%) Linear alkylbenzenesulfonate 8 7.1 7 6.5 AE3S 0 4.8 0 5.2 Alkyl Sulfate one 0 one 0 AE7 2.2 0 3.2 0 C _10-12 dimethylhydroxyethylammonium chloride 0.75 0.94 0.98 0.98 Crystalline Layered Silicate (δ-Na ₂ Si ₂ O ₅ ) 4.1 0 4.8 0 Zeolite A twenty 0 17 0 Lemon acid 3 5 3 four Sodium carbonate fifteen twenty fourteen twenty Silicate 2R (SiO ₂ : Na ₂ O in a 2: 1 ratio) 0.08 0 0.11 0 Dirt repellent agent 0.75 0.72 0.71 0.72 Acrylic Acid / Maleic Acid Copolymer 1,1 3,7 1,0 3,7 Carboxymethyl cellulose 0.15 1.4 0.2 1.4 Protease (56.00 mg of active substance / g) 0.37 0.4 0.4 0.4 Termamyl ^® (21.55 mg of active substance / g) 0.3 0.3 0.3 0.3 Lipex ^® (18.00 mg active substance / g) 0.05 0.15 0.1 0.5 Natalase ^® (8.65 mg of active substance / g) 0.1 0.14 0.14 0.3 TAED 3.6 4.0 3.6 4.0 Percarbonate 13 13,2 13 13,2 Na salt of ethylenediamine-N, N ¹ -disuccinic acid, (S, S) -isomer (EDDS) 0.2 0.2 0.2 0.2 Hydroxyethane diphosphonate (HEDP) 0.2 0.2 0.2 0.2 MgSO ₄ 0.42 0.42 0.42 0.42 Flavoring 0.5 0.6 0.5 0.6 Antifoam agglomerate 0.05 0.1 0.05 0.1 Soap 0.45 0.45 0.45 0.45 Sodium sulfate 22 33 24 thirty Sulfated Zinc Phthalocyanine (Active) 0,0007 0.0012 0,0007 - S-ACMC 0.01 0.01 - 0.01 Straight Purple 9 (Active) - - 0.0001 0.0001 Water and miscellaneous Up to 100% Up to 100% Up to 100% Up to 100%

Any of the foregoing compositions used for washing fabrics at a concentration of 10000 million ^-1 in water, 20-90 ° C and at vodatkan ratio of 25: 1. A typical pH is about 10.

Examples 11-16

Liquid detergent compositions for washing heavily soiled fabrics

Table 3 11 (wt.%) 12 (wt.%) 13 (wt.%) 14 (wt.%) 15 (wt.%) 16 (wt.%) AES C _12-15 -alkylethoxy (1.8) -sulfate eleven 10 four 6.32 6.0 8.2 Linear alkylbenzenesulfonate four 0 8 3.3 4.0 3.0 HSAS 0 5.1 3 0 2 0 Sodium formate 1,6 0.09 1,2 0.04 1,6 1,2 Sodium hydroxide 2,3 3.8 1.7 1.9 2,3 1.7 Monoethanolamine 1.4 1,490 1,0 0.7 1.35 1,0 Diethylene glycol 5.5 0,0 4.1 0,0 5,500 4.1 Nonionic 0.4 0.6 0.3 0.3 2 0.3 Chelator 0.15 0.15 0.11 0,07 0.15 0.11 Lemon acid 2.5 3.96 1.88 1.98 2.5 1.88 C _12-14 dimethylamine oxide 0.3 0.73 0.23 0.37 0.3 0.225 C _12-18 fatty acid 0.8 1.9 0.6 0.99 0.8 0.6 Borax 1.43 1,5 1,1 0.75 1.43 1,07 Ethanol 1,54 1.77 1.15 0.89 1,54 1.15 Ethoxylated (EO ₁₅ ) tetraethylenepentaimine ¹ 0.3 0.33 0.23 0.17 0,0 0,0 Ethoxylated Hexamethylenediamine ² 0.8 0.81 0.6 0.4 0,0 0,0 1,2-propanediol 0,0 6.6 0,0 3.3 0,0 0,0 Protease ^* 36,4 36,4 27.3 18.2 36,4 27.3 Mannaway ^{® *} 1,1 1,1 0.8 0.6 1,1 0.8 Natalase ^{® *} 7.3 7.3 5.5 3,7 7.3 5.5 Lipex ^{® *} 10 3.2 0.5 3.2 2,4 3.2 Liquitint ^® Purple CT (Active) 0.006 0.002 - - - 0.002 S-ACMC - - 0.01 0.05 0.01 0.02 Water, flavor, colorants and other components Rest Rest Rest Rest Rest Rest

Raw materials and notes on examples of compositions 1-16

Linear alkylbenzenesulfonate with an average C ₁₁ -C ₁₂ aliphatic carbon chain length was supplied by Stepan, Northfield, Illinois, USA.

C _12-14 dimethylhydroxyethylammonium chloride was supplied by Clariant GmbH, Sulzbach, Germany.

AE3S is C _12-15 -alkylethoxy (3) sulfate — supplied by Stepan, Northfield, Illinois, USA.

AE7 is a C _12-15 alcohol ethoxylate, with an average degree of ethoxylation of 7, supplied by Huntsman, Salt Lake City, Utah, USA.

Sodium tripolyphosphate - supplied by Rhodia, Paris, France.

Zeolite A - supplied by Industrial Zeolite (UK) Ltd /, Grays, Essex, UK.

1.6R silicate - supplied by Koma, Nestemica, Czech Republic.

Sodium Carbonate - available from Solvay, Houston, Texas, USA.

Polyacrylate MW 4500 - supplied by BASF, Ludwigshafen, Germany.

Carboxy Methyl Cellulose Finnfix ^® BDA - supplied by CPKelco, Arnhem, Netherlands.

Savinase ^® , Natalase ^® , Lipex ^® , Termamyl ^® , Mannaway ^® - supplied by Novozymes, Bagsvaerd, Denmark.

Fluorescent brightener 1 is Tinopal ^® AMS,

fluorescent brightener 2 is Tinopal ^® CBS-X.

Sulfonated zinc phthalocyanine and Direct Violet 9 which predstavlyaetsoboy Pergasol ^® Violet BN-Z - all supplied by Ciba Specialty Chemicals, Basel, Switzerland.

Diethylene triamine pentaacetic acid - available from Dow Chemical, Midland, Michigan, USA.

Sodium percarbonate - supplied by Solvay, Houston, Texas, USA.

Sodium perborate - supplied by Degussa, Hanau, Germany.

NOBS — sodium nonanoyloxybenzenesulfonate — available from Eastman, Batesville, Arkansas, USA.

TAED - tetraacetylethylenediamine, supplied under the tradename Peractive ^® by Clariant GmbH, Sulzbach, Germany.

S-ACMC is a carboxymethyl cellulose conjugated to C.I. Jet Blue 19, sold by Megazyme, Wicklow, Ireland under the trademark AZO-CM-CELLULOSE, product code S-ACMC.

Repel-o-tex ^® PF dirt repellent agent - available from Rhodia, Paris, France.

An acrylic acid / maleic acid copolymer with a molecular weight of 70,000 and an acrylagmaleate ratio of 70:30 was supplied by BASF, Ludwigshafen, Germany.

Protease FN3 - supplied by Genencor International, PaloAlto, California, USA.

Ethylene diamine-N, N'-disuccinic acid Na-salt, (S, S) -isomer (EDDS) was supplied by Octel, Ellesmere Port, UK.

Hydroxyethane diphosphonate (HEDP) - supplied by Dow Chemical, Midland, Michigan, USA.

Antifoam agglomerate - supplied by Dow Corning, Midland, Michigan, USA.

HSAS is a medium chain branched alkyl sulfate, as disclosed in US 6020303 and US 6060443.

From _12-14, dimethylamine oxide was supplied by Procter & Gamble Chemicals, Cincinnati, Ohio, USA.

Non-ionic - preferably represents C ₁₂ -C ₁₃ ethoxylate, preferably with an average degree of ethoxylation of 9.

Protease - supplied by Genencor International, Palo Alto, California, USA.

Liquitint ^® Violet CT - supplied by Milliken, Spartanburg, South Carolina, USA).

* Values are given in mg of enzyme / 100 g.

¹ as described in US 4,597,798.

² available under the tradename LUTENSIT ^® company BASF and such as those described in WO 01/05874.

Although specific embodiments of the present invention have been illustrated and described, it will be apparent to those skilled in the art that various other changes and modifications can be made without violating the spirit and scope of the invention. Therefore, it is intended that the appended claims cover all such changes and modifications that fall within the scope of the present invention.

Claims (17)

1. A composition containing a lipase and a tinting agent for tissue, wherein the lipase is a lipase having at least 90% homology with SEQ ID NO: 2 and containing a substitution of an electrically neutral or negatively charged amino acid by R or K in any of positions 3, 224, 229, 231 and 233, and said tinting agent for fabric is selected from the group consisting of dyes, dye-clay conjugates, and mixtures thereof. 2. The composition according to claim 1, characterized in that said lipase is present in an amount of from 0.0005% to 0.1% and said tinting agent for tissue is present in an amount of from 0.00003% to 0.1%. 3. The composition according to claim 1, characterized in that said lipase is selected from the group consisting of lipases having classification E.C.3.1.1, and mixtures thereof, these dyes are selected from the group consisting of dyes with small molecules, polymeric dyes and mixtures thereof, and said dye-clay conjugates are selected from the group consisting of dye-clay conjugates comprising at least one cationic / basic dye and smectite clay, and mixtures thereof. 4. The composition according to claim 2, characterized in that said lipase is selected from the group consisting of lipases having classification E.C.3.1.1, and mixtures thereof, these dyes are selected from the group consisting of dyes with small molecules, polymeric dyes and mixtures thereof, and said dye-clay conjugates are selected from the group consisting of dye-clay conjugates comprising at least one cationic / basic dye and smectite clay, and mixtures thereof. 5. The composition according to claim 3, characterized in that said lipase is selected from the group consisting of lipases having EC3.1.1.3 classification, and mixtures thereof, said dyes with small molecules are selected from the group consisting of direct violet 9, direct violet 35, direct violet 48, direct violet 51, direct violet 66, direct blue 1, direct blue 71, direct blue 80, direct blue 279, acid red 17, acid red 73, acid red 88, acid red 150, acid purple 15, acid violet 17, sour 24 violet 24, acid violet 43, acid violet 49, acid blue 15, acid blue 17, acid blue 25, acid blue 29, acid blue 40, acid blue 45, acid blue 75, acid blue 80, acid blue 83, acid blue 90 and acid blue 113, acid black 1, basic violet 1, basic violet 3, basic violet 4, basic violet 10, basic violet 35, basic blue 3, basic blue 16, basic blue 22, basic blue 47, basic blue 66,main blue 75, basic blue 159 and mixtures thereof, these polymer dyes are selected from the group consisting of polymers containing conjugated chromogens, polymers with chromogens copolymerized into the polymer backbone, and mixtures thereof, these dye-clay conjugates are selected from dye- clay comprising a dye selected from the group consisting of basic yellow CI 1-108, the main orange C.I. 1-69, major reds C.I. 1-118, the main violet C.I. 1-51, the main blue C.I. 1-164, Major Greens C.I. 1-14, basic brown C.I, 1-23, basic black C.I. 1-11, and clay selected from the group consisting of montmorillonite clay, hectorite clay, saponite clay, and mixtures thereof. 6. The composition according to claim 5, characterized in that the dye with a small molecule is selected from the group consisting of acid violet 17, acid violet 43, acid red 73, acid red 88, acid red 150, acid blue 25, acid blue 29, acid blue 45, acid blue 113, acid black 1, direct blue 1, direct blue 71, direct violet 51, and mixtures thereof. 7. The composition according to claim 6, characterized in that the dye with a small molecule is selected from the group consisting of acid violet 17, direct blue 71, direct violet 51, direct blue 1, acid red 88, acid red 150, acid blue 29, acid blue 113 or mixtures thereof. 8. The composition according to claim 5, characterized in that the dye with a small molecule is selected from the group consisting of acid violet 17, acid violet 43, acid red 73, acid red 88, acid red 150, acid blue 25, acid blue 29, acid blue 45, acid blue 113, acid black 1, direct blue 1, direct blue 71, direct violet 51, and mixtures thereof. 9. The composition of claim 8, wherein the small molecule dye is selected from the group consisting of acid violet 17, direct blue 71, direct violet 51, direct blue 1, acid red 88, acid red 150, acid blue 29, acid blue 113 or mixtures thereof. 10. The composition according to claim 5, characterized in that the lipase is a variant of SEQ ID NO: 2, and this option contains the substitution T231R and N233R. 11. The composition of claim 10, wherein the small molecule dye is selected from the group consisting of acid violet 17, acid violet 43, acid red 73, acid red 88, acid red 150, acid blue 25, acid blue 29, acid blue 45, acid blue 113, acid black 1, direct blue 1, direct blue 71, direct violet 51, and mixtures thereof. 12. The composition of claim 8, wherein the small molecule dye is selected from the group consisting of acid violet 17, direct blue 71, direct violet 51, direct blue 1, acid red 88, acid red 150, acid blue 29, acid blue 113 or mixtures thereof. 13. The composition according to claim 1, characterized in that said composition comprises an auxiliary material. 14. The composition according to item 13, wherein the auxiliary material is selected from the group consisting of sulfonated zinc phthalocyanine, sulfonated aluminum phthalocyanines, xanthene dyes and mixtures thereof. 15. The composition according to claim 1, characterized in that the composition is a composition for cleaning and / or processing. 16. The composition according to claim 1, characterized in that it contains a lipase and a tinting agent for tissue, and the specified tinting agent for tissue selected from the group of tinting agents for tissue that meet the requirements of Test Method 1 in the Test Methods section of the present description, provided that said fabric tint is not ultramarine blue. 17. The composition according to claim 1, characterized in that it is arranged to come into contact with the specified surface or fabric, and then optionally can be removed by washing and / or rinsing from the specified surface and / or fabric.