EP0736083B1 - Washing and cleaning powder - Google Patents

Abstract

Described is a washing and cleaning powder containing a surfactant, cellulase and a builder and including 0.15 to 10 % by wt. of a soil-release polymer containing ethylene terephthalate groups of the formula (I) and poly(ethylene oxide) terephthalate groups of the formula (II) in which n is a whole number from 17 to 110, the molar ratio of ethylene terephthalate to poly(ethylene oxide) terephthalate in the polymer being from about 50:50 to about 90:10, the polymer further containing cellulase at a concentration of 0.05 to 1,5 IU/g plus 1 to 40 % by wt. of terpolymers composed of the monomer units of two ethylenically unsaturated carboxylic acids and/or their salts while the third monomer unit is vinyl alcohol and/or a vinyl alcohol derivative or a carbohydrate. Such powders have improved cleaning power.

Description

The invention relates to detergents and cleaning agents, the surfactant, builder, Cellulase and a dirt-repellent polymer and a terpolymer cobuilder contain.

An important objective in the field of detergents and cleaning agents is to develop substances and mixtures that are capable of soiled surfaces, for example of fabrics, to remove the dirt. Such detergents and cleaning agents usually contain as main components Builders and surfactants from the group of anionic and nonionic Surfactants. Cobuilders can be used as further components in detergents such as polycarboxylates, peroxy bleaches, bleach activators, foam inhibitors, optical brighteners and enzymes or enzyme combinations to improve the cleaning effect.

The most commonly used enzymes include protease, amylase, cellulase and lipase. These enzymes each have different ones Properties and can come from different sources. The Use of cellulase is for example in the European patent application EP 468464 as well as in international patent applications WO 91/19807, WO 91/19794 or WO 90/02790.

Even if the washing and cleaning agents known from the prior art have a good cleaning effect occurs during the washing process however, the effect on that the detached contaminants to Example pigment or fat particles, again on the tissues respectively settle the surfaces. This effect leads to graying of white fabrics and a decrease in the luminosity of the color in colored Tissues. This effect is also known as the so-called "gray haze". To prevent the detached contaminants from coming back settling on the fabric and thus causing graying, connections became developed the dirt-repellent properties and thus also a graying-inhibiting effect, so-called soil repellent / soil release properties, have. Graying inhibitors in the true sense have the task of removing the dirt detached from the fiber to keep the fleet suspended and reloading the dirt and thus preventing the graying of the fibers while the above Soil repellent active ingredients presumably function in the sense of protective repellant Unfold fiber equipment. For example in the German patent specification DE 28 57 292 describes detergents that are dirt-repellent Compound is a polymer of ethylene terephthalate and polyethylene oxide terephthalate and anionic surfactants in the form of alcohol sulfates, with Ethylene oxide condensed alcohol sulfates and mixtures thereof.

European patent application EP 0 365 103 describes a surfactant composition described, which 4 to 30 wt .-% of a synthetic nonionic Surfactants, 25 to 80% by weight builder for this nonionic surfactant, 0.1 to 2% by weight of protease, 0 to 2% by weight of amylase, 0.2 to 1% by weight of cellulase, 1 to 15% by weight of water and poly (alkylene glycol terephthalate) as a further constituent contains.

The detergents known from the prior art are not always satisfactory dirt-repellent properties to a graying to prevent the washed fabric as permanently as possible. This will their cleaning effect is impaired.

The object of the present invention is to provide washing and cleaning agents To provide the excellent cleaning effect and at the same time have dirt-removing properties to the graying to prevent the tissue.

Surprisingly, it has now been found that the cleaning performance and the graying-inhibiting effect of powder detergents can be further increased by using the surfactant and builder system such agents by special combinations of dirt-removing polymer, Cobuilder and enzyme optimized.

und Polyethylenoxidterephthalatgruppen der Formel

worin n eine ganze Zahl von 17 bis 110 bedeutet, enthält, wobei das Molverhältnis von Ethylenterephthalat zu Polyethylenoxidterephthalat im Polymeren von 50:50 bis 90:10 beträgt, b) Cellulase in einer Aktivität von 0,05 IU/g bis 1,5 IU/g, sowie c) 1 Gew.-% bis 40 Gew.-% Terpolymere aus den Monomereinheiten von zwei ethylenisch ungesättigten Carbonsäuren und/oder deren Salzen sowie als dritte Monomereinheit Vinylalkohol und/oder ein Vinylalkohol-Derivat oder ein Kohlenhydrat.The present invention relates to a powdered detergent and cleaning agent containing surfactant, cellulase and builder, comprising a) 0.15 to 10% by weight of a dirt-repellent polymer which contains ethylene terephthalate groups of the formula

and polyethylene oxide terephthalate groups of the formula

where n is an integer from 17 to 110, the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate in the polymer being from 50:50 to 90:10, b) cellulase in an activity of 0.05 IU / g to 1.5 IU / g, and c) 1 wt .-% to 40 wt .-% terpolymers from the monomer units of two ethylenically unsaturated carboxylic acids and / or their salts and as a third monomer unit vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate.

Another object of the invention is an otherwise identical composition, component c) a terpolymer of the monomer units of a monoethylenically unsaturated C _3-8 carboxylic acid, a 2-alkyl-allylsulfonic acid or a 2-aryl-allylsulfonic acid and a carbohydrate and / or the salts of a monoethylenically unsaturated C _3-8 carboxylic acid, a 2-alkyl-allylsulfonic acid or a 2-aryl-allylsulfonic acid and a carbohydrate.

The dirt-repellent polymers contained according to the invention, the groups with the above Formulas I and II are contained in the washing and cleaning agents according to the invention in an amount of 0.15% by weight to 10% by weight, preferably 0.25% by weight to 5% by weight, particularly preferably contain 0.3% by weight to 3% by weight. It is in these connections Molecular weight of the linking polyethylene oxide units preferably in the range of 750 to 5000. The polymers can have an average molecular weight of 5000 to Own 200,000. In the polymer can be ethylene terephthalate and polyethylene oxide terephthalate arbitrarily distributed.

Preferred polymers are those with molar ratios of ethylene terephthalate / polyethylene oxide terephthalate from 65:35 to 90:10, preferably from 65:35 to 80:20, the linking polyethylene oxide units have a molecular weight of 750-5000, preferably 1000 to 3000 and the polymer has a molecular weight of 10,000 to 50,000. examples for Commercial polymers of this type are e.g. B. "Mileas®-T" from ICI United States, Inc., Repel-O-Tex® SRP 3 from Rhône-Poulenc and Zelcon® 8037 from DuPont.

The dirt-repellent polymers used in agents according to the invention can by known polymerization processes are prepared, the starting materials in such amounts are used to achieve the above ratios of ethylene terephthalate to get polyethylene oxide terephthalate. For example, those in US Pat 3479212 described methods for producing suitable polymers can be used.

As the main builder component, the detergents and cleaning agents of the invention contain in the Usually fine crystalline, synthetic and bound water containing zeolite and / or Alkali silicates, although agents according to the invention are not limited to these builder substances are. The zeolite used is preferably A and / or P type zeolite in Detergent quality. Their mixtures with zeolite NaX are also suitable, the proportion of the Zeolite NaX in such mixtures is advantageously below 30%. You point practically no particles larger than 30 µm and preferably consist of at least 80% from particles smaller than 10 µm. Suitable zeolites have a medium one Particle size of less than 10 µm (measurement method: Frauenhofer diffraction; average of the Volume distribution), preferably between 1.5 and 4.5 μm, in particular between 2.0 and 4.0 µm. Your calcium binding capacity, which according to the information in German patent DE 24 12 837 can be determined, is in the range of 100 to 200 mg CaO / g. The salary of the The average of finely divided, in particular crystalline, hydrated zeolite is preferably 30 up to 65 wt .-% and in particular 32 to 45 wt .-%, based on anhydrous active substance. The zeolite generally has a water content of 17 to 25% by weight, preferably 18 to 22% by weight, in particular 20 to 22% by weight.

The optionally contained alkali silicates are added as a solid and not in the form of a solution. They can be amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na ₂ O: SiO ₂ molar ratio of 1: 2 to 1: 2.8. Such amorphous alkali silicates are commercially available, for example, under the name Portil ^(R) . Crystalline sheet silicates of the formula (I) NaMSi _x O _{2x + 1} .yH ₂ O, in which M represents sodium, x is a number of 1.9, are preferably used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates to 4 and y is a number from 0 to 20 and are preferred values for x 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application 164 514. Preferred crystalline sheet silicates of the formula (I) are those in which M represents 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 can be obtained, for example, by the process described in international patent application WO91 / 08171. The content of alkali silicates in the compositions is preferably 1 to 15% by weight and in particular 2 to 8% by weight, based on the anhydrous active substance. The weight ratio of zeolite: amorphous silicate, based in each case on anhydrous active substance, is preferably 4: 1 to 10: 1. The crystalline layered silicates are used in zeolite-containing agents preferably in amounts of 1% by weight to 15% by weight and in particular 2 to 7% by weight, the weight ratio of zeolite to crystalline layered silicate, in each case based on anhydrous active substance, at least 5: 1 is. In compositions which contain both amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali silicate: crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.

According to the invention, the detergents and cleaning agents contain as cobuilder terpolymers in an amount of 1 to 40% by weight, preferably 2 to 25% by weight and particularly preferably 2 to 15% by weight. These terpolymers contain two carboxylic acids and / or their salts as monomer units and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as third monomer unit. The first acidic monomer unit or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ carboxylic acid and preferably from a C ₃ -C ₄ monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer unit or its salt can be a derivative of a C ₄ -C ₈ dicarboxylic acid; preferably a C ₄ -C ₈ dicarboxylic acid, maleic acid being particularly preferred. In this case, the third monomer unit is formed from vinyl alcohol and / or preferably an esterified vinyl alcohol. Vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example of C ₁ -C ₄ carboxylic acids, with vinyl alcohol are particularly preferred. Preferred terpolymers contain 60 to 95% by weight, in particular 70 to 90% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or maleate and 5 to 40% by weight. %, preferably 10 to 30% by weight of vinyl alcohol and / or vinyl acetate. Terpolymers in which the weight ratio (meth) acrylic acid or (meth) acrylate to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 are very particularly preferred and 2.5: 1. Both the amounts and the weight ratios are based on the acids.

The second acidic monomer unit or its salt can also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C ₁ -C ₄ -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives derives, is substituted. Preferred terpolymers contain 40 to 60% by weight, in particular 45 to 55% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10 to 30% by weight, preferably 15 to 25 % By weight of methallylsulfonic acid or methallylsulfonate and, as the third monomer unit, 15 to 40% by weight, preferably 20 to 40% by weight, of a carbohydrate. This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred, sucrose being particularly preferred. By using the third monomer unit, predetermined breaking points are built into the polymer, which are responsible for the degradability of the polymer. The terpolymers used can be produced by any of the known and customary processes.

Terpolymers which are either completely used are also preferably used or at least partially, in particular more than 50% are neutralized to the carboxyl groups present. Particularly preferred is a completely neutralized terpolymer the salts of the monomeric acids, especially the sodium or potassium salts the monomeric acids, and vinyl alcohol or a carbohydrate. The terpolymers generally have a relative molecular weight between 1000 and 200000, preferably between 200 and 50000 and in particular between 3000 and 10000. They usually become more watery in the form Solutions, preferably in the form of 30 to 50% by weight aqueous solutions. Particularly preferred terpolymers are produced by processes the in the German patent DE 42 21 381 and the international Patent application WO 94/15978 are described.

Customary polymeric carboxylates can also be used as additional builders or polymeric carboxylic acids consisting of one or two monomer units are composed. These polymeric carboxylates or Carboxylic acids in agents according to the invention can optionally in a Amounts of up to 15% by weight are present, but are preferably absent entirely. Coming polymeric carboxylates or polymeric carboxylic acids with a relative Molecular mass of at least 350 in the form of their water-soluble salts, in particular in the form of the sodium and / or potassium salts, such as polyacrylates, Polyhydroxyacrylates, polymethacrylates, polymaleates and in particular Copolymers of acrylic acid with maleic acid or maleic anhydride, preferably those from 50 to 70% acrylic acid and 50 to 10% Maleic acid. The relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on free acid. A usually particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000.

A washing and cleaning agent according to the invention contains an enzyme from the class of cellulases. The cellulase used according to the invention belongs to the enzymes obtainable from microorganisms, in particular bacteria or fungi, which have a pH optimum, preferably in the almost neutral to weakly alkaline pH range from 6 to 9.5. Such cellulases are known, for example, from German Offenlegungsschriften DT 22 47 832, DE 31 17 250, DE 32 07 825, DE 32 07 847 and DE 33 22 950, British patent application GB 2 232 983, European patent applications EP 0 265 832, EP 0 269 077, EP 0 270 974, EP 0 271 004, EP 0 339 550, EP 0 458 162 and EP 0 468 464 or the international patent applications WO 89/09259, WO 91/10732, WO 91/17243, WO 92 / 06209, WO 93/11249, WO 93/12224, WO 93/17101, WO 93/20193, WO 94/07998 and WO 94/14953. They are used in the agent according to the invention preferably in amounts such that the finished agent has a cellulolytic activity of 0.05 IU / g to 1.5 IU / g ("International Units" per gram, based on the enzymatic hydrolysis of Na-carboxymethylcellulose) pH 9.0 and 40 ° C, as described in Agric. Biol. Chem. 53, 1275 (1989) by S. Ito et al.), in particular 0.07 IU / g to 1.4 IU / g and particularly preferred 0.1 IU / g to 1.3 IU / g. Suitable commercial products include Celluzyme ^(R) from Novo Nordisk or KAC ^(R) from Kao.

The detergents according to the invention can comprise water-soluble complexing agents the group of phosphonates. There are salts of polyphosphonic acids like neutral reacting sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate and diethylene triamine pentamethylene phosphonate. The phosphonates can be used in amounts of up to 1.5% by weight.

Detergents and cleaning agents contain other common ingredients normally non-ionic surfactant compounds Surfactants, may also contain anionic and / or zwitterionic surfactants be. The surfactants are generally in the detergents according to the invention with a total content of 5 to 40% by weight, preferably 5 up to 30% by weight and in particular from 8 to 25% by weight.

The detergent according to the invention contains in particular as nonionic surfactants low ethoxylated and higher ethoxylated nonionic surfactants. The nonionic surfactants can be used in an amount of up to 25% by weight, preferably up to 15% by weight. The as non-ionic surfactants preferably used ethoxylated alcohols are derived from primary Alcohols with preferably 9 to 18 carbon atoms. The low ethoxylated Fatty alcohols have an average of 1 to 6 moles and that higher ethoxylated alcohols on average 7 to 20 moles of ethylene oxide. The degrees of ethoxylation given represent statistical averages, that are an integer or a fraction for a specific product can. The alcohol residue can be linear or methyl branched in the 2-position be, or contain linear and methyl branched radicals in the mixture, such as they are usually present in oxo alcohol residues. In particular, however Alcohol ethoxylates with linear residues from alcohols of native origin Preferably 12 to 18 carbon atoms, e.g. B. from coconut oil, tallow oil or Oleyl alcohol. The preferred low ethoxylated alcohols include for example fatty alcohols with 12 to 18 carbon atoms with an average 3 to 6 EO units. Among the preferred higher ethoxylated For example, alcohols include fatty alcohols with 16 to 18 carbon atoms with an average of 12 to 16 EO units, e.g. ethoxylated Palm alcohol. Preferred alcohol ethoxylates have a narrow homolog distribution on (narrow range ethoxylates, NRE). The invention Detergents preferably contain 1% to 10% by weight, in particular 1% to 5% by weight of low ethoxylated nonionic surfactants and 1% by weight up to 10 wt .-%, in particular 1 wt .-% to 5 wt .-% higher ethoxylated nonionic surfactants. The lower ethoxylated alcohols and the higher ethoxylated Alcohols are preferably in a weight ratio of 10: 1 to 1:10, preferably 5: 1 to 1: 5, in particular 2: 1 to 1: 1.

Further classes of nonionic surfactants that can be used alone or in combination with the above-mentioned nonionic surfactants are alkoxylated fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or preferably according to that in international patent application WO 90/13533 described processes are prepared, and alkyl glycosides of the general formula RO (G) _x , in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 C atoms and G for a Glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4. Alkyl glycosides can preferably be present in the detergents according to the invention in an amount of up to 5% by weight, in particular from 0.5% by weight to 3% by weight.

Anionic surfactants which can be used in the agents according to the invention are sulfates and, if appropriate, sulfonates and soaps composed of preferably natural fatty acids or fatty acid mixtures. In total, the anionic surfactants can be present in the agents according to the invention in an amount of up to 15 wt. Suitable sulfate-type surfactants are sulfuric acid monoesters from primary alcohols of natural and synthetic origin. The alk (en) yl sulfates are the sulfuric acid half esters of the C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C ₁₀ -C ₂₀ oxo alcohols, and those secondary alcohols of this chain length prefers. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. C ₁₆ -C ₁₈ alk (en) yl sulfates are particularly preferred from the point of view of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use C ₁₆ -C ₁₈ alk (en) yl sulfate in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and relatively low ones Washing temperatures of, for example, room temperature to 40 ° C. show a low tendency to crystallize. In a preferred embodiment of the invention, the compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C ₁₂ -C ₁₄ fatty alkyl sulfates or C ₁₂ -C ₁₆ fatty alkyl sulfates with C ₁₆ -C ₁₈ fatty alkyl sulfates. In a further preferred embodiment of the invention, however, not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C ₁₆ -C ₂₂ are used. Mixtures of saturated sulfated fatty alcohols predominantly consisting of C ₁₆ and unsaturated sulfated fatty alcohols predominantly consisting of C ₁₈ are particularly preferred, for example those derived from solid or liquid HD-Ocenol ^(R) fatty alcohol mixtures (commercial product of the applicant) . Weight ratios of alkyl sulfates to alkenyl sulfates from 10: 1 to 1: 2 and in particular from about 5: 1 to 1: 1 are preferred. The agents according to the invention can contain up to 12% by weight alk (en) yl sulfates, preferably 5% by weight to 8% by weight. The sulfuric acid monoesters of the straight-chain or branched C ₇ -C ₂₁ alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ alcohols with an average of 3.5 mol of ethylene oxide (EO) or C ₁₂ - C ₁₈ fatty alcohols with 2 to 4 EO are suitable. Because of their high foaming power, they are used in washing agents for machine use only in relatively small amounts, for example in amounts of 1 to 5% by weight. If surfactants of the sulfonate type are used, preference is given to C ₉ -C ₁₃ alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates, and also disulfonates of the kind obtained, for example, from C ₁₂ -C ₁₈ monoolefins having a terminal or internal double bond Sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products is considered. These surfactants can be up to 10% by weight on average, preferably up to 5% by weight. However, surfactants of the sulfonate type can also be dispensed with without significantly affecting the washing action.

Soaps are particularly suitable as further anionic surfactants, saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids, being suitable. In particular, those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C ₁₂ -C ₁₈ fatty acid soaps and 0 to 50% by weight of oleic acid soap. The detergents according to the invention preferably contain soap in amounts of 0.1% by weight to 1.5% by weight.

The detergents according to the invention preferably contain peroxy bleach, in particular in combination with bleach activators. Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and other peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperoxyazelaic acid or diperoxydodecanedioic acid. The detergents preferably contain 5 to 25% by weight and in particular 10 to 20% by weight of bleaching agent, preferably sodium perborate monohydrate, tetrahydrate or sodium percarbonate being used. In order to achieve an improved bleaching effect, especially when washing at temperatures of 60 ° C. and below, bleach activators can be incorporated into the preparations which form organic peracids with H ₂ O ₂ . Examples of these are N- or O-acyl compounds, for example multi-acylated alkylenediamines, in particular tetraacetylethylene diamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, triazines, urazoles, diketopiperazines, sulfurylamides and cyanuric acid hydrides, and also carboxylic acid hydrides , Carboxylic acid esters, especially sodium isonanoyloxybenzenesulfonate, and acylated sugar derivatives, especially pentaacetyl glucose. The bleach activator can be coated with coating substances in a known manner or, if necessary with the aid of auxiliaries, granulated or extruded / pelletized and, if desired, contain further additives, for example dye. Such granules preferably contain over 70% by weight, in particular from 90% by weight to 99% by weight, of bleach activator. A bleach activator is preferably used which forms peracetic acid under the washing conditions. Among these is tetraacetylethylenediamine (TAED) with average grain sizes of 0.01 to 0.8 mm, granulated with the help of carboxymethyl cellulose, as can be produced by the process described in European Patent EP 037 026, and / or granulated 1,5- Diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), as can be prepared by the process described in German Patent DD 255 884, is particularly preferred. Extruded TAED which contains 70 70% by weight of TAED, 15 to 25% by weight of C _12-18 fatty alcohol sulfate and 2 to 6% by weight of soda can also be used. The content of bleach activators in the detergents containing bleach is in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.

To the other detergent ingredients, the proportion of which depends on the composition the detergent is 0.1 to 5% by weight, foam inhibitors count, optical brighteners, fabric softening substances as well as colors and fragrances. It can also contain neutral salts in an amount of up to 20% by weight its proportion is preferably less than 10% by weight.

Furthermore, the agent according to the invention can contain additional graying inhibitors in an amount of 0.1 to 5 wt .-%, based on the agent. Water-soluble colloids are mostly additional graying inhibitors organic nature suitable, for example soluble starch preparations and for example degraded starch, aldehyde starches and so on. Carboxymethyl cellulose (Na salt), methyl cellulose, methyl hydroxyethyl cellulose and their Mixtures and polyvinylpyrrolidone are preferably used.

In addition to the cellulase used according to the invention, the washing and Detergents contain other enzymes such as protease, amylase and lipase.

The proteases which can be used in the agents according to the invention include the enzymes which can be obtained from microorganisms, in particular bacteria or fungi and have a pH optimum in the alkaline range, for example those from the international patent applications WO 92/07067, WO 91/02792, WO 88/03947 or WO 88/03946 or the European patent applications EP 471 265, EP 416 967 or EP 394 352 known proteases. Protease is preferably used in the agent according to the invention in amounts such that the finished agent 100 PE / g to 15000 PE / g (protease units per gram, determined by the method described in surfactants 7, 125 (1970)), in particular 125 PE / g to 7500 PE / g and particularly preferably 150 PE / g to 4500 PE / g. Suitable proteases are commercially available, for example under the names BLAP ^(R) , Savinase ^(R) , Durazym ^(R) , Esperase ^(R) , Naxatase ^(R) , Maxapem ^(R) , Optimase ^(R) , Opticlean ^(R) or Alcalase ^(R) .

The amylases which can be used in agents according to the invention include the enzymes which can be obtained from bacteria or fungi and which have a pH optimum, preferably in the alkaline range up to about pH 10. Useful commercial products include Termamyl ^(R) and Maxamyl ^(R) . Amylase is preferably used in the agent according to the invention in amounts such that the finished agent 0.01 KNU / g to 3 KNU / g ("Kilo-Novo-Units" per gram according to the Novo standard method, where 1 KNU is the amount of enzyme which breaks down 5.26 g of starch at pH 5.6 and 37 ° C., based on the method described by P. Bernfeld in SP Colowick and ND Kaplan, Methods in Enzymology, Volume 1, 1955, page 149), in particular 0.010 KNU / g to 1.8 KNU / g and particularly preferably 0.01 KNU / g to 1.6 KNU / g.

The lipase is an enzyme that can be obtained from microorganisms, in particular bacteria or fungi. Such is known, for example, from European patent applications EP 204 208, EP 214 761, EP 258 068, EP 407 225 or international patent application WO 87/859. Examples of useful commercially available lipases are Lipolase ^(R) and Lipozym ^(R) . Lipase is preferably used in the agent according to the invention in amounts such that the finished agent 10 LU / g to 10,000 LU / g ("lipase activity units" per gram, determined by the enzymatic hydrolysis of tributyrin at 30 ° C. and pH 7 after the method mentioned in EP 258 068), in particular 80 LU / g to 5,000 LU / g and particularly preferably 100 LU / g to 1000 LU / g.

The enzymes can be adsorbed onto carriers in a manner known per se, embedded in coating substances and / or with the aid of carrier substances have been granulated to make them easier to handle and against Protect premature inactivation when in detergent or cleaning products should be incorporated.

When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also advantageously used, for example those composed of silicones and paraffins or waxes. The foam inhibitors, in particular silicone- or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearoylethylene diamides are particularly preferred.

In a preferred embodiment, the washing agents according to the invention contain and cleaning agents 30% by weight to 55% by weight of water-insoluble inorganic Builder, 2.5% to 20% synthetic anionic surfactant, 1 % By weight to 20% by weight of nonionic surfactant component, up to 25% by weight, in particular 1% by weight to 15% by weight of bleach, up to 8% by weight, in particular 0.5 wt% to 6 wt% bleach activator and up to 20 wt%, in particular 0.1% to 15% by weight of inorganic salts, in particular alkali carbonate, sulfate and / or chloride, and up to 2% by weight, in particular 0.4 wt.% To 1.2 wt.% Further enzyme made up in particulate form, in particular protease, amylase and / or lipase.

The agents according to the invention can, for example, in a manner known per se by mixing, granulating, extruding and / or by spray drying getting produced. Preferably, the pourable powder, extruded or granular preparations from a dry homogeneous mixture of at least two powder components, the first of which is spray-dried Powder is present. This is through a conventional one Spray drying of a slurry available, at least the anionic surfactants and the zeolite in an aqueous suspension and optionally contains nonionic surfactants. Bleaching agents such as perborate are not together as usual because of their thermal sensitivity spray dried with the ingredients of the first powder component, but only added to the spray product afterwards. When extruding Perborate is usually shared with most other ingredients coextruded. There can be a pre-made tower powder as one the extrusion components as well as a non-tower extrudate or multi-extrudate technology be assumed. Alkali silicates are used because of the known zeolite / alkali silicate incompatibility under spray drying conditions not spray-dried with the zeolite-containing slurry. As well the layered silicates which may be present are preferably not spray dried, but in granular form or adsorbed onto a carrier, which consists, for example, of sulfate and / or carbonate. The layered silicates can also be coextruded in the extrusion process.

The preparation of the agents according to the invention can be done in the simplest way by admixing the enzyme particles in a conventional mixer, in particular a drum, roller, belt or free-fall mixer, optional other powdery components, in particular bleach, and if desired also liquid or liquefied components, to which in particular non-ionic surfactants but also colors and fragrances belong, can be mixed by spraying. Including the familiarization the other ingredients by admixing granules containing them or extrudate to the other components is possible and especially for the production of detergents with a relatively high bulk density from preferably 650 g / l to 900 g / l is preferred.

Examples

A granular basic detergent ( BW ) with the composition 12% by weight of synthetic anionic surfactant, 2% by weight of soap, 9% by weight of nonionic surfactant, 35% by weight of zeolite Na-A, 11% by weight of Na citrate was used , 10% by weight Na carbonate, 2% by weight Na silicate, 8% by weight Na sulfate, the remainder to 100% by weight water, with the amounts of the additives listed in Table 1 given there mixed and tested the inventive agent M1 with BW and the comparative agents V1 to V4 under practical conditions. For this purpose, 2.1 g of the tissue contaminated with the test soils indicated in the table below, each with 6.3, were in a launderometer, type Atlas Standard (liquor ratio 1:12, water hardness 16 ° dH, 8.4 grams of detergent per liter of washing solution) g Clean white cotton fill fabric at 40 ° C for 30 minutes each (including heating time (3 ° C / minute)) and then rinsed 3 times for 30 seconds. After drying, the reflectance of the test fabrics given in Table 2 was determined photometrically (measuring wavelength 460 nm, quadruple determination). Detergent composition [% by weight] medium BW Cellulase Cobuilder Cobuilder polymer M1 91 2nd 5 - 2nd V1 96 2nd - - 2nd V2 93 - 5 - 2nd V3 93 2nd 5 - - V4 91 2nd - 5 2nd Reflectance values [%] medium Remission when soiled A B C. D E F BW 49.1 57.0 60.8 65.5 64.7 61.3 V1 nb 58.6 nb nb nb nb V2 48.6 58.7 59.7 64.7 68.1 nb V3 46.0 58.2 nb 66.6 66.9 63.7 V4 48.8 60.7 64.8 67.8 nb nb M1 50.0 62.1 66.4 68.7 68.6 74.4 nb: not determined Soiling: A: Lipstick finished on mixed fabric polyester / cotton B: Make-up refined on mixed fabric polyester / cotton C: Dust on cotton D: Dust / skin fat refined on cotton E: Dust / skin fat refined on mixed fabric polyester / cotton F: Dust / skin fat on polyester

It can be seen that the agent M1 according to the invention has a significantly higher detergency than agents which lack a component of the active compound combination used according to the invention ( V1 , V2 and V3 ) or which contain a conventional cobuilder instead of the terpolymer.

Claims (8)

1. A powder-form surfactant-, cellulase- and builder-containing detergent, characterized in that it contains

   a) 0.15 to 10% by weight of a soil-release polymer containing ethylene terephthalate groups corresponding to the following formula:

   

   and polyethylene oxide terephthalate groups corresponding to the following formula:

   

   in which n is an integer of 17 to 110, the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate in the polymer being from 50:50 to 90:10,

   b) cellulase with an activity of 0.05 IU/g to 1.5 IU/g and

   c) 1% by weight to 40% by weight of terpolymers of the monomer units of two ethylenically unsaturated carboxylic acids and/or salts thereof and, as the third monomer unit, vinyl alcohol and/or a vinyl alcohol derivative or a carbohydrate.
2. A detergent as claimed in claim 1, characterized in that the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate in the soil-release polymer is 65:35 to 80:20, the molecular weight of the connecting polyethylene oxide links is 1,000 to 3,000 and the molecular weight of the soil-release polymer is in the range from 10,000 to 50,000.
3. A detergent as claimed in claim 1 or 2, characterized in that the terpolymer consists of the monomer units of a monoethylenically unsaturated C_3-8 carboxylic acid, a monoethylenically unsaturated C_4-8 dicarboxylic acid and vinyl alcohol and/or a vinyl alcohol derivative and/or the salts of a monoethylenically unsaturated C_3-8 carboxylic acid and a monoethylenically unsaturated C_4-8 dicarboxylic acid and vinyl alcohol and/or a vinyl alcohol derivative.
4. A powder-form surfactant-, cellulase- and builder-containing detergent, characterized in that it contains

   a) 0.15 to 10% by weight of a soil-release polymer containing ethylene terephthalate groups corresponding to formula (I) and polyethylene oxide terephthalate groups corresponding to formula (II) in which n is an integer of 17 to 110, the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate in the polymer being from 50:50 to 90:10,

   b) cellulase with an activity of 0.05 IU/g to 1.5 IU/g and

   c) 1% by weight to 40% by weight of terpolymer of the monomer units of a monoethylenically unsaturated C_3-8 carboxylic acid, a 2-alkyl allylsulfonic acid or 2-aryl allylsulfonic acid and a carbohydrate and/or the salts of a monoethylenically unsaturated C_3-8 carboxylic acid, a 2-alkyl allylsulfonic acid or 2-aryl allylsulfonic acid and a carbohydrate.
5. A detergent as claimed in any of claims 1 to 4, characterized in that the terpolymers are either completely or at least partly neutralized, preferably more than 50% neutralized and, more preferably, completely neutralized, based on the carboxyl groups present.
6. A detergent as claimed in any of claims 1 to 5, characterized in that it contains nonionic surfactants from the group consisting of alcohols with low and relatively high degrees of ethoxylation and glycosides in a quantity of 2 to 25% by weight and anionic surfactants from the group consisting of alkyl and alkenyl sulfates in a quantity of up to 15% by weight.
7. A detergent as claimed in any of claims 1 to 6, characterized in that it contains 30% by weight to 55% by weight of water-insoluble inorganic builders, 2.5% by weight to 20% by weight of synthetic anionic surfactant, 1% by weight to 20% by weight of nonionic surfactant component, up to 25% by weight and, more particularly, 1% by weight to 15% by weight of bleaching agent, up to 8% by weight and, more particularly, 0.5% by weight to 6% by weight of bleach activator, up to 20% by weight and, more particularly, 0.1% by weight to 15% by weight of inorganic salts, more especially alkali metal carbonate, sulfate and/or silicate, and up to 2% by weight and, more particularly, 0.4% by weight to 1.2% by weight of a particulate further enzyme, more especially protease, amylase and/or lipase.
8. A detergent as claimed in any of claims 1 to 7, characterized in that it is produced by spray drying, extrusion or granulation.