EP0736083A1 - Washing and cleaning powder - Google Patents

Washing and cleaning powder

Info

Publication number
EP0736083A1
EP0736083A1 EP95905070A EP95905070A EP0736083A1 EP 0736083 A1 EP0736083 A1 EP 0736083A1 EP 95905070 A EP95905070 A EP 95905070A EP 95905070 A EP95905070 A EP 95905070A EP 0736083 A1 EP0736083 A1 EP 0736083A1
Authority
EP
European Patent Office
Prior art keywords
weight
detergent
vinyl alcohol
acid
agent according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP95905070A
Other languages
German (de)
French (fr)
Other versions
EP0736083B1 (en
Inventor
Fred Schambil
Eduard Smulders
Horst Upadek
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0736083A1 publication Critical patent/EP0736083A1/en
Application granted granted Critical
Publication of EP0736083B1 publication Critical patent/EP0736083B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase

Definitions

  • the invention relates to detergents and cleaning agents which contain surfactant, builder, cellulase and a dirt-repellent polymer and a terpolymeric co-builder.
  • detergents and cleaning agents generally contain builders and surfactants from the group of anionic and nonionic surfactants as main components.
  • Detergents may contain co-builders such as polycarboxylates, peroxy bleach, bleach activators, foam inhibitors, optical brighteners and enzymes or enzyme combinations to improve the cleaning action as further constituents.
  • protease aylase
  • cellulase aylase
  • cellulase aylase
  • lipase aylase
  • protease aylase
  • cellulase aylase
  • lipase aylase
  • protease aylase
  • cellulase aylase
  • lipase aylase
  • cellulase aylase
  • lipase lipase.
  • cellulase is described, for example, in European patent application EP 468464 and in international patent applications WO 91/19807, WO 91/19794 or WO 90/02790.
  • Graying inhibitors in the actual sense have the task of keeping the dirt detached from the fibers suspended in the liquor and preventing the dirt from settling again and thus preventing the fibers from graying, while the above-mentioned soil repellent active substances presumably function in the sense of protecting them unfold pointing fiber equipment.
  • detergents which contain, as a dirt-repellent compound, a polymer of ethylene terephthalate and polyethylene oxide terephthalate, and also anionic surfactants in the form of alcohol sulfates, alcohol sulfates condensed with ethylene oxide, and mixtures thereof.
  • European patent application EP 0365103 describes a surfactant composition which comprises 4 to 30% by weight of a synthetic nonionic surfactant, 25 to 80% by weight builder for this nonionic surfactant, 0.1 to 2% by weight Protease, 0 to 2 wt .-% amylase, 0.2 to 1 wt .-% cellulase, 1 to 15 wt .-% water and as a further component poly (alkylene glycol terephthalate).
  • the detergents known from the prior art do not always have satisfactory dirt-repellent properties in order to prevent graying of the washed fabric as long as possible. This affects their cleaning effect.
  • the object of the present invention is to provide washing and cleaning agents which have excellent cleaning action and at the same time have dirt-removing properties in order to prevent the graying of the fabrics.
  • the present invention relates to a detergent and cleaning agent containing powdery surfactants, cellulase and builder, which a) contains 0.15 to 10% by weight of a dirt-repellent polymer which contains ethylene terephthalate groups of the formula
  • n is an integer from 17 to 110, the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate in the polymer being from about 50:50 to about 90:10, b) cellulase in an activity of 0.05 IU / g to 1.5 IU / g, and c) 1% by weight to 40% by weight of 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.
  • the soil-repellent polymers according to the invention which contain groups with the formulas I and II above, are in the washing and cleaning agents according to the invention in an amount of 0.15% by weight to about 10% by weight, preferably about 0.25% by weight % to about 5% by weight, particularly preferably about 0.3% by weight to about 3% by weight.
  • the molecular weight of the linking polyethylene oxide units is preferably in the range from 750 to 5000.
  • the polymers can have an average molecular weight from approximately 5000 to approximately 200000. Ethylene terephthalate and polyethylene oxide terephthalate can be distributed arbitrarily in the polymer.
  • Preferred polymers are those with molar ratios of ethylene terephthalate to polyethylene oxide terephthalate from about 65:35 to about 90:10, preferably from about 65:35 to about 80:20, the linking polyethylene oxide units having a molecular weight of 750-5000. preferably about 1000 to about 3000 and the polymer has a molecular weight of about 10,000 to about 50,000.
  • Examples of commercially available polymers of this type are, for example, "Milease ( R ) -T" from ICI United States, Inc., Repel-0-Te ⁇ ( R ) SRP 3 from Rhönen-Poulenc and Zelcon ( R ) 8037 from DuPont.
  • the dirt-repellent polymers used in agents according to the invention can be prepared by known polymerization processes, the starting materials being used in amounts such as to obtain the above-mentioned ratios of ethylene terephthalate to polyethylene oxide terephthalate.
  • the processes described in US Pat. No. 3,479,212 can be used to produce suitable polymers.
  • the washing and cleaning agents of the invention generally contain 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.
  • the zeolite used is preferably zeolite of the A and / or P type in detergent quality. Their mixtures with zeolite NaX are also suitable, the proportion of the zeolite NaX in such mixtures normally being below 30%. They have practically no particles larger than 30 ⁇ m and preferably consist at least 80% of particles smaller than 10 ⁇ m.
  • Preferred zeolites have an average particle size of less than 10 ⁇ m (measurement method: Fraunhofer diffraction; mean value of the volume distribution), preferably between 1.5 and 4.5 ⁇ m, in particular between 2.0 and 4.0 ⁇ m.
  • Their calcium binding capacity which can be determined according to the information in German patent DE 24 12837, is in the range from 100 to 200 mg CaO / g.
  • the content of finely divided, in particular crystalline, hydrated zeolite in the compositions is preferably 30 to 65% by weight and in particular 32 to 45% by weight, 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.
  • alkali silicates are added as a solid and not in the form of a solution. They can be amorphous or crystalline.
  • Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na2O: SiO2 molar ratio of 1: 2 to 1: 2.8.
  • Such amorphous alkali silicates are commercially available, for example, under the name Portil ( R ).
  • the crystalline silicates which may be present alone or in a mixture with amorphous silicates are preferably crystalline sheet silicates of the formula (I) NaMSi x ⁇ 2 ⁇ + ⁇ * yH2 ⁇ , in which M represents sodium, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 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.
  • both are preferably .beta.- and ⁇ 'Na2S ⁇ -sodium "2 ⁇ 5.yH2 ⁇ , wherein ß-Natriumdisil kat spielmud can be obtained by the method / described in interna ⁇ tional patent application W091 08,171th
  • the content of the agent of alkali silicates is preferably 1 to 15% by weight and in particular 2 to 8% by weight, based on anhydrous active substance, and the weight ratio of zeolite: amorphous silicate, based in each case on anhydrous active substance, is preferably 4: 1 to 10
  • 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, is at least 5: 1. In agents which contain both amorphous and crystalline alkali silicates, the weight ratio is
  • 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 C3-Cs carboxylic acid and preferably from a C3-C4 monocarboxylic acid, in particular from (meth) acrylic acid.
  • the second acidic monomer unit or its salt can be a derivative of a C4-C8 dicarboxylic acid, preferably a C4-C8 dicarboxylic acid, maleic acid being particularly preferred.
  • 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 C1-C4 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 wt .-% 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 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, in the 2-position, has an alkyl radical, preferably 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 methyl sulfonate 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.
  • 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 or at least partially, in particular to more than 50%, also preferably used are neutralized to the carboxyl groups present.
  • a completely neutralized terpolymer is particularly preferred, ie it consists of the salts of the monomeric acids, in particular the sodium or potassium salts of the monomeric acids, and vinyl alcohol or a carbohydrate.
  • the terpolymers generally have a relative molecular mass between 1000 and 200000, preferably between 200 and 50,000 and in particular between 3000 and 10,000. They are mostly used in the form of aqueous solutions, preferably in the form of 30 to 50% by weight aqueous solutions.
  • Particularly preferred terpolymers are prepared by processes which are described in German patent DE 4221 381 and international patent application WO 94/15978.
  • polymeric carboxylates or polymeric carboxylic acids which are composed of one or two monomer units can also be present as further builders. These polymeric carboxylates or carboxylic acids can be present in the agents according to the invention in an amount of up to 15% by weight, but are preferably absent entirely.
  • 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 are considered, such as polyacrylates, polyhydroxyacrylates, polymethacrylates, polymaleates and in particular copolymers of acrylic acid with maleic acid or maleic acid anhydride, preferably those made 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 200000, preferably 50,000 to 120,000, based on free acid.
  • a usually particularly preferred acrylic acid-maleic acid copolymer has a relative 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, for example, from German Offenlegungssschriften DT 2247832, DE 31 17 250, DE 3207825, DE 3207847 and DE 3322950, the British Patent application GB 2232983, European patent applications EP 0265832, EP 0269077, EP 0270974, EP 0271 004, EP 0339550, EP 0458162 and EP 0468464 or 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.
  • 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. Bio! Chem. 53, 1275 (1989) by S. Ito et al.), in particular 0.07 IU / g to 1.4 IU / g and particularly preferably 0.1 IU / g to 1.3 IU / g.
  • Suitable commercial products are, for example, Celluzyme ( R ) from Novo Nordisk or KAC ( R ) from Kao.
  • the detergents according to the invention can contain water-soluble complexing agents from the group of the phosphonates.
  • Salts of polyphosphonic acids such as neutral sodium salts of, for example, 1-hydroxyethane-l, l-diphosphonate and diethylenetriaminepentamethylenephosphonate are used.
  • the phosphonates can be used in amounts of up to 1.5% by weight.
  • the detergents and cleaning agents normally contain surfactant compounds from the group of nonionic surfactants as further customary constituents, and anionic and / or zwitterionic surfactants may also be present.
  • the surfactants are generally present in the detergents according to the invention with a total content of 5 to 40% by weight, preferably 5 to 30% by weight and in particular 8 to 25% by weight.
  • the detergent according to the invention contains in particular low-ethoxylated and higher-ethoxylated nonionic surfactants as nonionic surfactants.
  • the nonionic surfactants can be present in an amount of up to 25% by weight, preferably up to 15% by weight.
  • the ethoxylated alcohols preferably used as nonionic surfactants 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 the higher ethoxylated alcohols have an average of 7 to 20 moles of ethylene oxide.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • the alcohol radical can be linear or methyl-branched in the 2-position, or contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms are preferred, e.g. B. from coconut, tallow or oleyl alcohol.
  • the preferred low-ethoxylated alcohols include, for example, fatty alcohols having 12 to 18 carbon atoms with an average of 3 to 6 EO units.
  • the preferred higher ethoxylated alcohols include, for example, fatty alcohols with 16 to 18 carbon atoms with an average of 12 to 16 EO units, for example ethoxylated palm alcohol.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • the detergents according to the invention preferably contain 1% by weight to 10% by weight, in particular 1% by weight to 5% by weight of low-ethoxylated nonionic surfactants and 1% by weight to 10% by weight, in particular 1% by weight. % to 5% by weight of 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.
  • 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 described in international patent application WO 90 / 13533 are described, and alkyl glycosides of the general formula R0 (G) x , in which R is a primary straight-chain or methyl-branched, in particular in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G represents a glycose unit with 5 or 6 carbon atoms, preferably 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.
  • Suitable anionic surfactants which can be used in the agents according to the invention are sulphates and, if appropriate, sulphonates and soaps composed of preferably natural fatty acids or fatty acid mixtures. Overall, the anionic surfactants can be present in the agents according to the invention in an amount of up to 15% by weight.
  • Suitable sulfate-type surfactants are sulfuric acid monoesters from primary alcohols of natural and synthetic origin.
  • alk (en) yl sulfates the sulfuric acid half-esters of the Ci2-Ci8 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C ⁇ o-C2 ⁇ ⁇ 0xoalcohols, and those secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, petrochemical-based, straight-chain alkyl radical which have an analogous degradation behavior, as well as the adequate compounds based on oleochemical raw materials.
  • Ci6-Ci8-alk (en) yl sulfates are particularly preferred from the point of view of washing technology.
  • compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of Ci2-C ⁇ 4-fatty alkyl sulfates or Ci2-Ci6-fatty alkyl sulfates with Cjo-Cis-fatty alkyl sulfates.
  • saturated alkyl sulfates not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C16-C22 are used.
  • Mixtures of saturated sulfated fatty alcohols consisting predominantly of C ⁇ 6 and unsaturated sulfated fatty alcohols consisting predominantly of cis are particularly preferred, for example those which are derived from solid or liquid fatty alcohol mixtures of the type HD-0cenol ( R ) (commercial product of the applicant ).
  • Weight ratios of alkyl sulfates to alkenyl sulfates of 10: 1 to 1: 2 and in particular of 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 with 1 to 6 mol Ethylene oxide ethoxylated straight-chain or branched C7-C2i alcohols such as 2-methyl-branched Cg-Cji alcohols with an average of 3.5 mol of ethylene oxide (E0) or C ⁇ 2-Ci8 fatty alcohols with 2 to 4 E0, 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.
  • surfactants of the sulfonate type preference is given to Cg-Cis-alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates and also disulfonates of the type found, for example, in Ci2-Ci8-M ° n ° ° olefins - Or internal double bond obtained by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • These surfactants can be up to 10% by weight on average, preferably up to 5% by weight. However, it is also possible to dispense with sulfonate-type surfactants 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, as well as soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids, being suitable .
  • those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated Ci2-Ci8 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.
  • peroxy bleach in particular in combination with bleach activators.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other usable 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 is used.
  • bleach activators can be incorporated into the preparations which form organic peracids with H2O2.
  • these are N- or O-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, triazines, urazoles, diketopiperazines, sulfurylamides and cyanurate amides , in addition carboxylic anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyloxybenzenesulfonate, and acylated sugar derivatives, in particular pentaacetyl glucose.
  • N- or O-acyl compounds for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acy
  • 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.
  • TAED tetraacetylethylenediamine
  • DADHT 5-Diacetyl-2,4-dioxohexa- hydro-l, 3,5-triazine
  • Extruded TAED can also be used, which>. Contains 70% by weight of TAED, 15 to 25% by weight of C 1-5 fatty alcohol sulfate and 2 to 6% by weight of soda.
  • 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.
  • the other detergent components include foam inhibitors, optical brighteners, textile-softening substances and colorants and fragrances.
  • Neutral salts can also be present in an amount of up to 20% by weight, their proportion preferably being less than 10% by weight.
  • the agent according to the invention can contain additional graying inhibitors in an amount of 0.1 to 5% by weight, based on the agent.
  • Water-soluble colloids of mostly organic nature are suitable as additional graying inhibitors, for example soluble starch preparations and, for example, degraded starch, aldehyde starches and so on.
  • Carboxymethyl cellulose (sodium salt), methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof, and polyvinyl pyrrolidone are preferably used.
  • the detergents and cleaning agents can contain further enzymes such as protease, amylase and lipase.
  • 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, with a pH optimum in the alkaline range, for example those from the international patent applications WO 92/07067, WO 91/02792, WO 88/03947 or WO 88/03946 or the European patent applications EP 471 265, EP 416 967 or EP 394 352 known proteases.
  • Protease is preferably 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 Tenside 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 ), Maxatase ( R ), Maxapem ( R ), 0ptimase ( R ), 0pticlean ( R ) or Alcalase ( R ).
  • 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 are, for example, 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 that of P.
  • 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 204208, EP 214761, EP 258068, 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 via the enzymatic hydrolysis of tributyrin at 30 ° C. and pH 7 according to the method mentioned in EP 258 068), in particular 80 LU / g to 5,000 LU / g and particularly preferably 100 LU / g to 1000 LU / g.
  • the enzymes can be adsorbed onto carrier substances in a manner known per se, embedded in coating substances and / or granulated with the aid of carrier substances in order to make them easier to handle and to protect against premature inactivation when they are incorporated into washing or cleaning agents should.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of Ci8-C24 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 are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearoylethylene diamides are particularly preferred.
  • the washing and cleaning agents according to the invention contain 30% by weight to 55% by weight of water-insoluble inorganic builder, 2.5% by weight to 20% by weight of synthetic anionic surfactant, 1% by weight to 20% by weight of nonionic surfactant components, up to 25% by weight, in particular 1% by weight to 15% by weight of bleaching agent, up to 8% by weight, in particular 0.5% by weight to 6 %
  • bleach activator and up to 20% by weight in particular 0.1% by weight 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 .-% particulate assembled further enzyme,
  • the agents according to the invention can be prepared in a manner known per se, for example by mixing, granulating, extruding and / or by spray drying.
  • the pourable powdered, extruded or granular preparations preferably consist of a dry homogeneous mixture of at least two powder components, the first of which is in the form of a spray-dried powder. This can be obtained by spray drying a slurry which comprises at least the anionic surfactants and the zeolite in an aqueous suspension and, if appropriate, nonionic surfactants. Because of their thermal sensitivity, bleaching agents such as perboate are not spray-dried together with the constituents of the first powder component, but are only mixed into the sprayed product subsequently.
  • perborate When extruding, perborate is usually co-extruded with most other ingredients.
  • a pre-made tower powder as one of the extrusion components as well as a non-tower extrudate or multi-extrudate technology can be assumed there.
  • alkali silicates are not spray-dried with the zeolite-containing slurry under spray drying conditions.
  • the layered silicates which may be present are preferably not spray-dried, but mixed in 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 agents according to the invention can be produced in the simplest manner by admixing the enzyme particles in a conventional mixer, in particular a drum, roller, belt or free-fall mixer, optional other powdery constituents, in particular bleaching agents, and if desired also liquid or liquefied constituents , which include in particular nonionic surfactants but also colorants and fragrances, can be mixed in by spraying.
  • a conventional mixer in particular a drum, roller, belt or free-fall mixer
  • optional other powdery constituents in particular bleaching agents
  • liquid or liquefied constituents which include in particular nonionic surfactants but also colorants and fragrances
  • the incorporation of the other constituents by admixing a granulate or extrudate containing them with the other constituents is also possible and is particularly preferred for the production of detergents with a relatively high bulk density of preferably 650 g / 1 to 900 g / 1.
  • 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 (VI, V2 and V3) or which contain a conventional cobuilder instead of the terpolymer.

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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

Pulverförmiqes Wasch- und Reinigungsmittel Powder detergent and cleaning agent
Die Erfindung betrifft Wasch- und Reinigungsmittel, die Tensid, Builder, Cellulase und ein schmutzabweisendes Polymer sowie einen terpolymeren Co- builder enthalten.The invention relates to detergents and cleaning agents which contain surfactant, builder, cellulase and a dirt-repellent polymer and a terpolymeric co-builder.
Eine wichtige Zielsetzung auf dem Gebiet der Wasch- und Reinigungsmittel ist, Substanzen und Gemische zu entwickeln, die dazu in der Lage sind, von verschmutzten Oberflächen, zum Beispiel von Geweben, den Schmutz abzulösen. Derartige Wasch- und Reinigungsmittel enthalten in der Regel als Hauptkom¬ ponenten Builder und Tenside aus der Gruppe der anionischen und nichtioni¬ schen Tenside. Als weiterere Bestandteile können in Waschmitteln Cobuilder wie Polycarboxylate, Peroxybleichmittel, Bleichaktivatoren, Schauminhibi¬ toren, optische Aufheller und Enzyme beziehungsweise Enzymkombinationen zur Verbesserung der Reinigungswirkung enthalten sein.An important objective in the field of detergents and cleaning agents is to develop substances and mixtures that are able to remove dirt from soiled surfaces, for example fabrics. Such detergents and cleaning agents generally contain builders and surfactants from the group of anionic and nonionic surfactants as main components. Detergents may contain co-builders such as polycarboxylates, peroxy bleach, bleach activators, foam inhibitors, optical brighteners and enzymes or enzyme combinations to improve the cleaning action as further constituents.
Zu den am häufigsten eingesetzten Enzymen zählen Protease, A ylase, Cel¬ lulase und Lipase. Diese Enzyme weisen jeweils untereinander unterschied¬ liche Eigenschaften auf und können aus verschiedenen Quellen stammen. Die Verwendung von Cellulase wird zum Beispiel in der europäischen Patentan¬ meldung EP 468464 sowie in den internationalen Patentanmeldungen WO 91/19807, WO 91/19794 oder WO 90/02790 beschrieben.The most frequently used enzymes include protease, aylase, cellulase and lipase. These enzymes each have different properties from one another and can come from different sources. The use of cellulase is described, for example, in European patent application EP 468464 and in international patent applications WO 91/19807, WO 91/19794 or WO 90/02790.
Auch wenn die aus dem Stand der Technik bekannten Wasch- und Reinigungs¬ mittel eine gute Reinigungswirkung besitzen, tritt während des Waschvor¬ gangs jedoch der Effekt auf, daß sich die abgelösten Schmutzstoffe, zum Beispiel Pigment oder Fettpartikel, wieder auf den Geweben beziehungsweise den Oberflächen absetzen. Diese Wirkung führt zu einer Vergrauung von weißen Geweben und einer Verminderung der Leuchtkraft der Farbe bei far¬ bigen Geweben. Dieser Effekt wird auch als sogenannter "Grauschleier" be¬ zeichnet. Um zu verhindern, daß sich die abgelösten Schmutzstoffe wieder auf dem Gewebe absetzen und somit zu einer Vergrauung führen, wurden Ver- bindungen entwickelt, die schmutzabweisende Eigenschaften und somit auch eine vergrauungsinhibierende Wirkung, sogenannte Soil repellent-/Soil re- lease-Eigenschaften, besitzen. Vergrauungsinhibitoren im eigentlichen Sinne haben demgegenüber die Aufgabe, den von der Faser abgelösten Schmutz in der Flotte suspendiert zu halten und das Wiederabsetzen des Schmutzes und somit das Vergrauen der Fasern zu verhindern, während die obengenannten Soil repellent-Wirkstoffe vermutlich ihre Funktion im Sinne der schutzab¬ weisenden Faserausrüstung entfalten. Zum Beispiel in der deutschen Patent¬ schrift DE 28 57 292 werden Waschmittel beschrieben, die als schmutzab¬ weisende Verbindung ein Polymer aus Ethylenterephthalat und Polyethylen¬ oxidterephthalat sowie anionische Tenside in Form von Alkoholsulfaten, mit Ethylenoxid kondensierten Alkoholsulfaten und Gemische davon enthalten.Even if the washing and cleaning agents known from the prior art have a good cleaning effect, the effect occurs during the washing process that the detached contaminants, for example pigment or fat particles, are again on the fabrics or the surfaces drop. This effect leads to graying of white fabrics and a reduction in the luminosity of the color in colored fabrics. This effect is also referred to as a so-called "gray haze". In order to prevent the detached contaminants from settling on the fabric again and thus leading to graying, Developed bonds that have dirt-repellent properties and thus also a graying-inhibiting effect, so-called soil repellent / soil release properties. Graying inhibitors in the actual sense, on the other hand, have the task of keeping the dirt detached from the fibers suspended in the liquor and preventing the dirt from settling again and thus preventing the fibers from graying, while the above-mentioned soil repellent active substances presumably function in the sense of protecting them unfold pointing fiber equipment. For example, in German Patent DE 28 57 292, detergents are described which contain, as a dirt-repellent compound, a polymer of ethylene terephthalate and polyethylene oxide terephthalate, and also anionic surfactants in the form of alcohol sulfates, alcohol sulfates condensed with ethylene oxide, and mixtures thereof.
In der europäischen Patentanmeldung EP 0365103 wird eine Tensidzusammen- setzung beschrieben, welche 4 bis 30 Gew.-% eines synthetischen nichtioni¬ schen Tensids, 25 bis 80 Gew.-% Builder für dieses nichtionische Tensid, 0,1 bis 2 Gew.-% Protease, 0 bis 2 Gew.-% Amylase, 0,2 bis 1 Gew.-% Cellu¬ lase, 1 bis 15 Gew.-% Wasser und als weiteren Bestandteil Poly(alkylen- glykolterephthalat) enthält.European patent application EP 0365103 describes a surfactant composition which comprises 4 to 30% by weight of a synthetic nonionic surfactant, 25 to 80% by weight builder for this nonionic surfactant, 0.1 to 2% by weight Protease, 0 to 2 wt .-% amylase, 0.2 to 1 wt .-% cellulase, 1 to 15 wt .-% water and as a further component poly (alkylene glycol terephthalate).
Die aus dem Stand der Technik bekannten Waschmittel weisen nicht immer zu¬ friedenstellende schmutzabweisende Eigenschaften auf, um eine Vergrauung des gewaschenen Gewebes möglichst dauerhaft zu verhindern. Dadurch wird ihre Reinigungswirkung beeinträchtigt.The detergents known from the prior art do not always have satisfactory dirt-repellent properties in order to prevent graying of the washed fabric as long as possible. This affects their cleaning effect.
Aufgabe der vorliegenden Erfindung ist es, Wasch- und Reinigungsmittel zur Verfügung zu stellen, die ausgezeichnete Reinigungswirkung zeigen und gleichzeitig schmutzablösende Eigenschaften aufweisen, um das Vergrauen der Gewebe zu verhindern.The object of the present invention is to provide washing and cleaning agents which have excellent cleaning action and at the same time have dirt-removing properties in order to prevent the graying of the fabrics.
Überraschenderweise wurde nun gefunden, daß die Reinigungsleistung und die vergrauungsinhibierende Wirkung von pulverförmigen Wasch- und Reinigungs¬ mitteln weiter erhöht werden kann, indem man das Tensid- und Buildersystem solcher Mittel durch speziellen Kombinationen aus schmutzablösendem Poly¬ mer, Cobuilder und Enzym optimiert. Gegenstand der vorliegenden Erfindung ist ein pulverför iges tensid-, cellulase- und builderhaltiges Wasch- und Reinigungsmittel, das a) 0,15 bis 10 Gew.-% eines schmutzabweisendes Polymers welches Ethylenterephthalat- gruppen der FormelSurprisingly, it has now been found that the cleaning performance and the graying-inhibiting effect of powdered detergents and cleaning agents can be further increased by optimizing the surfactant and builder system of such agents by means of special combinations of dirt-removing polymer, cobuilder and enzyme. The present invention relates to a detergent and cleaning agent containing powdery surfactants, cellulase and builder, which a) contains 0.15 to 10% by weight of a dirt-repellent polymer which contains ethylene terephthalate groups of the formula
und Polyethylenoxidterephthalatgruppen der Formeland polyethylene oxide terephthalate groups of the formula
worin n eine ganze Zahl von 17 bis 110 bedeutet, enthält, wobei das Mol- verhältnis von Ethylenterephthalat zu Polyethylenoxidterephthalat im Poly¬ meren von etwa 50:50 bis etwa 90:10 beträgt, b) Cellulase in einer Akti¬ vität von 0,05 IU/g bis 1,5 IU/g, sowie c) 1 Gew.-% bis 40 Gew.-% Terpoly¬ mere aus den Monomereinheiten von zwei ethylenisch ungesättigten Carbon¬ säuren und/oder deren Salze sowie als dritte Monomereinheit Vinylalkohol und/oder ein Vinylalkohol-Derivat oder ein Kohlenhydrat, enthält.where n is an integer from 17 to 110, the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate in the polymer being from about 50:50 to about 90:10, b) cellulase in an activity of 0.05 IU / g to 1.5 IU / g, and c) 1% by weight to 40% by weight of 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.
Die erfindungsgemäß enthaltenen schmutzabweisenden Polymere, die Gruppen mit den obigen Formeln I und II enthalten, sind in den erfindungsgemäßen Wasch- und Reinigungsmitteln in einer Menge von 0,15 Gew.-% bis etwa 10 Gew.-%, vorzugsweise etwa 0,25 Gew.-% bis etwa 5 Gew.-%, besonders bevor¬ zugt etwa 0,3 Gew.-% bis etwa 3 Gew.- enthalten. In diesen Verbindungen liegt das Molekulargewicht der verknüpfenden Polyethylenoxideinheiten be¬ vorzugt im Bereich von 750 bis 5000. Die Polymere können ein durchschnitt¬ liches Molekulargewicht von etwa 5000 bis etwa 200000 besitzen. Im Polymer können Ethylenterephthalat und Polyethylenoxidterephthalat willkürlich verteilt vorliegen. Bevorzugte Polymere sind solche mit Molverhältnissen von Ethylenterephtha¬ lat zu Polyethylenoxidterephthalat von etwa 65:35 bis etwa 90:10, vorzugs¬ weise von etwa 65:35 bis etwa 80:20, wobei die verknüpfenden Polyethylen- oxideinheiten ein Molekulargewicht von 750 - 5000, bevorzugt etwa 1000 bis etwa 3000 und das Polymere ein Molekulargewicht von etwa 10000 bis etwa 50000 aufweist. Beispiele für handelsübliche Polymere dieser Art sind zum Beispiel "Milease(R)-T" von ICI United States, Inc., Repel-0-Teχ(R) SRP 3 von Rhöne-Poulenc und Zelcon(R) 8037 von DuPont.The soil-repellent polymers according to the invention, which contain groups with the formulas I and II above, are in the washing and cleaning agents according to the invention in an amount of 0.15% by weight to about 10% by weight, preferably about 0.25% by weight % to about 5% by weight, particularly preferably about 0.3% by weight to about 3% by weight. In these compounds, the molecular weight of the linking polyethylene oxide units is preferably in the range from 750 to 5000. The polymers can have an average molecular weight from approximately 5000 to approximately 200000. Ethylene terephthalate and polyethylene oxide terephthalate can be distributed arbitrarily in the polymer. Preferred polymers are those with molar ratios of ethylene terephthalate to polyethylene oxide terephthalate from about 65:35 to about 90:10, preferably from about 65:35 to about 80:20, the linking polyethylene oxide units having a molecular weight of 750-5000. preferably about 1000 to about 3000 and the polymer has a molecular weight of about 10,000 to about 50,000. Examples of commercially available polymers of this type are, for example, "Milease ( R ) -T" from ICI United States, Inc., Repel-0-Teχ ( R ) SRP 3 from Rhönen-Poulenc and Zelcon ( R ) 8037 from DuPont.
Die in erfindungsgemäßen Mitteln verwendeten schmutzabweisenden Polymere können durch bekannte Polymersationsverfahren hergestellt werden, wobei die Ausgangsmaterialien in solchen Mengen eingesetzt werden, um die oben genannten Verhältnisse von Ethylenterephthalat zu Polyethylenoxidterephtha¬ lat zu erhalten. Beispielsweise können die in der US-PS 3479212 beschrie¬ benen Verfahren zur Herstellung geeigneter Polymere verwendet werden.The dirt-repellent polymers used in agents according to the invention can be prepared by known polymerization processes, the starting materials being used in amounts such as to obtain the above-mentioned ratios of ethylene terephthalate to polyethylene oxide terephthalate. For example, the processes described in US Pat. No. 3,479,212 can be used to produce suitable polymers.
Als Hauptbuilderkomponente enthalten die Wasch- und Reinigungsmittel der Erfindung in der Regel feinkristallinen, synthetischen und gebundenes Was¬ ser enthaltenden Zeolith und/oder Alkalisilikate, obwohl erfindungsgemäße Mittel nicht auf diese Buildersubstanzen beschränkt sind. Der eingesetzte Zeolith ist vorzugsweise Zeolith vom A- und/oder P-Typ in Waschmittelqua¬ lität. Geeignet sind auch deren Gemische mit Zeolith NaX, wobei der Anteil des Zeoliths NaX in derartigen Gemischen normalerweise unter 30 % liegt. Sie weisen praktisch keine Teilchen größer als 30 μm auf und bestehen vor¬ zugsweise zu wenigstens 80 % aus Teilchen einer Größe kleiner als 10 μm. Bevorzugte Zeolithe weisen eine mittlere Teilchengröße von weniger als 10 μm (Meßmethode: Fraunhofer-Beugung; Mittelwert der VolumenVerteilung), bevorzugt zwischen 1,5 und 4,5 μm, insbesondere zwischen 2,0 und 4,0 μm auf. Ihr Calciumbindevermögen, das nach den Angaben der deutschen Patent¬ schrift DE 24 12837 bestimmt werden kann, liegt im Bereich von 100 bis 200 mg CaO/g. Der Gehalt der Mittel an feinteiligem, insbesondere kristal¬ linem, hydratisiertem Zeolith beträgt vorzugsweise 30 bis 65 Gew.-% und insbesondere 32 bis 45 Gew.- , bezogen auf wasserfreie Aktivsubstanz. Der Zeolith weist im allgemeinen einen Wassergehalt von 17 bis 25 Gew.-% auf, vorzugsweise 18 bis 22 Gew.-%, insbesondere 20 bis 22 Gew.-%. Die fakultativ enthaltenen Alkalisilikate werden als Feststoff und nicht in Form einer Lösung zugegeben. Sie können amorph oder kristallin vor¬ liegen. Bevorzugte Alkalisil kate sind die Natriumsilikate, insbesondere die amorphen Natriumsilikate, mit einem molaren Verhältnis Na2θ:Siθ2 von 1:2 bis 1:2,8. Derartige amorphe Alkalisilikate sind beispielsweise unter dem Namen Portil(R) im Handel erhältlich. Als kristalline Silikate, die allein oder im Gemisch mit amorphen Silikaten vorliegen können, werden vorzugsweise kristalline Schichtsilikate der Formel (I) NaMSixθ2χ+ι * yH2θ eingesetzt, in denen M für Natrium steht, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 ist und bevorzugte Werte für x 2, 3 oder 4 sind. Derartige kristalline Schichtsilikate werden beispielsweise in der euro¬ päischen Patentanmeldung 164 514 beschrieben. Bevorzugte kristalline Schichtsilikate der Formel (I) sind solche, in denen M für Natrium steht und x die Werte 2 oder 3 annimmt. Insbesondere sind sowohl ß- als auch δ'-Natriumdisilikate Na2Sι"2θ5.yH2θ bevorzugt, wobei ß-Natriumdisil kat bei¬ spielsweise nach dem Verfahren erhalten werden kann, das in der interna¬ tionalen Patentanmeldung W091/08171 beschrieben ist. Der Gehalt der Mittel an Alkalisilikaten beträgt vorzugsweise 1 bis 15 Gew.-% und insbesondere 2 bis 8 Gew.-%, bezogen auf wasserfreie Aktivsubstanz. Das Gewichtsverhält¬ nis Zeolith:amorphes Silikat, jeweils bezogen auf wasserfreie Aktivsub¬ stanz, beträgt vorzugsweise 4:1 bis 10:1. Die kristallinen Schichtsilikate werden in zeolithhaltigen Mitteln vorzugsweise in Mengen von 1 Gew.-% bis 15 Gew.-% und insbesondere 2 bis 7 Gew.-% eingesetzt, wobei das Gewichts¬ verhältnis Zeolith zu kristallinem Schichtsilikat, jeweils bezogen auf wasserfreie Aktivsubstanz, mindestens 5:1 beträgt. In Mitteln, die sowohl amorphe als auch kristalline Alkalisilikate enthalten, beträgt das Ge¬ wichtsverhältnis amorphes Alkalisilikat:kristallines Alkalisilikat vorzugs¬ weise 1:2 bis 2:1 und insbesondere 1:1 bis 2:1.As the main builder component, the washing and cleaning agents of the invention generally contain 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. The zeolite used is preferably zeolite of the A and / or P type in detergent quality. Their mixtures with zeolite NaX are also suitable, the proportion of the zeolite NaX in such mixtures normally being below 30%. They have practically no particles larger than 30 μm and preferably consist at least 80% of particles smaller than 10 μm. Preferred zeolites have an average particle size of less than 10 μm (measurement method: Fraunhofer diffraction; mean value of the volume distribution), preferably between 1.5 and 4.5 μm, in particular between 2.0 and 4.0 μm. Their calcium binding capacity, which can be determined according to the information in German patent DE 24 12837, is in the range from 100 to 200 mg CaO / g. The content of finely divided, in particular crystalline, hydrated zeolite in the compositions is preferably 30 to 65% by weight and in particular 32 to 45% by weight, 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 metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na2O: SiO2 molar ratio of 1: 2 to 1: 2.8. Such amorphous alkali silicates are commercially available, for example, under the name Portil ( R ). The crystalline silicates which may be present alone or in a mixture with amorphous silicates are preferably crystalline sheet silicates of the formula (I) NaMSi x θ2χ + ι * yH2θ, in which M represents sodium, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 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 are preferably .beta.- and δ 'Na2Sι-sodium "2θ5.yH2θ, wherein ß-Natriumdisil kat spielsweise can be obtained by the method / described in interna¬ tional patent application W091 08,171th The content of the agent of alkali silicates is preferably 1 to 15% by weight and in particular 2 to 8% by weight, based on anhydrous active substance, and the weight ratio of zeolite: amorphous silicate, based in each case on anhydrous active substance, is preferably 4: 1 to 10 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, is at least 5: 1. In agents which contain both amorphous and crystalline alkali silicates, the weight ratio is amorphous alkali silicate: crystalline Al potash silicate preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.
Erfindungsgemäß enthalten die Wasch- und Reinigungsmittel als Cobuilder Terpolymere in einer Menge von 1 bis 40 Gew.-%, bevorzugt 2 bis 25 Gew.-% und besonders bevorzugt 2 bis 15 Gew.-%. Diese Terpolymere enthalten als Monomereinheiten zwei Carbonsäuren und/oder deren Salze sowie als dritte Monomereinheit Vinylalkohol und/oder ein Vinylalkohol-Derivat oder ein Kohlenhydrat. Die erste saure Monomereinheit bzw. deren Salz leitet sich von einer monoethylenisch ungesättigten C3-Cs-Carbonsäure und vorzugsweise von einer C3-C4-Monocarbonsäure, insbesondere von der (Meth)acrylsäure ab. Die zweite saure Monomereinheit bzw. deren Salz kann ein Derivat einer C4-C8-Dicarbonsäure, vorzugsweise einer C4-C8-Dicarbonsäure sein, wobei Maleinsäure insbesondere bevorzugt ist. Die dritte Monomereeinheit wird in diesem Fall von Vinylalkohol und/oder vorzugsweise einem veresterten Vi¬ nylalkohol gebildet. Insbesondere sind Vinylalkohol-Derivate bevorzugt, welche einen Ester aus kurzkettigen Carbonsäuren, beispielsweise von C1-C4- Carbonsäuren, mit Vinylalkohol darstellen. Bevorzugte Terpolymere enthal¬ ten dabei 60 bis 95 Gew.-%, insbesondere 70 bis 90 Gew.-% (Meth)acrylsäure bzw. (Meth)acrylat, besonders bevorzugt Acrylsäure bzw. Acrylat, und Maleinsäure bzw. Maleat sowie 5 bis 40 Gew.-%, vorzugsweise 10 bis 30 Gew.-% Vinylalkohol und/oder Vinylacetat. Ganz besonders bevorzugt sind dabei Terpolymere, in denen das GewichtsVerhältnis (Meth)acrylsäure bzw. (Meth)acrylat zu Maleinsäure bzw. Maleat zwischen 1:1 und 4:1, vorzugs¬ weise zwischen 2:1 und 3:1 und insbesondere 2:1 und 2,5:1 liegt. Dabei sind sowohl die Mengen als auch die Gewichtsverhältnisse auf die Säuren bezogen.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 C3-Cs carboxylic acid and preferably from a C3-C4 monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer unit or its salt can be a derivative of a C4-C8 dicarboxylic acid, preferably a C4-C8 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 C1-C4 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 wt .-% 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 and 2.5: 1. Both the amounts and the weight ratios are based on the acids.
Die zweite saure Monomereinheit bzw. deren Salz kann auch ein Derivat ei¬ ner Allylsulfonsäure sein, die in 2-Stellung mit einem Alkylrest, vorzugs¬ weise mit einem Cι-C4-Alkylrest, oder einem aromatischen Rest, der sich vorzugsweise von Benzol oder Benzol-Derivaten ableitet, substituiert ist. Bevorzugte Terpolymere enthalten dabei 40 bis 60 Gew.-%, insbesondere 45 bis 55 Gew.-% (Meth)acrylsäure bzw. (Meth)acrylat, besonders bevorzugt Acrylsäure bzw. Acrylat, 10 bis 30 Gew.-%, vorzugsweise 15 bis 25 Gew.-% Methallylsulfonsäure bzw. Methailylsulfonat und als dritte Monomereinheit 15 bis 40 Gew.-%, vorzugsweise 20 bis 40 Gew.-% eines Kohlenhydrats. Dieses Kohlenhydrat kann dabei beispielsweise ein Mono-, Di-, Oligo- oder Poly- saccharid sein, wobei Mono-, Di- oder Oligosaccharide bevorzugt sind, be¬ sonders bevorzugt ist Saccharose. Durch den Einsatz der dritten Monomer¬ einheit werden Sollbruchstellen in dem Polymer eingebaut, die für die Ab- baubarkeit des Polymers verantwortlich sind. Die eingesetzten Terpolymere lassen sich nach jedem der bekannten und üblichen Verfahren herstellen.The second acidic monomer unit or its salt can also be a derivative of an allylsulfonic acid which, in the 2-position, has an alkyl radical, preferably 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 methyl sulfonate 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.
Bevorzugt werden auch solche Terpolymere eingesetzt, die entweder voll¬ ständig oder zumindest partiell, insbesondere zu mehr als 50 %, bezogen auf die vorhandenen Carboxylgruppen, neutralisiert sind. Besonders bevor¬ zugt ist dabei ein vollständig neutralisiertes Terpolymer, das also aus den Salzen der monomeren Säuren, insbesondere den Natrium- oder Kalium¬ salzen der monomeren Säuren, und Vinylalkohol oder einem Kohlenhydrat be¬ steht. Die Terpolymere weisen im allgemeinen eine relative Molekülmasse zwischen 1000 und 200000, vorzugsweise zwischen 200 und 50000 und insbe¬ sondere zwischen 3000 und 10000 auf. Sie werden zumeist in Form wäßriger Lösungen, vorzugsweise in Form 30 bis 50 gew.-%iger wäßriger Lösungen ein¬ gesetzt. Insbesondere bevorzugte Terpolymere werden nach Verfahren herge¬ stellt, die in der deutschen Patentschrift DE 4221 381 und der internatio¬ nalen Patentanmeldung WO 94/15978 beschrieben sind.Terpolymers which are either completely or at least partially, in particular to more than 50%, also preferably used are neutralized to the carboxyl groups present. A completely neutralized terpolymer is particularly preferred, ie it consists of the salts of the monomeric acids, in particular the sodium or potassium salts of the monomeric acids, and vinyl alcohol or a carbohydrate. The terpolymers generally have a relative molecular mass between 1000 and 200000, preferably between 200 and 50,000 and in particular between 3000 and 10,000. They are mostly used in the form of aqueous solutions, preferably in the form of 30 to 50% by weight aqueous solutions. Particularly preferred terpolymers are prepared by processes which are described in German patent DE 4221 381 and international patent application WO 94/15978.
Als weitere Gerüststoffe können zusätzlich auch übliche polymere Carboxy¬ late bzw. polymere Carbonsäuren, die aus einer oder zwei Monomereinheiten zusammengesetzt sind, enthalten sein. Diese polymeren Carboxylate bzw. Carbonsäuren können in erfindungsgemäßen Mitteln gegebenenfalls in einer Menge bis zu 15 Gew.-% vorliegen, fehlen jedoch vorzugsweise ganz. Es kom¬ men polymere Carboxylate bzw. polymere Carbonsäureπ mit einer relativen Molekülmasse von mindestens 350 in Form ihrer wasserlöslichen Salze, ins¬ besondere in Form der Natrium- und/oder Kaliumsalze, in Betracht, wie Poly- acrylate, Polyhydroxyacrylate, Polymethacrylate, Polymaleate und insbe¬ sondere Copoly ere der Acrylsäure mit Maleinsäure bzw. Maleinsäureanhy¬ drid, vorzugsweise solche aus 50 bis 70 % Acrylsäure und 50 bis 10 % Maleinsäure. Die relative Molekülmasse der Homopolymeren liegt im allge¬ meinen zwischen 1000 und 100000, die der Copolymeren zwischen 2000 und 200000, vorzugsweise 50000 bis 120000, bezogen auf freie Säure. Ein üblicherweise besonders bevorzugtes Acrylsäure-Maleinsäure-Copolymer weist eine relative Molekülmasse von 50000 bis 100000 auf.Conventional polymeric carboxylates or polymeric carboxylic acids which are composed of one or two monomer units can also be present as further builders. These polymeric carboxylates or carboxylic acids can be present in the agents according to the invention in an amount of up to 15% by weight, but are preferably absent entirely. 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, are considered, such as polyacrylates, polyhydroxyacrylates, polymethacrylates, polymaleates and in particular copolymers of acrylic acid with maleic acid or maleic acid anhydride, preferably those made 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 200000, preferably 50,000 to 120,000, based on free acid. A usually particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000.
Ein erfindungsgemäßes Wasch- und Reinigungsmittel enthält ein Enzym aus der Klasse der Cellulasen. Die erfindungsgemäß verwendete Cellulase gehört zu den aus Mikroorganismen, insbesondere Bakterien oder Pilzen gewinnbaren Enzymen, welche ein pH-Optimum vorzugsweise im fast neutralen bis schwach alkalischen pH-Bereich von 6 bis 9,5 aufweisen. Derartige Cellulasen sind beispielsweise aus den deutschen Offenlegüngsschriften DT 2247832, DE 31 17 250, DE 3207825, DE 3207847 sowie DE 3322950, der britischen Patentanmeldung GB 2232983, den europäischen Patentanmeldungen EP 0265832, EP 0269077, EP 0270974, EP 0271 004, EP 0339550, EP 0458162 sowie EP 0468464 oder den internationalen Patentanmeldungen 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 sowie WO 94/14953 be¬ kannt. Sie werden im erfindungsgemäßen Mittel vorzugsweise in solchen Mengen eingesetzt, daß das fertige Mittel eine cellulolytische Aktivität von 0,05 IU/g bis 1,5 IU/g ("International Units" pro Gramm, basierend auf der enzymatischen Hydrolyse von Na-Carboxymethylcellulose bei pH 9,0 und 40 °C, wie in Agric. Bio!. Chem. 53, 1275 (1989) von S. Ito et al. be¬ schrieben), insbesondere 0,07 IU/g bis 1,4 IU/g und besonders bevorzugt 0,1 IU/g bis 1,3 IU/g aufweist. Geeignete Handelsprodukte sind beispiels¬ weise Celluzyme(R) der Novo Nordisk oder KAC(R) von Kao.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, for example, from German Offenlegungssschriften DT 2247832, DE 31 17 250, DE 3207825, DE 3207847 and DE 3322950, the British Patent application GB 2232983, European patent applications EP 0265832, EP 0269077, EP 0270974, EP 0271 004, EP 0339550, EP 0458162 and EP 0468464 or 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. Bio! Chem. 53, 1275 (1989) by S. Ito et al.), in particular 0.07 IU / g to 1.4 IU / g and particularly preferably 0.1 IU / g to 1.3 IU / g. Suitable commercial products are, for example, Celluzyme ( R ) from Novo Nordisk or KAC ( R ) from Kao.
Die erfindungsgemäßen Waschmittel können wasserlösliche Komplexbildner aus der Gruppe der Phosphonate enthalten. Es werden Salze von Polyphosphon¬ säuren wie neutral reagierende Natriumsalze von beispielsweise 1-Hydroxy- ethan-l,l-diphosphonat und Diethylentriaminpentamethylenphosphonat verwen¬ det. Die Phosphonate können in Mengen bis zu 1,5 Gew.-% eingesetzt werden.The detergents according to the invention can contain water-soluble complexing agents from the group of the phosphonates. Salts of polyphosphonic acids, such as neutral sodium salts of, for example, 1-hydroxyethane-l, l-diphosphonate and diethylenetriaminepentamethylenephosphonate are used. The phosphonates can be used in amounts of up to 1.5% by weight.
Als weitere übliche Bestandteile enthalten die Wasch- und Reinigungsmittel normalerweise tensidische Verbindungen aus der Gruppe der nichtionischen Tenside, ferner können anionische und/oder zwitterionische Tenside enthal¬ ten sein. Die Tenside liegen im allgemeinen in den erfindungsgemäßen Wasch¬ mitteln mit einem Gesamtgehalt von 5 bis 40 Gew.-%, vorzugsweise von 5 bis 30 Gew.-% und insbesondere von 8 bis 25 Gew.-% vor.The detergents and cleaning agents normally contain surfactant compounds from the group of nonionic surfactants as further customary constituents, and anionic and / or zwitterionic surfactants may also be present. The surfactants are generally present in the detergents according to the invention with a total content of 5 to 40% by weight, preferably 5 to 30% by weight and in particular 8 to 25% by weight.
Als nichtionische Tenside enthält das erfindungsgemäße Waschmittel ins¬ besondere niedrigethoxylierte und höherethoxylierte nichtionische Tenside. Die nichtionischen Tenside können in einer Menge von bis zu 25 Gew.-%, vorzugsweise bis zu 15 Gew.-%, vorliegen. Die als nichtionische Tenside vorzugsweise eingesetzten ethoxylierten Alkohole leiten sich von primären Alkoholen mit vorzugsweise 9 bis 18 Kohlenstoffatomen ab. Die niedrig- ethoxylierten Fettalkohole weisen durchschnittlich 1 bis 6 Mol und die höherethoxylierten Alkohole durchschnittlich 7 bis 20 Mol Ethylenoxid auf. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Der Alkoholrest kann linear oder in 2-Stellung methylverzweigt sein, bzw. lineare und methylverzweigte Reste im Gemisch enthalten, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch Alkoholethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 Kohlenstoffatomen bevorzugt, z. B. aus Kokos-, Taigfett- oder Oleylalkohol. Zu den bevorzugten niedrigethoxylierten Alkoholen gehören beispielsweise Fettalkohole mit 12 bis 18 Kohlenstoffatomen mit durch¬ schnittlich 3 bis 6 EO-Einheiten. Zu den bevorzugten höherethoxylierten Alkoholen gehören beispielsweise Fettalkohole mit 16 bis 18 Kohlenstoff¬ atomen mit durchschnittlich 12 bis 16 EO-Einheiten, z.B. ethoxylierter Palmalkohol. Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologen- verteilung auf (narrow ränge ethoxylates, NRE). Die erfindungsgemäßen Waschmittel enthalten vorzugsweise 1 Gew.-% bis 10 Gew.-%, insbesondere 1 Gew.-% bis 5 Gew.-% niedrigethoxylierte nichtionische Tenside und 1 - Gew.-% bis 10 Gew.-%, insbesondere 1 Gew.-% bis 5 Gew.-% höherethoxylierte nichtionische Tenside. Die niedrigethoxylierten Alkohole und die höher¬ ethoxylierten Alkohole liegen vorzugsweise in einem GewichtsVerhältnis von 10:1 bis 1:10, bevorzugt 5:1 bis 1:5, insbesondere 2:1 bis 1:1 vor.The detergent according to the invention contains in particular low-ethoxylated and higher-ethoxylated nonionic surfactants as nonionic surfactants. The nonionic surfactants can be present in an amount of up to 25% by weight, preferably up to 15% by weight. The ethoxylated alcohols preferably used as nonionic surfactants 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 the higher ethoxylated alcohols have an average of 7 to 20 moles of ethylene oxide. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. The alcohol radical can be linear or methyl-branched in the 2-position, or contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms are preferred, e.g. B. from coconut, tallow or oleyl alcohol. The preferred low-ethoxylated alcohols include, for example, fatty alcohols having 12 to 18 carbon atoms with an average of 3 to 6 EO units. The preferred higher ethoxylated alcohols include, for example, fatty alcohols with 16 to 18 carbon atoms with an average of 12 to 16 EO units, for example ethoxylated palm alcohol. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). The detergents according to the invention preferably contain 1% by weight to 10% by weight, in particular 1% by weight to 5% by weight of low-ethoxylated nonionic surfactants and 1% by weight to 10% by weight, in particular 1% by weight. % to 5% by weight of 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.
Weitere Klassen nichtionischer Tenside, die allein oder in Kombination mit den oben genannten nichtionischen Tensiden eingesetzt werden können, sind alkoxylierte Fettsäuremethylester, wie sie beispielsweise in der japani¬ schen Patentanmeldung JP 58/217598 beschrieben sind oder die vorzugsweise nach dem in der internationalen Patentanmeldung WO 90/13533 beschriebenen Verfahren hergestellt werden, und Alkylglykoside der allgemeinen Formel R0(G)x, in der R einen primären geradkettigen oder methylverzweigten, ins¬ besondere in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet und G für eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glukose, steht. Der Oligomerisierungs- grad x, der die Verteilung von Monoglykosiden und Oligoglykosiden angibt, ist eine beliebige Zahl zwischen 1 und 10; vorzugsweise liegt x bei 1,2 bis 1,4. Alkylglykoside können bevorzugt in einer Menge von bis zu 5 Gew.-%, insbesondere von 0,5 Gew.-% bis 3 Gew.-% in den erfindungsge¬ mäßen Waschmitteln enthalten sein. Als in den erfindungsgemäßen Mitteln brauchbare Aπiontenside kommen Sul¬ fate und gegebenenfalls Sulfonate sowie Seifen aus vorzugsweise natür¬ lichen Fettsäuren bzw. Fettsäuregemischen in Betracht. Insgesamt können die Aniontenside in den erfindungsgemäßen Mitteln in einer Menge bis zu 15 Gew.-% vorliegen. Geeignete Tenside vom Sulfat-Typ sind Schwefelsäuremono¬ ester aus primären Alkoholen natürlichen und synthetischen Ursprungs. Als Alk(en)ylsulfate werden die Schwefelsäurehalbester der Ci2-Ci8-Fettalkohole beispielsweise aus Kokosfettalkohol, Taigfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol, oder den Cιo-C2θ~0xoalkoholen, und diejenigen sekundären Alkohole dieser Kettenlänge bevorzugt. Weiterhin bevorzugt sind Alk(en)ylsulfate der genannten Kettenlänge, welche einen synthetischen, auf petrochemischer Basis hergestellten geradkettigen Alkylrest enthalten, die ein analoges Abbauverhalten besitzen, wie- die adäquaten Verbindungen auf der Basis von fettchemischen Rohstoffen. Aus waschtechnischem Inter¬ esse sind Ci6-Ci8-Alk(en)ylsulfate insbesondere bevorzugt. Dabei kann es auch von besonderem Vorteil und insbesondere für maschinelle Waschmittel von Vorteil sein, Ci6-Ci8-Alk(en)ylsulfat in Kombination mit niedriger schmelzenden Aniontensiden und insbesondere mit solchen Aniontensiden, die einen niedrigeren Krafft-Punkt aufweisen und bei relativ niedrigen Wasch¬ temperaturen von beispielsweise Raumtemperatur bis 40°C eine geringe Kristallisationsneigung zeigen, einzusetzen. In einer bevorzugten Aus¬ führungsform der Erfindung enthalten die Mittel daher Mischungen auf kurz¬ kettigen und langkettigen Fettalkylsulfaten, vorzugsweise Mischungen aus Ci2-Cχ4-Fettalkylsulfaten oder Ci2-Ci6-Fettalkylsulfaten mit Cjö-Cis-Fett- alkylsulfaten. In einer weiteren bevorzugten Ausführungsform der Erfindung werden jedoch nicht nur gesättigte Alkylsulfate, sondern auch ungesättigte Alkenylsulfate mit einer Alkenylkettenlänge von vorzugsweise C16-C22 ein¬ gesetzt. Dabei sind insbesondere Mischungen aus gesättigten, überwiegend aus Cχ6 bestehenden sulfatierten Fettalkoholen und ungesättigten, überwie¬ gend aus Cis bestehenden sulfatierten Fettalkoholen bevorzugt, beispiels¬ weise solche, die sich von festen oder flüssigen Fettalkoholmischungen des Typs HD-0cenol(R) (Handelsprodukt des Anmelders) ableiten. Dabei sind Ge¬ wichtsverhältnisse von Alkylsulfaten zu Alkenylsulfaten von 10:1 bis 1:2 und insbesondere von etwa 5:1 bis 1:1 bevorzugt. Die erfindungsgemäßen Mittel können bis zu 12 Gew.-% Alk(en)ylsulfate enthalten, vorzugsweise 5 Gew.-% bis 8 Gew.-%. Auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten geradkettigen oder verzweigten C7-C2i-Alkohole, wie 2-Methyl-verzweigte Cg-Cji-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (E0) oder Cχ2-Ci8-Fettalkohole mit 2 bis 4 E0, sind geeignet. Sie werden in Waschmitteln für den maschinellen Einsatz aufgrund ihres hohen Schaumvermögens nur in relativ geringen Mengen, beispielsweise in Mengen von 1 bis 5 Gew.-%, eingesetzt. Werden Tenside vom Sulfonat-Typ verwendet, kommen vorzugsweise Cg-Cis-Alkylbenzolsulfonate, Olefinsulfo- nate, das heißt Gemische aus Alken- und Hydroxyalkansulfonaten sowie Di- sulfonaten, wie man sie beispielsweise aus Ci2-Ci8-M°n°°lefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließender alkalischer oder saurer Hydrolyse der Sulfonierungsprodukte erhält, in Betracht. Diese Tenside können mit einem Gehalt bis zu 10 Gew.-% im Mittel vorliegen, vorzugsweise bis zu 5 Gew.-%. Es kann aber auch auf Tenside vom Sulfonat-Typ ohne wesentliche Beein¬ trächtigung der Waschwirkung verzichtet werden.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 described in international patent application WO 90 / 13533 are described, and alkyl glycosides of the general formula R0 (G) x , in which R is a primary straight-chain or methyl-branched, in particular in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G represents a glycose unit with 5 or 6 carbon atoms, preferably 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. Suitable anionic surfactants which can be used in the agents according to the invention are sulphates and, if appropriate, sulphonates and soaps composed of preferably natural fatty acids or fatty acid mixtures. Overall, the anionic surfactants can be present in the agents according to the invention in an amount of up to 15% by weight. Suitable sulfate-type surfactants are sulfuric acid monoesters from primary alcohols of natural and synthetic origin. As alk (en) yl sulfates, the sulfuric acid half-esters of the Ci2-Ci8 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the Cιo-C2θ ~ 0xoalcohols, and those secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based, straight-chain alkyl radical which have an analogous degradation behavior, as well as the adequate compounds based on oleochemical raw materials. Ci6-Ci8-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 Ci6-Ci8-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 with relatively low detergents temperatures from, 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 Ci2-Cχ4-fatty alkyl sulfates or Ci2-Ci6-fatty alkyl sulfates with Cjo-Cis-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 C16-C22 are used. Mixtures of saturated sulfated fatty alcohols consisting predominantly of Cχ6 and unsaturated sulfated fatty alcohols consisting predominantly of cis are particularly preferred, for example those which are derived from solid or liquid fatty alcohol mixtures of the type HD-0cenol ( R ) (commercial product of the applicant ). Weight ratios of alkyl sulfates to alkenyl sulfates of 10: 1 to 1: 2 and in particular of 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. Also the sulfuric acid monoesters with 1 to 6 mol Ethylene oxide ethoxylated straight-chain or branched C7-C2i alcohols, such as 2-methyl-branched Cg-Cji alcohols with an average of 3.5 mol of ethylene oxide (E0) or Cχ2-Ci8 fatty alcohols with 2 to 4 E0, 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 Cg-Cis-alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates and also disulfonates of the type found, for example, in Ci2-Ci8-M ° n ° ° olefins - Or internal double bond obtained by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. These surfactants can be up to 10% by weight on average, preferably up to 5% by weight. However, it is also possible to dispense with sulfonate-type surfactants without significantly affecting the washing action.
Als weitere anionische Tenside kommen insbesondere Seifen in Betracht, wobei gesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristin- säure, Palmitinsäure oder Stearinsäure, sowie aus natürlichen Fettsäuren, zum Beispiel Kokos-, Palmkern-, oder Taigfettsäuren, abgeleitete Seifen¬ gemische geeignet sind. Insbesondere sind solche Seifengemische bevorzugt, die zu 50 bis 100 Gew.-% aus gesättigten Ci2-Ci8-Fettsäureseifen und zu 0 bis 50 Gew.- aus Ölsäureseife zusammengesetzt sind. Bevorzugt enthalten die erfindungsgemäßen Waschmittel Seife in Mengen von 0,1 Gew.- bis 1,5 Gew.-%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, as well as 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 Ci2-Ci8 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.
Die erfindungsgemäßen Waschmittel enthalten vorzugsweise Peroxybleichmit- tel, insbesondere in Kombination mit Bleichaktivatoren. Unter den als Bleichmittel dienenden, in Wasser H2O2 liefernden Verbindungen haben das Natriumperborattetrahydrat und das Natriumperboratmonohydrat besondere Be¬ deutung. Weitere brauchbare Bleichmittel sind beispielsweise Natriumper- carbonat, Peroxypyrophosphate, Citratperhydrate sowie sonstige persaure Salze oder Persäuren, wie Perbenzoate, Peroxophthalate, Diperoxyazelain- säure oder Diperoxydodecandisäure. Die Waschmittel enthalten vorzugsweise 5 bis 25 Gew.-% und insbesondere 10 bis 20 Gew.-% Bleichmittel, wobei be¬ vorzugt Natriumperboratmonohydrat, -tetrahydrat oder Natriumpercarbonat eingesetzt wird. Um insbesondere beim Waschen bei Temperaturen von 60°C und darunter eine verbesserte Bleichwirkung zu erreichen, können Bleich¬ aktivatoren in die Präparate eingearbeitet werden, die mit H2O2 organische Persäuren bilden. Beispiele hierfür sind N- oder O-Acyl-Verbindungen, bei¬ spielsweise mehrfach acylierte Alkylendiamine, insbesondere Tetraacetyl- ethylendiamin, acylierte Glykolurile, insbesondere Tetraacetylglykoluril, N-acylierte Hydantoine, Hydrazide, Triazole, Triazine, Urazole, Diketopi- perazine, Sulfurylamide und Cyanurate, außerdem Carbonsäureanhydride, ins¬ besondere Phthalsäureanhydrid, Carbonsäureester, insbesondere Natriu - isononanoyloxybenzolsulfonat, und acylierte Zuckerderivate, insbesondere Pentaacetylglukose. Der Bleichaktivator kann in bekannter Weise mit Hüll- substanzen überzogen oder, gegebenenfalls unter Einsatz von Hilfsmitteln, granuliert oder extrudiert/pelletiesiert worden sein und gewünschtenfalls weitere Zusatzstoffe, beispielsweise Farbstoff, enthalten. Vorzugsweise enthält ein derartiges Granulat über 70 Gew.-%, insbesondere von 90 Gew.-% bis 99 Gew.-%, Bleichaktivator. Vorzugsweise wird ein Bleichaktivator ein¬ gesetzt, der unter den Waschbedingungen Peressigsäure bildet. Unter diesen ist mit Hilfe von Carboxymethylcellulose granuliertes Tetraacetylethylen- diamin (TAED) mit mittleren Korngrößen von 0,01 bis 0,8 mm, wie es nach dem in der europäischen Patentschrift EP 037 026 beschriebenen Verfahren hergestellt werden kann, und/oder granuliertes l,5-Diacetyl-2,4-dioxohexa- hydro-l,3,5-triazin (DADHT), wie es nach dem in der deutschen Patentschrift DD 255 884 beschriebenen Verfahren hergestellt werden kann, besonders be¬ vorzugt. Es kann auch extrudiertes TAED eingesetzt werden, welches >. 70 Gew.-% TAED, 15 bis 25 Gew.-% C^-is-Fettalkoholsulfat und 2 bis 6 Gew.-% Soda enthält. Der Gehalt an Bleichaktivatoren in den bleichmittelhaltigen Waschmitteln liegt in dem üblichen Bereich, vorzugsweise zwischen 1 und 10 Gew.-% und insbesondere zwischen 3 und 8 Gew.-%.The detergents according to the invention preferably contain peroxy bleach, in particular in combination with bleach activators. Of the compounds which provide H2O2 in water and serve as bleaching agents, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other usable 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 is used. In order to achieve an improved bleaching effect, particularly when washing at temperatures of 60 ° C. and below, bleach activators can be incorporated into the preparations which form organic peracids with H2O2. Examples of these are N- or O-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, triazines, urazoles, diketopiperazines, sulfurylamides and cyanurate amides , in addition carboxylic anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyloxybenzenesulfonate, and acylated sugar derivatives, in particular 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 oil, 5-Diacetyl-2,4-dioxohexa- hydro-l, 3,5-triazine (DADHT), as can be prepared by the process described in German Patent DD 255 884, is particularly preferred. Extruded TAED can also be used, which>. Contains 70% by weight of TAED, 15 to 25% by weight of C 1-5 fatty alcohol sulfate and 2 to 6% by weight of soda. 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.
Zu den sonstigen Waschmittelbestandteilen, deren Anteil je nach Zusammen¬ setzung der Waschmittel 0,1 bis 5 Gew.-% beträgt, zählen Schauminhibito¬ ren, optische Aufheller, textilweichmachende Stoffe sowie Färb- und Duft¬ stoffe. Es können auch Neutralsalze in einer Menge bis zu 20 Gew.-% ent¬ halten sein, ihr Anteil liegt bevorzugt unter 10 Gew.- ^%°. Ferner kann das erfindungsgemäße Mittel zusätzliche Vergrauungsinhibitoren in einer Menge von 0,1 bis 5 Gew.-%, bezogen auf die Mittel, enthalten. Als zusätzliche Vergrauungsinhibitoren sind wasserlösliche Kolloide meist organischer Natur geeignet, beispielsweise lösliche Stärkepräparate und zum Beispiel abgebaute Stärke, Aldehydstärken und so weiter. Carboxymethyl- cellulose (Na-Salz), Methylcellulose, Methylhydroxyethylcellulose und deren Gemische sowie Polyvinylpyrrolidon werden bevorzugt eingesetzt.The other detergent components, the proportion of which, depending on the composition of the detergent, is 0.1 to 5% by weight, include foam inhibitors, optical brighteners, textile-softening substances and colorants and fragrances. Neutral salts can also be present in an amount of up to 20% by weight, their proportion preferably being 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% by weight, based on the agent. Water-soluble colloids of mostly organic nature are suitable as additional graying inhibitors, for example soluble starch preparations and, for example, degraded starch, aldehyde starches and so on. Carboxymethyl cellulose (sodium salt), methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof, and polyvinyl pyrrolidone are preferably used.
Neben der erfindungsgemäß eingesetzten Cellulase können die Wasch- und Reinigungsmittel weitere Enzyme wie Protease, Amylase und Lipase enthal¬ ten.In addition to the cellulase used according to the invention, the detergents and cleaning agents can contain further enzymes such as protease, amylase and lipase.
Zu den in den erfindungsgemäßen Mitteln einsetzbaren Proteasen gehören die aus Mikroorganismen, insbesondere Bakterien oder Pilzen, gewinnbaren Enzyme mit einem pH-Optimum im alkalischen Bereich, beispielsweise die aus den internationalen Patentanmeldungen WO 92/07067, WO 91/02792, WO 88/03947 oder WO 88/03946 oder den europäischen Patentanmeldungen EP 471 265, EP 416 967 oder EP 394 352 bekannten Proteasen. Protease wird im erfindungs¬ gemäßen Mittel vorzugsweise in solchen Mengen eingesetzt, daß das fertige Mittel 100 PE/g bis 15000 PE/g (Protease-Einheiten pro Gramm, bestimmt nach der in Tenside 7, 125 (1970) beschriebenen Methode), insbesondere 125 PE/g bis 7500 PE/g und besonders bevorzugt 150 PE/g bis 4500 PE/g aufweist. Geeignete Proteasen sind im Handel erhältlich, beispielsweise unter den Namen BLAP(R), Savinase(R), Durazym(R), Esperase(R), Maxatase(R), Maxa- pem(R), 0ptimase(R), 0pticlean(R) oder Alcalase(R).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, with a pH optimum in the alkaline range, for example those from the international patent applications WO 92/07067, WO 91/02792, WO 88/03947 or WO 88/03946 or the European patent applications EP 471 265, EP 416 967 or EP 394 352 known proteases. Protease is preferably 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 Tenside 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 ), Maxatase ( R ), Maxapem ( R ), 0ptimase ( R ), 0pticlean ( R ) or Alcalase ( R ).
Zu den in erfindungsgemäßen Mitteln einsetzbaren Amylasen gehören die aus Bakterien oder Pilzen gewinnbaren Enzyme, welche ein pH-Optimum vorzugs¬ weise im alkalischen Bereich bis etwa pH 10 aufweisen. Brauchbare Handels¬ produkte sind beispielsweise Termamyl(R) und Maxamyl(R). Amylase wird im erfindungsgemäßen Mittel vorzugseise in solchen Mengen eingesetzt, daß das fertige Mittel 0,01 KNU/g bis 3 KNU/g ("Kilo-Novo-Units" pro Gramm gemäß der Standard-Methode der Firma Novo, wobei 1 KNU die Enzymmenge ist, die 5,26 g Stärke bei pH 5,6 und 37°C abbaut, basierend auf der von P. Bern¬ feld in S.P. Colowick und N.D. Kaplan, Methods in Enzymology, Band 1, 1955, Seite 149 beschriebenen Methode), insbesondere 0,010 KNU/g bis 1,8 KNU/g und besonders bevorzugt 0,01 KNU/g bis 1,6 KNU/g aufweist.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 are, for example, 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 that of P. Bernfeld in SP Colowick and ND Kaplan, Methods in Enzymology, Volume 1, 1955, Page 149 described method), in particular 0.010 KNU / g to 1.8 KNU / g and particularly preferably 0.01 KNU / g to 1.6 KNU / g.
Bei der Lipase handelt es sich um ein aus Mikroorganismen, insbesondere Bakterien oder Pilzen, gewinnbares Enzym. Ein solches ist beispielsweisse aus den europäischen Patentanmeldungen EP 204208, EP 214761, EP 258068, EP 407 225 oder der internationalen Patentanmeldung WO 87/859 bekannt. Brauchbare im Handel erhältiche Lipasen sind beispielsweise Lipolase(R) und Lipozym(R). Lipase wird im erfindungsgemäßen Mittel vorzugsweise in solchen Mengen eingesetzt, daß das fertige Mittel 10 LU/g bis 10 000 LU/g ("Lipase-activity Units" pro Gramm, bestimmt über die enzy atische Hydro¬ lyse von Tributyrin bei 30°C und pH 7 nach der in EP 258 068 genannten Methode), insbesondere 80 LU/g bis 5 000 LU/g und besonders bevorzugt 100 LU/g bis 1000 LU/g aufweist.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 204208, EP 214761, EP 258068, 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 via the enzymatic hydrolysis of tributyrin at 30 ° C. and pH 7 according to the method mentioned in EP 258 068), in particular 80 LU / g to 5,000 LU / g and particularly preferably 100 LU / g to 1000 LU / g.
Die Enzyme können in an sich bekannter Weise an Trägerstoffen adsorbiert, in Hüllsubstanzen eingebettet und/oder mit Hilfe von Trägersubstanzen granuliert worden sein, um sie leichter handhabbar zu machen und gegen vorzeitige Inaktivierung zu schützen, wenn sie in Wasch- oder Reinigungs¬ mittel eingearbeitet werden sollen.The enzymes can be adsorbed onto carrier substances in a manner known per se, embedded in coating substances and / or granulated with the aid of carrier substances in order to make them easier to handle and to protect against premature inactivation when they are incorporated into washing or cleaning agents should.
Beim Einsatz in maschinellen Waschverfahren kann es von Vorteil sein, den Mitteln übliche Schauminhibitoren zuzusetzen. Als Schauminhibitoren eignen sich beispielsweise Seifen natürlicher oder synthetischer Herkunft, die einen hohen Anteil an Ci8-C24-Fettsäuren aufweisen. Geeignete nichttensid- artige Schauminhibitoren sind beispielsweise Organopolysiloxane und deren Gemische mit mikrofeiner, gegebenenfalls silanierter Kieselsäure sowie Paraffine, Wachse, Mikrokristallinwachse und deren Gemische mit silanierter Kieselsäure oder Bistearylethylendiamid. Vorteilhafterweise werden auch Gemische verschiedener Schauminhibitoren verwendet, zum Beispiel solche aus Silikonen und Paraffinen oder Wachsen. Vorzugsweise sind die Schaum¬ inhibitoren, insbesondere Silikon- oder paraffinhaltige Schauminhibitoren, an eine granuläre, in Wasser lösliche beziehungsweise dispergierbare Trägersubstanz gebunden. Insbesondere sind dabei Mischungen aus Paraffinen und Bistearoylethylendiamiden bevorzugt. In einer bevorzugten Ausführungsform enthalten die erfindungsgemäßen Wasch- und Reinigungsmittel 30 Gew.-% bis 55 Gew.-% wasserunlöslichen anor¬ ganischen Builder, 2,5 Gew.-% bis 20 Gew.-% synthetisches Aniontensid, 1 Gew.-% bis 20 Gew.-% nichtionische Tensidkomponeπte, bis zu 25 Gew.-%, insbesondere 1 Gew.-% bis 15 Gew.-% Bleichmittel, bis zu 8 Gew.-%, insbe¬ sondere 0,5 Gew.-% bis 6 Gew.-% Bleichaktivator und bis zu 20 Gew.- , ins¬ besondere 0,1 Gew.-% bis 15 Gew.-% anorganische Salze, insbesondere Alkali- carbonat, -sulfat und/oder -chlorid, sowie bis zu 2 Gew.-%, insbesondere 0,4 Gew.-% bis 1,2 Gew.-% teilchenförmig konfektioniertes weiteres Enzym, insbesondere Protease, Amylase und/oder Lipase.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 Ci8-C24 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 and cleaning agents according to the invention contain 30% by weight to 55% by weight of water-insoluble inorganic builder, 2.5% by weight to 20% by weight of synthetic anionic surfactant, 1% by weight to 20% by weight of nonionic surfactant components, up to 25% by weight, in particular 1% by weight to 15% by weight of bleaching agent, up to 8% by weight, in particular 0.5% by weight to 6 % By weight of bleach activator and up to 20% by weight, in particular 0.1% by weight 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 .-% particulate assembled further enzyme, in particular protease, amylase and / or lipase.
Die erfindungsgemäßen Mittel können in an sich bekannter Weise, beispiels¬ weise durch Mischen, Granulieren, Extrudieren und/oder durch Sprühtrocknung hergestellt werden. Vorzugsweise bestehen die schüttfähigen pulverförmigen, extrudierten oder granulären Präparate aus einem trockenen homogenen Ge¬ misch von mindestens zwei Pulverkomponenten, wovon die erste als sprüh¬ getrocknetes Pulver vorliegt. Dieses ist durch eine in konventioneller Weise durchgeführte Sprühtrocknung eines Slurries erhältlich, der zumin¬ dest die anionischen Tenside und den Zeolith in einer wäßrigen Suspension sowie gegebenenfalls nichtionische Tenside enthält. Bleichmittel wie Perbo¬ rat werden wie üblich wegen ihrer thermischen Empfindlichkeit nicht zu¬ sammen mit den Bestandteilen der ersten Pulverkomponente sprühgetrocknet, sondern erst nachträglich dem Sprühprodukt zugemischt. Beim Extrudieren wird Perborat in der Regel gemeinsam mit den mei-sten anderen Bestandteilen coextrudiert. Es kann dort von einem vorgefertigten Turmpulver als einer der Extrusionskomponenten sowie von einem Non-tower-Extrudat oder der Mehr- Extrudattechnologie ausgegangen werden. Alkalisilikate werden wegen der bekannten Zeolith/Alkalisilikat-Unverträglichkeit unter Sprühtrocknungsbe¬ dingungen nicht mit dem zeolithhaltigen Slurry sprühgetrocknet. Ebenso werden die gegebenenfalls vorhandenen Schichtsilikate vorzugsweise nicht sprühgetrocknet, sondern in granulärer Form oder adsorbiert an einen Trä¬ ger, der beispielsweise aus Sulfat und/oder Carbonat besteht, zugemischt. Die Schichtsilikate können aber auch im Extrusionsprozeß coextrudiert wer¬ den. Die Herstellung der erfindungsgemäßen Mittel kann in einfachster Weise durch Zumischen der Enzympartikel in einem üblichen Mischer, insbesondere einem Trommel-, Rollen-, Band- oder Freifallmischer erfolgen, wobei fakul¬ tative sonstige pulverförmige Bestandteile, insbesondere Bleichmittel, und gewünschtenfalls auch flüssige beziehungsweise verflüssigte Bestandteile, zu denen insbesondere nichtionische Tenside aber auch Färb- und Duftstoffe gehören, durch Aufsprühen zugemischt werden können. Auch die Einarbeitung der sonstigen Bestandteile durch Zumischen eines diese enthaltenden Granu¬ lats beziehungsweise Extrudats zu den weiteren Bestandteilen ist möglich und insbesondere zur Herstellung von Waschmitteln mit relativ hohem Schütt¬ gewicht von vorzugsweise 650 g/1 bis 900 g/1 bevorzugt.The agents according to the invention can be prepared in a manner known per se, for example by mixing, granulating, extruding and / or by spray drying. The pourable powdered, extruded or granular preparations preferably consist of a dry homogeneous mixture of at least two powder components, the first of which is in the form of a spray-dried powder. This can be obtained by spray drying a slurry which comprises at least the anionic surfactants and the zeolite in an aqueous suspension and, if appropriate, nonionic surfactants. Because of their thermal sensitivity, bleaching agents such as perboate are not spray-dried together with the constituents of the first powder component, but are only mixed into the sprayed product subsequently. When extruding, perborate is usually co-extruded with most other ingredients. A pre-made tower powder as one of the extrusion components as well as a non-tower extrudate or multi-extrudate technology can be assumed there. Because of the known incompatibility with zeolite / alkali silicate, alkali silicates are not spray-dried with the zeolite-containing slurry under spray drying conditions. Likewise, the layered silicates which may be present are preferably not spray-dried, but mixed in in granular form or adsorbed onto a carrier which consists, for example, of sulfate and / or carbonate. However, the layered silicates can also be coextruded in the extrusion process. The agents according to the invention can be produced in the simplest manner by admixing the enzyme particles in a conventional mixer, in particular a drum, roller, belt or free-fall mixer, optional other powdery constituents, in particular bleaching agents, and if desired also liquid or liquefied constituents , which include in particular nonionic surfactants but also colorants and fragrances, can be mixed in by spraying. The incorporation of the other constituents by admixing a granulate or extrudate containing them with the other constituents is also possible and is particularly preferred for the production of detergents with a relatively high bulk density of preferably 650 g / 1 to 900 g / 1.
BeispieleExamples
Es wurde ein granuläres Basiswaschmittel (BW) der Zusammensetzung 12 Gew.- synthetisches Aniontensid, 2 Gew.-% Seife, 9 Gew.-% Niotensid, 35 Gew.-% Zeolith Na-A, 11 Gew.-% Na-Citrat, 10 Gew.-% Na-Carbonat, 2 Gew.-% Na- Silikat, 8 Gew.-% Na-Sulfat, Rest auf 100 Gew.-% Wasser, hergestellt, mit den in Tabelle 1 angegebenen Mengen der dort aufgeführten Zusätze vermischt und das erfindungsgemäße Mittel Hl mit BW und den Vergleichsmitteln VI bis V4 unter praxisnahen Bedingungen getestet. Dazu wurden in einem Laundero- meter, Typ Atlas Standard (FlottenVerhältnis 1:12, Wasserhärte 16 °dH, 8,4 Gramm Waschmittel pro Liter Waschlösung) jeweils 2,1 g der mit den in der nachfolgenden Tabelle angegebenen Testanschmutzungen verunreinigten Gewebe mit jeweils 6,3 g sauberem Füllgewebe aus weißer Baumwolle bei 40 °C jeweils 30 Minuten (einschließlich Aufheizzeit (3°C/Minute)) gewa¬ schen und anschließend 3 Mal je 30 Sekunden gespült. Nach dem Trocknen wurde die in Tabelle 2 angegebene Remission der Testgewebe photometrisch bestimmt (Meßwellenlänge 460 nm, Vierfachbestimmung). Tabelle 1: Waschmittelzusammensetzung TGew.-%1A granular basic detergent (BW) with the composition 12% synthetic anionic surfactant, 2% by weight soap, 9% by weight nonionic surfactant, 35% by weight zeolite Na-A, 11% by weight Na citrate, 10% by weight of Na carbonate, 2% by weight of Na silicate, 8% by weight of Na sulfate, the remainder to 100% by weight of water, mixed with the amounts of the additives listed in Table 1 and the agent Hl according to the invention with BW and the comparative agents VI to V4 tested under practical conditions. For this purpose, 2.1 g of the tissue contaminated with the test soiling indicated in the table below, each with 6, were in each case in a Launderometer, type Atlas Standard (liquor ratio 1:12, water hardness 16 ° dH, 8.4 grams of detergent per liter of washing solution) , 3 g of 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). Table 1: Detergent composition TGew .-% 1
Mittel BW Cellulase9) Cobuilder0) Cobuilderc) Poly erd)Medium BW Cellulase 9 ) Cobuilder 0 ) Cobuilder c ) Poly earth)
Ml 91 2 5 - 2Ml 91 2 5 - 2
VI 96 2 - - 2VI 96 2 - - 2
V2 93 - 5 - 2V2 93 - 5 - 2
V3 93 2 5 - -V3 93 2 5 - -
V4 91 2 - 5 2V4 91 2 - 5 2
a) Celluzyme(R) 0,7 T (Hersteller Novo Nordisk) b) Terpolymer, hergestellt nach Beispiel 1 der WO 94/15978 c) Acrylsäure-Maleinsäure-Copoly er (Sokalan(R) CP 5, Hersteller BASF) d) Polymer aus Ethylenterephthalat und Polyethylenoxidterephthalat (Repel-0-Teχ(R) SRP 3, Hersteller Rhδne-Poulenc) a) Celluzyme ( R ) 0.7 T (manufacturer Novo Nordisk) b) terpolymer, prepared according to Example 1 of WO 94/15978 c) acrylic acid-maleic acid copolymer (Sokalan ( R ) CP 5, manufacturer BASF) d) polymer from ethylene terephthalate and polyethylene oxide terephthalate (Repel-0-Teχ ( R ) SRP 3, manufacturer Rhδne-Poulenc)
Tabelle 2 : Remissionswerte T%1Table 2: Remission values T% 1
Mittel Remission bei Anschmutzung A | B | C | D | E | FMedium remission when soiled A | B | C | D | E | F
BW 49,1 57,0 60,8 65,5 64,7 61,3BW 49.1 57.0 60.8 65.5 64.7 61.3
VI nb 58,6 nb nb nb nbVI nb 58.6 nb nb nb nb
V2 48,6 58,7 59,7 64,7 68,1 nbV2 48.6 58.7 59.7 64.7 68.1 nb
V3 46,0 58,2 nb 66,6 66,9 63,7V3 46.0 58.2 nb 66.6 66.9 63.7
V4 48,8 60,7 64,8 67,8 nb nbV4 48.8 60.7 64.8 67.8 nb nb
Ml 50,0 62,1 66,4 68,7 68,6 74,4Ml 50.0 62.1 66.4 68.7 68.6 74.4
nb: nicht bestimmtnb: not determined
Anschmutzungen :Soiling:
A Lippenstift auf Mischgewebe Polyester/Baumwolle veredelt B Makeup auf Mischgewebe Polyester/Baumwolle veredelt C Staub auf Baumwolle D Staub/Hautfett auf Baumwolle veredeltA Lipstick on mixed fabric polyester / cotton refined B Makeup on mixed fabric polyester / cotton refined C Dust on cotton D Dust / skin fat refined on cotton
E Staub/Hautfett auf Mischgewebe Polyester/Baumwolle veredelt F Staub/Hautfett auf PolyesterE Dust / skin fat on mixed fabric polyester / cotton finished F Dust / skin fat on polyester
Man erkennt, daß das erfindungsgemäße Mittel Ml eine signifikant höhere Waschkraft besitzt als Mittel, denen eine Komponente der erfindungsgemäß eingesetzten Wirkstoffkombination fehlt (VI, V2 und V3) oder bei dem statt des Terpolymers ein konventioneller Cobuilder enthalten ist. 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 (VI, V2 and V3) or which contain a conventional cobuilder instead of the terpolymer.

Claims

Patentansprüche claims
1. Pulverförmiges tensid-, cellulase- und builderhaltiges Wasch- oder Rei¬ nigungsmittel, enthaltend a) 0,15 bis 10 Gew.-% eines schmutzablösenden Polymers welches Ethylen¬ terephthalatgruppen der Formel1. Powdered detergent or cleaner containing surfactant, cellulase and builder, comprising a) 0.15 to 10% by weight of a dirt-releasing polymer which contains ethylene terephthalate groups of the formula
und Polyethylenoxidterephthalatgruppen der Formeland polyethylene oxide terephthalate groups of the formula
worin n eine ganze Zahl von 17 bis 110 bedeutet, enthält, wobei das Molverhältnis von Ethylenterephthalat zu Polyethylenoxidterephthalat im Polymeren von etwa 50:50 bis etwa 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 Salze sowie als dritte Monomereinheit Vinylalkohol und/oder ein Vinylalkohol- Derivat oder ein Kohlenhydrat.where n is an integer from 17 to 110, the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate in the polymer being from about 50:50 to about 90:10, b) cellulase in an activity of 0.05 IU / g to 1, 5 IU / g, and c) 1% by weight to 40% by weight of 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.
2. Wasch- und Reinigungsmittel nach Anspruch 1, dadurch gekennzeichnet, daß das schmutzablösende Polymer ein Molverhältnis von Ethylenterephtha¬ lat zu Polyethylenoxidterephthalat von etwa 65:35 bis etwa 80:20 auf¬ weist, das Molekulargewicht der verknüpfenden Polyethylenoxid-Binde- glieder etwa 1000 bis etwa 3000 ist, und das Molekulargewicht des schmutzablösenden Polymers im Bereich von etwa 10 000 bis etwa 50 000 liegt.2. Detergent and cleaning agent according to claim 1, characterized in that the dirt-removing polymer has a molar ratio of ethylene terephthalate to polyethylene oxide terephthalate from about 65:35 to about 80:20, the molecular weight of the linking polyethylene oxide links about 1000 to about 3000 and the molecular weight of the soil release polymer is in the range of about 10,000 to about 50,000.
3. Wasch- und Reinigungsmittel nach Anspruch 1 oder 2, dadurch gekennzeich¬ net, daß das Terpolymer aus den Monomereinheiten einer monoethylenisch ungesättigten Cj-Cβ-Carbonsäure, einer monoethylenisch ungesättigten C4-C8-Dicarbonsäure und Vinylalkohol und/oder einem Vinylalkohol-Derivat und/oder den Salzen einer monoethylenisch ungesättigten C3-Cs-Carbon- säure und einer monoethylenisch ungesättigten C4-C8-Dicarbonsäure sowie Vinylalkohol und/oder einem Vinylalkohol-Derivat besteht.3. Detergent and cleaning agent according to claim 1 or 2, characterized gekennzeich¬ net that the terpolymer from the monomer units of a monoethylenically unsaturated Cj-Cβ-carboxylic acid, a monoethylenically unsaturated C4-C8-dicarboxylic acid and vinyl alcohol and / or a vinyl alcohol derivative and / or the salts of a monoethylenically unsaturated C3-Cs-carboxylic acid and a monoethylenically unsaturated C4-C8-dicarboxylic acid as well as vinyl alcohol and / or a vinyl alcohol derivative.
4. Wasch- und Reinigungsmittel nach Anspruch 1 oder 2, dadurch gekenn¬ zeichnet, daß das Terpolymer aus den Monomereinheiten einer mono¬ ethylenisch ungesättigten C3-Cs-Carbonsäure, einer 2-Alkyl-allylsulfon- säure oder 2-Aryl-allylsulfonsäure und einem Kohlenhydrat und/oder den Salzen einer monoethylenisch ungesättigten C3-C8-Carbonsäure, einer 2-Alkyl-allylsulfonsäure oder 2-Aryl-allylsulfonsäure sowie einem Kohlenhydrat besteht.4. Detergent and cleaning agent according to claim 1 or 2, characterized gekenn¬ characterized in that the terpolymer from the monomer units of a mono¬ ethylenically unsaturated C3-Cs carboxylic acid, a 2-alkyl-allylsulfonic acid or 2-aryl-allylsulfonic acid and one Carbohydrate and / or the salts of a monoethylenically unsaturated C3-C8 carboxylic acid, a 2-alkyl-allylsulfonic acid or 2-aryl-allylsulfonic acid and a carbohydrate.
5. Wasch- und Reinigungsmittel nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Terpolymere entweder vollständig oder zumindest partiell, bevorzugt zu mehr als 50 % und besonders bevorzugt vollstän¬ dig, bezogen auf die vorhandenen Carboxylgruppen, neutralisiert sind.5. Detergent and cleaning agent according to one of claims 1 to 4, characterized in that the terpolymers are either completely or at least partially, preferably more than 50% and particularly preferably completely, based on the carboxyl groups present, neutralized.
6. Wasch- und Reinigungsmittel nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß es nichtionische Tenside aus der Gruppe der niedrigethoxylierten und höherethoxylierten Alkohole und der Glykoside in einer Menge von 2 bis 25 Gew.-% und anionische Tenside aus der Grup¬ pe der Alkyl- bzw. Alkenylsulfate in einer Menge bis zu 15 Gew.-% ent¬ hält.6. Detergent and cleaning agent according to one of claims 1 to 5, characterized in that it contains nonionic surfactants from the group of low ethoxylated and higher ethoxylated alcohols and glycosides in an amount of 2 to 25% by weight and anionic surfactants from the group pe contains the alkyl or alkenyl sulfates in an amount of up to 15% by weight.
7. Wasch- und Reinigungsmittel nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß es 30 Gew.-% bis 55 Gew.-% wasserunlöslichen anor¬ ganischen Builder, 2,5 Gew.-% bis 20 Gew.-% synthetisches Aniontensid, 1 Gew.-% bis 20 Gew.-% nichtionische Tensidkomponente, bis zu 25 Gew.-%, insbesondere 1 Gew.-% bis 15 Gew.-% Bleichmittel, bis zu 8 Gew.-%, ins¬ besondere 0,5 Gew.-% bis 6 Gew.-% Bleichaktivator und bis zu 20 Gew.-%, insbesondere 0,1 Gew.-% bis 15 Gew.-% anorganische Salze, insbesondere Alkalicarbonat, -sulfat und/oder -chlorid, sowie bis zu 2 Gew.-%, ins¬ besondere 0,4 Gew.-% bis 1,2 Gew.-% teilchenförmig konfektioniertes weiteres Enzym, insbesondere Protease, Amylase und/oder Lipase enthält. 7. Detergent and cleaning agent according to one of claims 1 to 6, characterized in that it is 30 wt .-% to 55 wt .-% water-insoluble inorganic builder, 2.5 wt .-% to 20 wt .-% 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% by weight to 6% by weight of bleach activator and up to 20% by weight, in particular 0.1% by weight to 15% by weight, of inorganic salts, in particular alkali metal carbonate, sulfate and / or chloride, and also contains up to 2% by weight, in particular 0.4% by weight to 1.2% by weight, of further enzyme, in particular in the form of particles, in particular protease, amylase and / or lipase.
8. Wasch- und Reinigungsmittel nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß es nach den Verfahren der Sprühtrocknung, Extrusion oder Granulation hergestellt wird. 8. washing and cleaning agent according to one of claims 1 to 7, characterized in that it is produced by the processes of spray drying, extrusion or granulation.
EP95905070A 1993-12-24 1994-12-15 Washing and cleaning powder Expired - Lifetime EP0736083B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4344490A DE4344490A1 (en) 1993-12-24 1993-12-24 Powdered detergent and cleaning agent
DE4344490 1993-12-24
PCT/EP1994/004173 WO1995018208A1 (en) 1993-12-24 1994-12-15 Washing and cleaning powder

Publications (2)

Publication Number Publication Date
EP0736083A1 true EP0736083A1 (en) 1996-10-09
EP0736083B1 EP0736083B1 (en) 1999-08-04

Family

ID=6506227

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95905070A Expired - Lifetime EP0736083B1 (en) 1993-12-24 1994-12-15 Washing and cleaning powder

Country Status (4)

Country Link
EP (1) EP0736083B1 (en)
AT (1) ATE182922T1 (en)
DE (2) DE4344490A1 (en)
WO (1) WO1995018208A1 (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4433027A1 (en) * 1994-09-16 1996-03-21 Henkel Kgaa Powdery, enzyme-containing bleach and detergent
DE19540524A1 (en) * 1995-10-31 1997-05-07 Henkel Kgaa Process for the production of dirt-dissolving granules
DE19543196A1 (en) * 1995-11-20 1997-05-22 Henkel Kgaa Dirt-repellent polymer-containing enzyme preparation
US5919697A (en) * 1996-10-18 1999-07-06 Novo Nordisk A/S Color clarification methods
ES2386496T3 (en) * 2008-01-04 2012-08-21 The Procter & Gamble Company Use of a cellulase to transmit advantages of release of dirt to cotton during a subsequent washing process
WO2021067984A1 (en) * 2019-09-30 2021-04-08 The Procter & Gamble Company Fabric care compositions that include a copolymer and related methods

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4571303A (en) * 1985-01-23 1986-02-18 Colgate-Palmolive Company Built nonionic detergent composition containing stabilized polyethylene terephthalate-polyoxyethylene terephthalate soil release promoting polymer
NZ230842A (en) * 1988-10-21 1992-05-26 Colgate Palmolive Co Nonionic heavy duty particulate detergent containing protease, amylase and cellulase
JPH0356598A (en) * 1989-07-26 1991-03-12 Kao Corp Detergent composition for wear

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9518208A1 *

Also Published As

Publication number Publication date
DE59408596D1 (en) 1999-09-09
DE4344490A1 (en) 1995-06-29
EP0736083B1 (en) 1999-08-04
ATE182922T1 (en) 1999-08-15
WO1995018208A1 (en) 1995-07-06

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