EP0736083B1 - Poudre de lavage et de nettoyage - Google Patents

Poudre de lavage et de nettoyage Download PDF

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Publication number
EP0736083B1
EP0736083B1 EP95905070A EP95905070A EP0736083B1 EP 0736083 B1 EP0736083 B1 EP 0736083B1 EP 95905070 A EP95905070 A EP 95905070A EP 95905070 A EP95905070 A EP 95905070A EP 0736083 B1 EP0736083 B1 EP 0736083B1
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EP
European Patent Office
Prior art keywords
weight
detergent
acid
vinyl alcohol
terephthalate
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.)
Expired - Lifetime
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EP95905070A
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German (de)
English (en)
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EP0736083A1 (fr
Inventor
Fred Schambil
Eduard Smulders
Horst Upadek
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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, the surfactant, builder, Cellulase and a dirt-repellent polymer and a terpolymer cobuilder contain.
  • detergents and cleaning agents usually contain as main components Builders and surfactants from the group of anionic and nonionic Surfactants.
  • Cobuilders can be used as further components in detergents such as polycarboxylates, peroxy bleaches, bleach activators, foam inhibitors, optical brighteners and enzymes or enzyme combinations to improve the cleaning effect.
  • the most commonly used enzymes include protease, amylase, cellulase and lipase. These enzymes each have different ones Properties and can come from different sources.
  • the Use of cellulase is for example in the European patent application EP 468464 as well as in international patent applications WO 91/19807, WO 91/19794 or WO 90/02790.
  • Graying inhibitors in the true sense have the task of removing the dirt detached from the fiber to keep the fleet suspended and reloading the dirt and thus preventing the graying of the fibers while the above Soil repellent active ingredients presumably function in the sense of protective repellant Unfold fiber equipment.
  • detergents that are dirt-repellent Compound is a polymer of ethylene terephthalate and polyethylene oxide terephthalate and anionic surfactants in the form of alcohol sulfates, with Ethylene oxide condensed alcohol sulfates and mixtures thereof.
  • European patent application EP 0 365 103 describes a surfactant composition described, which 4 to 30 wt .-% of a synthetic nonionic Surfactants, 25 to 80% by weight builder for this nonionic surfactant, 0.1 to 2% by weight of protease, 0 to 2% by weight of amylase, 0.2 to 1% by weight of cellulase, 1 to 15% by weight of water and poly (alkylene glycol terephthalate) as a further constituent contains.
  • the detergents known from the prior art are not always satisfactory dirt-repellent properties to a graying to prevent the washed fabric as permanently as possible. This will their cleaning effect is impaired.
  • the object of the present invention is to provide washing and cleaning agents To provide the excellent cleaning effect and at the same time have dirt-removing properties to the graying to prevent the tissue.
  • the present invention relates to a powdered detergent and cleaning agent containing surfactant, cellulase and builder, comprising a) 0.15 to 10% by weight of a dirt-repellent polymer which contains ethylene terephthalate groups of the formula and polyethylene oxide terephthalate groups of the formula where n is an integer from 17 to 110, the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate in the polymer being from 50:50 to 90:10, b) cellulase in an activity of 0.05 IU / g to 1.5 IU / g, and c) 1 wt .-% to 40 wt .-% terpolymers from the monomer units of two ethylenically unsaturated carboxylic acids and / or their salts and as a third monomer unit vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate.
  • a dirt-repellent polymer which contains ethylene terephthalate groups
  • Another object of the invention is an otherwise identical composition, component c) a terpolymer of the monomer units of a monoethylenically unsaturated C 3-8 carboxylic acid, a 2-alkyl-allylsulfonic acid or a 2-aryl-allylsulfonic acid and a carbohydrate and / or the salts of a monoethylenically unsaturated C 3-8 carboxylic acid, a 2-alkyl-allylsulfonic acid or a 2-aryl-allylsulfonic acid and a carbohydrate.
  • the dirt-repellent polymers contained according to the invention, the groups with the above Formulas I and II are contained in the washing and cleaning agents according to the invention in an amount of 0.15% by weight to 10% by weight, preferably 0.25% by weight to 5% by weight, particularly preferably contain 0.3% by weight to 3% by weight. It is in these connections Molecular weight of the linking polyethylene oxide units preferably in the range of 750 to 5000.
  • the polymers can have an average molecular weight of 5000 to Own 200,000. In the polymer can be ethylene terephthalate and polyethylene oxide terephthalate arbitrarily distributed.
  • Preferred polymers are those with molar ratios of ethylene terephthalate / polyethylene oxide terephthalate from 65:35 to 90:10, preferably from 65:35 to 80:20, the linking polyethylene oxide units have a molecular weight of 750-5000, preferably 1000 to 3000 and the polymer has a molecular weight of 10,000 to 50,000.
  • examples for Commercial polymers of this type are e.g. B. "Mileas®-T" from ICI United States, Inc., Repel-O-Tex® SRP 3 from Rhône-Poulenc and Zelcon® 8037 from DuPont.
  • the dirt-repellent polymers used in agents according to the invention can by known polymerization processes are prepared, the starting materials in such amounts are used to achieve the above ratios of ethylene terephthalate to get polyethylene oxide terephthalate.
  • those in US Pat 3479212 described methods for producing suitable polymers can be used.
  • the detergents and cleaning agents of the invention contain in the Usually fine crystalline, synthetic and bound water containing zeolite and / or Alkali silicates, although agents according to the invention are not limited to these builder substances are.
  • the zeolite used is preferably A and / or P type zeolite in Detergent quality. Their mixtures with zeolite NaX are also suitable, the proportion of the Zeolite NaX in such mixtures is advantageously below 30%. You point practically no particles larger than 30 ⁇ m and preferably consist of at least 80% from particles smaller than 10 ⁇ m.
  • Suitable zeolites have a medium one Particle size of less than 10 ⁇ m (measurement method: Eisenhofer diffraction; average of the Volume distribution), preferably between 1.5 and 4.5 ⁇ m, in particular between 2.0 and 4.0 ⁇ m.
  • Your calcium binding capacity which according to the information in German patent DE 24 12 837 can be determined, is in the range of 100 to 200 mg CaO / g.
  • the salary of the The average of finely divided, in particular crystalline, hydrated zeolite is preferably 30 up to 65 wt .-% and in particular 32 to 45 wt .-%, based on anhydrous active substance.
  • the zeolite generally has a water content of 17 to 25% by weight, preferably 18 to 22% by weight, in particular 20 to 22% by weight.
  • alkali silicates are added as a solid and not in the form of a solution. They can be amorphous or crystalline.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na 2 O: SiO 2 molar ratio of 1: 2 to 1: 2.8.
  • Such amorphous alkali silicates are commercially available, for example, under the name Portil (R) .
  • 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 ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O can be obtained, for example, by the process described in international patent application WO91 / 08171.
  • the content of alkali silicates in the compositions is preferably 1 to 15% by weight and in particular 2 to 8% by weight, based on the anhydrous active substance.
  • the weight ratio of zeolite: amorphous silicate, based in each case on anhydrous active substance, is preferably 4: 1 to 10: 1.
  • the crystalline layered silicates are used in zeolite-containing agents preferably in amounts of 1% by weight to 15% by weight and in particular 2 to 7% by weight, the weight ratio of zeolite to crystalline layered silicate, in each case based on anhydrous active substance, at least 5: 1 is.
  • the weight ratio of amorphous alkali silicate: crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.
  • the detergents and cleaning agents contain as cobuilder terpolymers in an amount of 1 to 40% by weight, preferably 2 to 25% by weight and particularly preferably 2 to 15% by weight.
  • These terpolymers contain two carboxylic acids and / or their salts as monomer units and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as third monomer unit.
  • the first acidic monomer unit or its salt is derived from a monoethylenically unsaturated C 3 -C 8 carboxylic acid and preferably from a C 3 -C 4 monocarboxylic acid, in particular from (meth) acrylic acid.
  • the second acidic monomer unit or its salt can be a derivative of a C 4 -C 8 dicarboxylic acid; preferably a C 4 -C 8 dicarboxylic acid, maleic acid being particularly preferred.
  • the third monomer unit is formed from vinyl alcohol and / or preferably an esterified vinyl alcohol.
  • Vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example of C 1 -C 4 carboxylic acids, with vinyl alcohol are particularly preferred.
  • Preferred terpolymers contain 60 to 95% by weight, in particular 70 to 90% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or maleate and 5 to 40% by weight.
  • the second acidic monomer unit or its salt can also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C 1 -C 4 -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives derives, is substituted.
  • Preferred terpolymers contain 40 to 60% by weight, in particular 45 to 55% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10 to 30% by weight, preferably 15 to 25 %
  • 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 used are also preferably used or at least partially, in particular more than 50% are neutralized to the carboxyl groups present.
  • Particularly preferred is a completely neutralized terpolymer the salts of the monomeric acids, especially the sodium or potassium salts the monomeric acids, and vinyl alcohol or a carbohydrate.
  • the terpolymers generally have a relative molecular weight between 1000 and 200000, preferably between 200 and 50000 and in particular between 3000 and 10000. They usually become more watery in the form Solutions, preferably in the form of 30 to 50% by weight aqueous solutions.
  • Particularly preferred terpolymers are produced by processes the in the German patent DE 42 21 381 and the international Patent application WO 94/15978 are described.
  • Customary polymeric carboxylates can also be used as additional builders or polymeric carboxylic acids consisting of one or two monomer units are composed. These polymeric carboxylates or Carboxylic acids in agents according to the invention can optionally in a Amounts of up to 15% by weight are present, but are preferably absent entirely.
  • the relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on free acid.
  • a usually particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000.
  • a washing and cleaning agent according to the invention contains an enzyme from the class of cellulases.
  • the cellulase used according to the invention belongs to the enzymes obtainable from microorganisms, in particular bacteria or fungi, which have a pH optimum, preferably in the almost neutral to weakly alkaline pH range from 6 to 9.5.
  • Such cellulases are known, for example, from German Offenlegungsschriften DT 22 47 832, DE 31 17 250, DE 32 07 825, DE 32 07 847 and DE 33 22 950, British patent application GB 2 232 983, European patent applications EP 0 265 832, EP 0 269 077, EP 0 270 974, EP 0 271 004, EP 0 339 550, EP 0 458 162 and EP 0 468 464 or the international patent applications WO 89/09259, WO 91/10732, WO 91/17243, WO 92 / 06209, WO 93/11249, WO 93/12224, WO 93/17101, WO 93/20193, WO 94/07998 and WO 94/14953.
  • the agent according to the invention preferably in amounts such that the finished agent has a cellulolytic activity of 0.05 IU / g to 1.5 IU / g ("International Units" per gram, based on the enzymatic hydrolysis of Na-carboxymethylcellulose) pH 9.0 and 40 ° C, as described in Agric. Biol. Chem. 53, 1275 (1989) by S. Ito et al.), in particular 0.07 IU / g to 1.4 IU / g and particularly preferred 0.1 IU / g to 1.3 IU / g.
  • Suitable commercial products include Celluzyme (R) from Novo Nordisk or KAC (R) from Kao.
  • the detergents according to the invention can comprise water-soluble complexing agents the group of phosphonates.
  • the phosphonates can be used in amounts of up to 1.5% by weight.
  • Detergents and cleaning agents contain other common ingredients normally non-ionic surfactant compounds
  • Surfactants may also contain anionic and / or zwitterionic surfactants be.
  • the surfactants are generally in the detergents according to the invention with a total content of 5 to 40% by weight, preferably 5 up to 30% by weight and in particular from 8 to 25% by weight.
  • the detergent according to the invention contains in particular as nonionic surfactants low ethoxylated and higher ethoxylated nonionic surfactants.
  • the nonionic surfactants can be used in an amount of up to 25% by weight, preferably up to 15% by weight.
  • the as non-ionic surfactants preferably used ethoxylated alcohols are derived from primary Alcohols with preferably 9 to 18 carbon atoms.
  • the low ethoxylated Fatty alcohols have an average of 1 to 6 moles and that higher ethoxylated alcohols on average 7 to 20 moles of ethylene oxide.
  • the degrees of ethoxylation given represent statistical averages, that are an integer or a fraction for a specific product can.
  • the alcohol residue can be linear or methyl branched in the 2-position be, or contain linear and methyl branched radicals in the mixture, such as they are usually present in oxo alcohol residues.
  • Alcohol ethoxylates with linear residues from alcohols of native origin Preferably 12 to 18 carbon atoms, e.g. B. from coconut oil, tallow oil or Oleyl alcohol.
  • the preferred low ethoxylated alcohols include for example fatty alcohols with 12 to 18 carbon atoms with an average 3 to 6 EO units.
  • alcohols include fatty alcohols with 16 to 18 carbon atoms with an average of 12 to 16 EO units, e.g. ethoxylated Palm alcohol.
  • Preferred alcohol ethoxylates have a narrow homolog distribution on (narrow range ethoxylates, NRE).
  • the invention Detergents preferably contain 1% to 10% by weight, in particular 1% to 5% by weight of low ethoxylated nonionic surfactants and 1% by weight up to 10 wt .-%, in particular 1 wt .-% to 5 wt .-% higher ethoxylated nonionic surfactants.
  • the lower ethoxylated alcohols and the higher ethoxylated Alcohols are preferably in a weight ratio of 10: 1 to 1:10, preferably 5: 1 to 1: 5, in particular 2: 1 to 1: 1.
  • nonionic surfactants that can be used alone or in combination with the above-mentioned nonionic surfactants are alkoxylated fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or preferably according to that in international patent application WO 90/13533 described processes are prepared, and alkyl glycosides of the general formula RO (G) x , in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 C atoms and G for a Glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 C atoms and G for a Glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • Alkyl glycosides can preferably be present in the detergents according to the invention in an amount of up to 5% by weight, in particular from 0.5% by weight to 3% by weight.
  • Anionic surfactants which can be used in the agents according to the invention are sulfates and, if appropriate, sulfonates and soaps composed of preferably natural fatty acids or fatty acid mixtures.
  • the anionic surfactants can be present in the agents according to the invention in an amount of up to 15 wt.
  • Suitable sulfate-type surfactants are sulfuric acid monoesters from primary alcohols of natural and synthetic origin.
  • the alk (en) yl sulfates are the sulfuric acid half esters of the C 12 -C 18 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C 10 -C 20 oxo alcohols, and those secondary alcohols of this chain length prefers. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. C 16 -C 18 alk (en) yl sulfates are particularly preferred from the point of view of washing technology.
  • the compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C 12 -C 14 fatty alkyl sulfates or C 12 -C 16 fatty alkyl sulfates with C 16 -C 18 fatty alkyl sulfates.
  • saturated alkyl sulfates not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C 16 -C 22 are used.
  • Mixtures of saturated sulfated fatty alcohols predominantly consisting of C 16 and unsaturated sulfated fatty alcohols predominantly consisting of C 18 are particularly preferred, for example those derived from solid or liquid HD-Ocenol (R) fatty alcohol mixtures (commercial product of the applicant) .
  • Weight ratios of alkyl sulfates to alkenyl sulfates from 10: 1 to 1: 2 and in particular from about 5: 1 to 1: 1 are preferred.
  • the agents according to the invention can contain up to 12% by weight alk (en) yl sulfates, preferably 5% by weight to 8% by weight.
  • the sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C 9 -C 11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12 - C 18 fatty alcohols with 2 to 4 EO are suitable. Because of their high foaming power, they are used in washing agents for machine use only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • surfactants of the sulfonate type preference is given to C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates, and also disulfonates of the kind obtained, for example, from C 12 -C 18 monoolefins having a terminal or internal double bond Sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products is considered.
  • These surfactants can be up to 10% by weight on average, preferably up to 5% by weight. However, surfactants of the sulfonate type can also be dispensed with without significantly affecting the washing action.
  • Soaps are particularly suitable as further anionic surfactants, saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids, being suitable.
  • those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C 12 -C 18 fatty acid soaps and 0 to 50% by weight of oleic acid soap.
  • the detergents according to the invention preferably contain soap in amounts of 0.1% by weight to 1.5% by weight.
  • the detergents according to the invention preferably contain peroxy bleach, in particular in combination with bleach activators.
  • peroxy bleach in particular in combination with bleach activators.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and other peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperoxyazelaic acid or diperoxydodecanedioic acid.
  • the detergents preferably contain 5 to 25% by weight and in particular 10 to 20% by weight of bleaching agent, preferably sodium perborate monohydrate, tetrahydrate or sodium percarbonate being used.
  • bleach activators can be incorporated into the preparations which form organic peracids with H 2 O 2 .
  • these are N- or O-acyl compounds, for example multi-acylated alkylenediamines, in particular tetraacetylethylene diamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, triazines, urazoles, diketopiperazines, sulfurylamides and cyanuric acid hydrides, and also carboxylic acid hydrides , Carboxylic acid esters, especially sodium isonanoyloxybenzenesulfonate, and acylated sugar derivatives, especially pentaacetyl glucose.
  • N- or O-acyl compounds for example multi-acylated alkylenediamines, in particular tetraacetylethylene diamine, acylated glycolurils, in particular
  • 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 1,5- Diacetyl-2,4-dioxohexahydro-1,3,5-triazine
  • Extruded TAED which contains 70 70% by weight of TAED, 15 to 25% by weight of C 12-18 fatty alcohol sulfate and 2 to 6% by weight of soda can also be used.
  • the content of bleach activators in the detergents containing bleach is in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
  • the detergent is 0.1 to 5% by weight, foam inhibitors count, optical brighteners, fabric softening substances as well as colors and fragrances. It can also contain neutral salts in an amount of up to 20% by weight its proportion is preferably less than 10% by weight.
  • the agent according to the invention can contain additional graying inhibitors in an amount of 0.1 to 5 wt .-%, based on the agent.
  • Water-soluble colloids are mostly additional graying inhibitors organic nature suitable, for example soluble starch preparations and for example degraded starch, aldehyde starches and so on.
  • Carboxymethyl cellulose (Na salt), methyl cellulose, methyl hydroxyethyl cellulose and their Mixtures and polyvinylpyrrolidone are preferably used.
  • the washing and Detergents contain other 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 and have a pH optimum in the alkaline range, for example those from the international patent applications WO 92/07067, WO 91/02792, WO 88/03947 or WO 88/03946 or the European patent applications EP 471 265, EP 416 967 or EP 394 352 known proteases.
  • Protease is preferably used in the agent according to the invention in amounts such that the finished agent 100 PE / g to 15000 PE / g (protease units per gram, determined by the method described in surfactants 7, 125 (1970)), in particular 125 PE / g to 7500 PE / g and particularly preferably 150 PE / g to 4500 PE / g.
  • Suitable proteases are commercially available, for example under the names BLAP (R) , Savinase (R) , Durazym (R) , Esperase (R) , Naxatase (R) , Maxapem (R) , Optimase (R) , Opticlean (R) or Alcalase (R) .
  • amylases which can be used in agents according to the invention include the enzymes which can be obtained from bacteria or fungi and which have a pH optimum, preferably in the alkaline range up to about pH 10.
  • Useful commercial products include Termamyl (R) and Maxamyl (R) .
  • Amylase is preferably used in the agent according to the invention in amounts such that the finished agent 0.01 KNU / g to 3 KNU / g ("Kilo-Novo-Units" per gram according to the Novo standard method, where 1 KNU is the amount of enzyme which breaks down 5.26 g of starch at pH 5.6 and 37 ° C., based on the method described by P.
  • the lipase is an enzyme that can be obtained from microorganisms, in particular bacteria or fungi. Such is known, for example, from European patent applications EP 204 208, EP 214 761, EP 258 068, EP 407 225 or international patent application WO 87/859. Examples of useful commercially available lipases are Lipolase (R) and Lipozym (R) .
  • Lipase is preferably used in the agent according to the invention in amounts such that the finished agent 10 LU / g to 10,000 LU / g ("lipase activity units" per gram, determined by the enzymatic hydrolysis of tributyrin at 30 ° C. and pH 7 after the method mentioned in EP 258 068), in particular 80 LU / g to 5,000 LU / g and particularly preferably 100 LU / g to 1000 LU / g.
  • the enzymes can be adsorbed onto carriers in a manner known per se, embedded in coating substances and / or with the aid of carrier substances have been granulated to make them easier to handle and against Protect premature inactivation when in detergent or cleaning products should be incorporated.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also advantageously used, for example those composed of silicones and paraffins or waxes.
  • the foam inhibitors, in particular silicone- or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearoylethylene diamides are particularly preferred.
  • the washing agents according to the invention contain and cleaning agents 30% by weight to 55% by weight of water-insoluble inorganic Builder, 2.5% to 20% synthetic anionic surfactant, 1 %
  • nonionic surfactant component up to 25% by weight, in particular 1% by weight to 15% by weight of bleach, up to 8% by weight, in particular 0.5 wt% to 6 wt% bleach activator and up to 20 wt%, in particular 0.1% to 15% by weight of inorganic salts, in particular alkali carbonate, sulfate and / or chloride, and up to 2% by weight, in particular 0.4 wt.% To 1.2 wt.%
  • Further enzyme made up in particulate form, in particular protease, amylase and / or lipase.
  • the agents according to the invention can, for example, in a manner known per se by mixing, granulating, extruding and / or by spray drying getting produced.
  • the pourable powder, extruded or granular preparations from a dry homogeneous mixture of at least two powder components, the first of which is spray-dried Powder is present.
  • This is through a conventional one Spray drying of a slurry available, at least the anionic surfactants and the zeolite in an aqueous suspension and optionally contains nonionic surfactants.
  • Bleaching agents such as perborate are not together as usual because of their thermal sensitivity spray dried with the ingredients of the first powder component, but only added to the spray product afterwards.
  • the preparation of the agents according to the invention can be done in the simplest way by admixing the enzyme particles in a conventional mixer, in particular a drum, roller, belt or free-fall mixer, optional other powdery components, in particular bleach, and if desired also liquid or liquefied components, to which in particular non-ionic surfactants but also colors and fragrances belong, can be mixed by spraying.
  • a conventional mixer in particular a drum, roller, belt or free-fall mixer
  • optional other powdery components in particular bleach
  • liquid or liquefied components to which in particular non-ionic surfactants but also colors and fragrances belong
  • Including the familiarization the other ingredients by admixing granules containing them or extrudate to the other components is possible and especially for the production of detergents with a relatively high bulk density from preferably 650 g / l to 900 g / l is preferred.
  • a granular basic detergent ( BW ) with the composition 12% by weight of synthetic anionic surfactant, 2% by weight of soap, 9% by weight of nonionic surfactant, 35% by weight of zeolite Na-A, 11% by weight of Na citrate was used , 10% by weight Na carbonate, 2% by weight Na silicate, 8% by weight Na sulfate, the remainder to 100% by weight water, with the amounts of the additives listed in Table 1 given there mixed and tested the inventive agent M1 with BW and the comparative agents V1 to V4 under practical conditions.
  • Detergent composition [% by weight] medium BW Cellulase Cobuilder Cobuilder polymer M1 91 2nd 5 - 2nd V1 96 2nd - - 2nd V2 93 - 5 - 2nd V3 93 2nd 5 - - V4 91 2nd - 5 2nd Reflectance values [%] medium Remission when soiled A B C.
  • agent M1 according to the invention has a significantly higher detergency than agents which lack a component of the active compound combination used according to the invention ( V1 , V2 and V3 ) or which contain a conventional cobuilder instead of the terpolymer.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Polyesters Or Polycarbonates (AREA)

Claims (8)

  1. Agent de lavage et de nettoyage pulvérulent, renfermant des tensioactifs, des cellulases et des adjuvants, contenant :
    a) de 0,15 à 10% en poids d'un polymère enlevant les salissures, qui contient des radicaux téréphtalate d'éthylène de formule :
    Figure 00250001
       et des radicaux téréphtalate de poly(oxyde d'éthylène) de formule :
    Figure 00250002
       dans laquelle n représente une nombre entier allant de 17 à 110, où le rapport molaire du téréphtalate d'éthylène au téréphtalate de poly(oxyde d'éthylène) dans le polymère se situe dans l'intervalle allant de 50:50 à 90:10 ;
    b) une cellulase ayant une activité allant de 0,05 UI/g à 1,5 UI/g, ainsi que
    c) de 1% en poids à 40% en poids d'un terpolymère constitué des unités monomériques de deux acides carboxyliques éthyléniquement insaturés et/ou leurs sels, ainsi que comme troisième unité monomérique, l'alcool vinylique et/ou un dérivé de l'alcool vinylique ou un hydrate de carbone.
  2. Agent de lavage et de nettoyage suivant la revendication 1, caractérisé en ce que le polymère enlevant les salissures présente un rapport molaire du téréphtalate d'éthylène au téréphtalate de poly(oxyde d'éthylène) allant de 65:35 à 80:20, que le poids moléculaire du lien de jonction - poly(oxyde d'éthylène) se situe dans l'intervalle allant de 1000 à 3000, et que le poids moléculaire du polymère enlevant les salissures se situe dans l'intervalle allant de 10 000 à 50 000.
  3. Agent de lavage et de nettoyage suivant la revendication 1 ou 2, caractérisé en ce que le terpolymère consiste en les unités monomériques d'un acide carboxylique en C3-C8 monoéthyléniquement insaturé, d'un diacide carboxylique en C4-C8 monoéthyléniquement insaturé et d'alcool vinylique et/ou un dérivé de l'alcool vinylique et/ou des sels d'un acide carboxylique en C3-C8 monoéthyléniquement insaturé et d'un diacide carboxylique en C4-C8 monoéthyléniquement insaturé ainsi que de l'alcool vinylique et/ou d'un dérivé de l'alcool vinylique.
  4. Agent de lavage et de nettoyage pulvérulent, renfermant des tensioactifs, des cellulases et des adjuvants, contenant :
    a) de 0,15 à 10% en poids d'un polymère enlevant les salissures, qui contient des radicaux téréphtalate d'éthylène de formule (I) et des radicaux téréphtalate de poly(oxyde d'éthylène) de formule (II) dans laquelle n représente une nombre entier allant de 17 à 110, où le rapport molaire du téréphtalate d'éthylène au téréphtalate de poly(oxyde d'éthylène) dans le polymère se situe dans l'intervalle allant de 50:50 à 90:10 ;
    b) une cellulase ayant une activité allant de 0,05 UI/g à 1,5 UI/g, ainsi que
    c) de 1% en poids à 40% en poids d'un terpolymère constitué des unités monomériques d'un acide carboxylique en C3-C8 monoéthyléniquement insaturé, d'un acide 2-alcoylallylsulfonique ou d'un acide 2-arylallylsulfonique et d'un hydrate de carbone et/ou les sels d'un acide carboxylique en C3-C8 monoéthyléniquement insaturé, d'un acide 2-alcoylallylsulfonique ou d'un acide 2-arylallylsulfonique, ainsi qu'un hydrate de carbone.
  5. Agent de lavage et de nettoyage suivant l'une quelconque des revendications 1 à 4, caractérisé en ce que les terpolymères sont neutralisés complètement ou au moins partiellement, de préférence à plus de 50% et de manière particulièrement préférée complètement, sur base des radicaux carboxyle présents.
  6. Agent de lavage et de nettoyage suivant l'une quelconque des revendications 1 à 5, caractérisé en ce qu'il contient des tensioactifs non ioniques du groupe des alcools faiblement éthoxylés et fortement éthoxylés et des glycosides, en une quantité allant de 2 à 25% en poids, et des tensioactifs anioniques du groupe des alcoyl- ou alcénylsulfates, en une quantité allant jusqu'à 15% en poids.
  7. Agent de lavage et de nettoyage suivant l'une quelconque des revendications 1 à 6, caractérisé en ce qu'il contient de 30% en poids à 55% en poids d'adjuvants inorganiques insolubles dans l'eau, de 2,5% en poids à 20% en poids de tensioactifs anioniques, de 1% en poids à 20% en poids de composants tensioactifs non ioniques, jusqu'à 25% en poids, en particulier de 1% en poids à 15% en poids d'agents de blanchiment, jusqu'à 8% en poids, en particulier de 0,5% en poids à 6% en poids d'activateurs du blanchiment et jusqu'à 20% en poids, en particulier de 0,1% en poids à 15% en poids de sels inorganiques, en particulier de carbonate, sulfate et/ou silicate alcalin, ainsi que jusqu'à 2% en poids, en particulier de 0,4% en poids à 1,2% en poids d'autres enzymes présentées sous forme de particules, en particulier de protéases, amylases et/ou lipases.
  8. Agent de lavage et de nettoyage suivant l'une quelconque des revendications 1 à 7, caractérisé en ce qu'il est préparé par le procédé de séchage par pulvérisation, extrusion ou granulation.
EP95905070A 1993-12-24 1994-12-15 Poudre de lavage et de nettoyage Expired - Lifetime EP0736083B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4344490A DE4344490A1 (de) 1993-12-24 1993-12-24 Pulverförmiges Wasch- und Reinigungsmittel
DE4344490 1993-12-24
PCT/EP1994/004173 WO1995018208A1 (fr) 1993-12-24 1994-12-15 Poudre de lavage et de nettoyage

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EP0736083A1 EP0736083A1 (fr) 1996-10-09
EP0736083B1 true EP0736083B1 (fr) 1999-08-04

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AT (1) ATE182922T1 (fr)
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WO (1) WO1995018208A1 (fr)

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Publication number Priority date Publication date Assignee Title
DE4433027A1 (de) * 1994-09-16 1996-03-21 Henkel Kgaa Pulverförmiges, enzymhaltiges Bleich- und Waschmittel
DE19540524A1 (de) * 1995-10-31 1997-05-07 Henkel Kgaa Verfahren zur Herstellung schmutzlösender Granulate
DE19543196A1 (de) * 1995-11-20 1997-05-22 Henkel Kgaa Schmutzabweisendes Polymer enthaltende Enzymzubereitung
US5919697A (en) * 1996-10-18 1999-07-06 Novo Nordisk A/S Color clarification methods
WO2009087526A1 (fr) * 2008-01-04 2009-07-16 The Procter & Gamble Company Utilisation d'une cellulase pour conférer des avantages d'élimination des salissures à du coton pendant un procédé de blanchissage ultérieur
CN114302946A (zh) * 2019-09-30 2022-04-08 宝洁公司 包含共聚物的织物护理组合物及相关方法

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* 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 (ja) * 1989-07-26 1991-03-12 Kao Corp 衣料用洗浄剤組成物

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DE4344490A1 (de) 1995-06-29
EP0736083A1 (fr) 1996-10-09
DE59408596D1 (de) 1999-09-09
WO1995018208A1 (fr) 1995-07-06
ATE182922T1 (de) 1999-08-15

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