WO1995018208A1 - Poudre de lavage et de nettoyage - Google Patents

Poudre de lavage et de nettoyage Download PDF

Info

Publication number
WO1995018208A1
WO1995018208A1 PCT/EP1994/004173 EP9404173W WO9518208A1 WO 1995018208 A1 WO1995018208 A1 WO 1995018208A1 EP 9404173 W EP9404173 W EP 9404173W WO 9518208 A1 WO9518208 A1 WO 9518208A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
detergent
vinyl alcohol
acid
agent according
Prior art date
Application number
PCT/EP1994/004173
Other languages
German (de)
English (en)
Inventor
Fred Schambil
Eduard Smulders
Horst Upadek
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to EP95905070A priority Critical patent/EP0736083B1/fr
Priority to DE59408596T priority patent/DE59408596D1/de
Publication of WO1995018208A1 publication Critical patent/WO1995018208A1/fr

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.

Landscapes

  • 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)

Abstract

L'invention a pour objet une poudre de lavage et de nettoyage comprenant un tensioactif, de la cellulase et un adjuvant, contenant 0,15 à 10 % en poids d'un polymère séparant les impuretés et renfermant des groupes téréphtalate d'éthylène selon la formule (I) et des groupes téréphtalate d'oxyde de polyéthylène selon la formule (II), où n est un nombre entier compris entre 17 et 110, le rapport molaire téréphtalate d'éthylène/ téréphtalate d'oxyde de polyéthylène dans le polymère étant compris entre environ 50:50 et environ 90:10, de la cellulase présentant une activité de 0,05 IU/g à 1,5 IU/g, ainsi que 1 à 40 % en poids de terpolymères composés des motifs monomères de deux acides carboxyliques éthyléniquement insaturés et/ou de leurs sels ainsi que, comme troisième motif monomère, d'alcool vinylique et/ou de dérivé d'alcool vinylique ou d'un hydrate de carbone. Ladite poudre présente une efficacité accrue.
PCT/EP1994/004173 1993-12-24 1994-12-15 Poudre de lavage et de nettoyage WO1995018208A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP95905070A EP0736083B1 (fr) 1993-12-24 1994-12-15 Poudre de lavage et de nettoyage
DE59408596T DE59408596D1 (de) 1993-12-24 1994-12-15 Pulverförmiges wasch- und reinigungsmittel

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4344490.3 1993-12-24
DE4344490A DE4344490A1 (de) 1993-12-24 1993-12-24 Pulverförmiges Wasch- und Reinigungsmittel

Publications (1)

Publication Number Publication Date
WO1995018208A1 true WO1995018208A1 (fr) 1995-07-06

Family

ID=6506227

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1994/004173 WO1995018208A1 (fr) 1993-12-24 1994-12-15 Poudre de lavage et de nettoyage

Country Status (4)

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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
EP3798288A1 (fr) * 2019-09-30 2021-03-31 The Procter & Gamble Company Compositions d'entretien de tissus comprenant un copolymère et procédés associés

Families Citing this family (4)

* Cited by examiner, † Cited by third party
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

Citations (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
EP0365103A2 (fr) * 1988-10-21 1990-04-25 Colgate-Palmolive Company Compositions détergentes à usage universel avec un agent tensioactif non ionique synthétique, organique ayant une action nettoyante modifiée sur le linge contenant de la salissure difficile à éliminer
JPH0356598A (ja) * 1989-07-26 1991-03-12 Kao Corp 衣料用洗浄剤組成物

Patent Citations (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
EP0365103A2 (fr) * 1988-10-21 1990-04-25 Colgate-Palmolive Company Compositions détergentes à usage universel avec un agent tensioactif non ionique synthétique, organique ayant une action nettoyante modifiée sur le linge contenant de la salissure difficile à éliminer
JPH0356598A (ja) * 1989-07-26 1991-03-12 Kao Corp 衣料用洗浄剤組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 015, no. 202 (C - 0834) 23 May 1991 (1991-05-23) *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
EP3798288A1 (fr) * 2019-09-30 2021-03-31 The Procter & Gamble Company Compositions d'entretien de tissus comprenant un copolymère et procédés associés
EP3798289A1 (fr) * 2019-09-30 2021-03-31 The Procter & Gamble Company Compositions d'entretien de tissus comprenant un copolymère et procédés associés
WO2021067983A1 (fr) * 2019-09-30 2021-04-08 The Procter & Gamble Company Compositions de soin de tissu comprenant un copolymère et procédés associés
WO2021067984A1 (fr) * 2019-09-30 2021-04-08 The Procter & Gamble Company Compositions d'entretien de tissu comprenant un copolymère et procédés associés

Also Published As

Publication number Publication date
EP0736083B1 (fr) 1999-08-04
DE59408596D1 (de) 1999-09-09
ATE182922T1 (de) 1999-08-15
EP0736083A1 (fr) 1996-10-09
DE4344490A1 (de) 1995-06-29

Similar Documents

Publication Publication Date Title
EP0767830B1 (fr) Production de granules d'enzymes multiples
EP0815196B1 (fr) Procede de fabrication d'un detergent ou nettoyant en poudre
WO1995022592A1 (fr) Produit de lavage a adjuvants au silicate amorphes
DE19936613B4 (de) Verfahren zur Herstellung eines Waschmittels mit löslichem Buildersystem
EP0888449B1 (fr) Detergent et nettoyant solide a masse volumique apparente elevee contenant des tensioactifs et des adjuvants, et compose approprie
EP0698079B1 (fr) Produits de lavage et de nettoyage contenant une lipase
EP0736083B1 (fr) Poudre de lavage et de nettoyage
EP0814152A2 (fr) Procédé de préparation des détergents solides
EP0767829B1 (fr) Production des granules d'enzymes multiples et leur utilisation
EP0986629B1 (fr) Detergent granule
DE4313949A1 (de) Pulverwaschmittel mit ökologisch unbedenklichem Buildersystem, spezieller Tensidkombination und Lipase
DE19804656A1 (de) Cellulasehaltiges Waschmittel
EP0682693B1 (fr) Adjuvant pour detergents ou nettoyants
DE19624415A1 (de) Verfahren zur Herstellung von festen Wasch- oder Reinigungsmitteln
EP0769045B1 (fr) Detergent contenant de la cellulase
EP1058722B1 (fr) Combinaison de tensioactifs contenant des tensioactifs anioniques speciaux
WO1999043774A1 (fr) Detergent et nettoyant pulverulent a granulaire
WO1997009404A1 (fr) Systeme inhibiteur de grisage a base d'enzyme
WO1998055568A1 (fr) Agents de lavage ou de nettoyage a pouvoir nettoyant eleve
DE19834382A1 (de) Alkylpolyglycoside als Cobuilder
DE19846439A1 (de) Waschmittel mit kationischen Alkyl- und/oder Alkenylpolyglykosiden
DE19854083A1 (de) Citronensäurehaltiges Waschmittel
DE19632284A1 (de) Wasch- oder Reinigungsmitteladditiv sowie ein Verfahren zu seiner Herstellung

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1995905070

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1995905070

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 1995905070

Country of ref document: EP