EP0991743B1 - Wasch- und reinigungsmittel - Google Patents

Wasch- und reinigungsmittel Download PDF

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Publication number
EP0991743B1
EP0991743B1 EP98937453A EP98937453A EP0991743B1 EP 0991743 B1 EP0991743 B1 EP 0991743B1 EP 98937453 A EP98937453 A EP 98937453A EP 98937453 A EP98937453 A EP 98937453A EP 0991743 B1 EP0991743 B1 EP 0991743B1
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EP
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Prior art keywords
acid
weight
soil release
alkyl
srp
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EP98937453A
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German (de)
English (en)
French (fr)
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EP0991743A1 (de
Inventor
Frank-Peter Lang
Gerd Reinhardt
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Clariant Produkte Deutschland GmbH
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Clariant Produkte Deutschland GmbH
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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
    • C11D3/0005—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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters

Definitions

  • the invention relates to detergents and cleaners which contain a soil-repellent polymer and also alkanesulfonate and / or olefinsulfonate as anionic surfactant.
  • Detergents contain, in addition to the indispensable for the washing process ingredients such as surfactants and builders usually other ingredients that can be summarized under the term washing aids and include as different active ingredients such as foam regulators, graying inhibitors, bleach, bleach activators and dye transfer inhibitors. Such excipients also include substances which impart soil repellent properties to the laundry fiber and which, if present during the wash, aid the soil release properties of the remaining detergent ingredients. The same applies mutatis mutandis to cleaners for hard surfaces. Such soil release agents are often referred to as “soil release” agents or because of their ability to provide the treated surface, e.g., fabric, with soil repellency, as “soil repellents".
  • copolyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. Dirt-releasing copolyesters of the type mentioned as well as their use in detergents have been known for a long time.
  • soil release polymers with molar masses in the range from 600 to 100,000 g / mol and with softening temperatures or melting points in the range from 30 ° C. to 170 ° C., preferably in the range from 40 ° C. to 80 ° C., are preferably used.
  • German laid-open specification DE 16 17 141 describes a washing process using polyethylene terephthalate-polyoxyethylene glycol copolymers.
  • German laid-open specification DE 22 00 911 relates to detergents which contain nonionic surfactant and a copolymer of polyoxyethylene glycol and polyethylene terephthalate.
  • acidic textile finishing agent is called, which is a copolymer a dibasic carboxylic acid and an alkylene or cycloalkylene polyglycol and optionally an alkylene or cycloalkylene glycol.
  • European patent EP 066 944 relates to textile treatment compositions containing a copolyester of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios.
  • European Patent EP 185,427 discloses methyl or ethyl end-capped polyesters having ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and detergents containing such soil release polymer.
  • European Patent EP 241 984 relates to a polyester which, besides oxethylene groups and terephthalic acid units, also contains substituted ethylene units and also glycerol units.
  • European Patent EP 241 985 are known polyester containing in addition to oxyethylene groups and terephthalic acid units, 1,2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene groups and glycerol units and with C 1 -C 4 alkyl groups are end lawver liability.
  • European Patent EP 253 567 relates to soil release polymers having a molecular weight of 900 to 9000 from ethylene terephthalate and polyethylene oxide terephthalate, wherein the polyethylene glycol units have molecular weights of 300 to 3000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate 0.6 to 0.95.
  • European Patent Application EP 272 033 discloses polyesters having polypropylene terephthalate and polyoxyethylene terephthalate units which are at least partially capped by C 1 -C 4 -alkyl or acyl radicals.
  • European Patent EP 274,907 describes sulfoethyl end-capped terephthalate-containing soil release polyesters.
  • EP 357,280 are prepared by sulfonation of unsaturated end groups soil release polyester with terephthalate, alkylene glycol and poly-C 2 -C 4 glycol units.
  • Such soil release polymers are marketed under the names Sokalan® HP 40, Sokalan 9976 (BASF) or Velvetol® (Rhone-Poulenc), Repel-O-Tex® (Rhone-Poulenc), Zelcon® (Dupont), Permalose® (ICI) or Milease® (ICI) commercially available.
  • Preferred soil release polyesters include those compounds which are formally accessible by esterification of two monomeric moieties, the first monomer being a dicarboxylic acid HOOC-Ph-COOH and the second monomer being a diol HO- (CHR 3 -) a OH, also known as polymeric diol H- (O- (CHR 3 -) a ) b OH may be present.
  • Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof
  • R 3 is hydrogen, an alkyl radical having 1 to 22 C atoms and mixtures thereof
  • a is a number from 2 to 6
  • b is a number from 1 to 300.
  • the molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10.
  • the degree of polymerization b is preferably in the range from 1 to 500, in particular from 12 to 140.
  • the molecular weight or the average molecular weight or the maximum of the molecular weight distribution is more preferred
  • the soil release polymer is preferably in the range from 250 to 100,000, especially from 500 to 50,000.
  • the acid underlying Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof , If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferable.
  • the soil release-capable polyester may be present in the soil release-capable polyester.
  • these include, for example, alkylene and alkenylene dicarboxylic acids, such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
  • the preferred diols HO- (CHR 3 -) a OH include those in which R 3 is hydrogen and a is a number from 2 to 6, and those in which a is 2 and R 3 is hydrogen or alkyl with 1 to 10, in particular 1 to 3 carbon atoms.
  • R 3 is hydrogen and a is a number from 2 to 6
  • R 3 is hydrogen or alkyl with 1 to 10, in particular 1 to 3 carbon atoms.
  • those of the formula HO-CH 2 -CHR 3 -OH, in which R 3 has the abovementioned meaning are particularly preferred.
  • diol components are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-decanediol, 1, 2-dodecanediol and neopentyl glycol.
  • Particularly preferred among the polymeric diols is polyethylene glycol having an average molecular weight in the range of 1000 to 6000.
  • the polyesters composed as described above may also be end-capped, alkyl groups having from 1 to 22 carbon atoms and esters of monocarboxylic acids being suitable as end groups.
  • the ester groups bound by end groups alkyl, alkenyl and Arylmonocarbonklaren with 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms, based.
  • the end groups may also be based on hydroxymonocarboxylic acids having 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, their hydrogenation product hydroxystearic acid, and o-, m- and p-hydroxybenzoic acid.
  • the hydroxymonocarboxylic acids may in turn be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group.
  • the number of hydroxymonocarboxylic acid units per end group is in the range from 1 to 50, in particular from 1 to 10.
  • the washing or cleaning agent contains polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molecular weights of 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10.
  • oligoesters are prepared from dimethyl terephthalate, ethylene glycol and / or propylene glycol, polyethylene glycol and C 1 -C 18 -alkylpolyethylene glycol with the addition of a catalyst first by transesterification at from 160 to about 220 ° C. and distillative removal of the methanol at normal pressure and subsequent separation by distillation the excess glycols obtained at temperatures of 160 to about 240 ° C.
  • the alkyl group may be either saturated or unsaturated, branched or linear and optionally substituted with a hydroxyl group.
  • the sulfo group is preferably attached to a secondary carbon atom but may also be terminally attached to a primary carbon atom.
  • the alkanesulfonate may be a primary or secondary alkanesulfonate or mixtures thereof. Sec. Alkanesulfonates are preferred.
  • the preferred alkanesulfonates contain linear alkyl chains of about 9 to 25 carbon atoms, preferably about 10 to about 22 carbon atoms, and more preferably about 13 to 17 or 16 to 18 carbon atoms.
  • the cation is, for example, sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium and mixtures thereof. Preference is given to secondary alkanesulfonates with sodium as cation.
  • the ⁇ -olefinsulfonates are obtained by sulfonation of C 12 -C 24 -, preferably C 14 -C 16 -alpha-olefins with sulfur trioxide and subsequent neutralization. Due to the preparation process, these olefin sulfonates may contain minor amounts of hydroxyalkanesulfonates and alkanedisulfonates. Specific blends of alpha olefin sulfonates are described in US 3,332,880.
  • the weight ratio of soil release-active polyester to the sum of the surfactants is preferably 1:25 to 1: 2, in particular 1:20 to 1: 3.5.
  • Detergents or cleaners containing the active ingredient combination according to the invention may contain all the usual other ingredients of such agents.
  • the active ingredient combination according to the invention in amounts of 5 wt .-% to 50 wt .-%, in particular 8 wt .-% to 25 wt .-% incorporated in detergents or cleaning agents.
  • Suitable nonionic surfactants include the alkoxylates, in particular the ethoxylates and / or propoxylates of native or synthetic, saturated or mono- to polyunsaturated linear or branched-chain alcohols which carry a primary or secondary OH group, with 10 to 22 C Atoms, preferably 12 to 18 carbon atoms.
  • the degree of alkoxylation of the alcohols is generally between 1 and 15, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides.
  • alkoxylates in particular the ethoxylates, primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof.
  • alkoxylation products of alkylamines, vicinal diols and carboxylic acid amides which correspond in terms of the alkyl part of said alcohols, usable.
  • alkylpolyglycosides which are suitable for incorporation in the compositions according to the invention are compounds of the general formula (G) p-OR 4 , in which R 4 is an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and p is a number between 1 and 10 mean.
  • Glycoside component (G) p are oligomers or polymers of naturally occurring aldose or ketose monomers, which include, in particular, glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, xylose and Include lyxose.
  • the oligomers consisting of such glycosidically linked monomers are characterized not only by the nature of the sugars contained in them by their number, the so-called Oligomertechnischsgrad.
  • the degree of oligomerization p generally assumes fractional numerical values as the quantity to be determined analytically; it is between 1 and 10, with the glycosides preferably used below a value of 1.5, in particular between 1.2 and 1.4.
  • Preferred monomer building block is glucose because of its good availability.
  • the alkyl or alkenyl moiety R4 of the glycosides preferably also originates from readily available derivatives of renewable raw materials, in particular from fatty alcohols, although their branched-chain isomers, in particular so-called oxoalcohols, can also be used for the preparation of useful glycosides.
  • the primary alcohols having linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly suitable.
  • Additional nonionic surfactant is contained in agents which contain the combination of active substances on which the invention is based, preferably in amounts of up to 30% by weight, in particular from 1% by weight to 25% by weight, based in each case on the total agent.
  • compositions according to the invention may instead or additionally comprise further surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type, in amounts of preferably not more than 20% by weight, in particular from 0.1% by weight to 18% by weight, in each case based on total resources.
  • particularly suitable synthetic anionic surfactants are the alkyl and / or alkenyl sulfates having 8 to 22 carbon atoms, an alkali metal, ammonium or Wear alkyl- or hydroxyalkyl-substituted ammonium ion as a counter cation to call.
  • alkyl and alkenyl sulfates can be prepared in a known manner by reaction of the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases.
  • a conventional sulfating reagent in particular sulfur trioxide or chlorosulfonic acid
  • alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases Such alkyl and / or alkenyl sulfates are preferably contained in amounts of from 0.1% by weight to 20% by weight, in particular from 0.5% by weight to 18% by weight.
  • Suitable anionic surfactants of the sulfonate type include the ⁇ -sulfoesters obtainable by reaction of fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those of fatty acids having 8 to 22 C atoms, preferably 12 to 18 C atoms, and linear alcohols having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derivative sulfonation products, as well as the sulfonated fatty acids resulting from formal saponification thereof.
  • alkenyl or alkylbenzenesulfonates are alkenyl or alkylbenzenesulfonates.
  • the alkenyl or alkyl group may be branched or linear and optionally substituted with a hydroxyl group.
  • the preferred alkylbenzenesulfonates contain linear alkyl chains of about 9 to 25 carbon atoms, preferably from about 10 to about 13 carbon atoms, the cation being sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium and mixtures thereof.
  • alkyl ether sulfates are also suitable as anionic surfactants of the sulfate type.
  • alkyl ether sulfates are water-soluble salts or acids of the formula RO (A) m SO 3 M, where R is an unsubstituted C 10 -C 24 -alkyl or hydroxyalkyl radical, preferably a C 12 -C 20 -alkyl or hydroxyalkyl radical, particularly preferred a C 12 -C 18 alkyl or hydroxyalkyl radical.
  • A is an ethoxy or propoxy moiety
  • m is a number greater than 0, preferably between about 0.5 and about 6, more preferably between about 1.5 and about 3
  • M is a hydrogen atom or a cation such as
  • substituted ammonium cations are methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethytpiperidinium cations, as well as those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof.
  • alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof.
  • Examples which may be mentioned are C 12 -C 18 fatty alcohol ether sulfates, the content of ethylene oxide being 1, 2, 2.5, 3 or 4 mol per mole of fatty alcohol ether sulfate, and M being sodium or potassium.
  • soaps suitable being saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids.
  • those soap mixtures are preferred which are composed of 50% to 100% by weight of saturated C 12 -C 18 fatty acid soaps and up to 50% by weight of oleic acid soap.
  • soap is included in amounts of from 0.1% to 5% by weight.
  • liquid detergents of the invention may also contain higher amounts of soap, generally up to 20% by weight.
  • an agent according to the invention contains water-soluble and / or water-insoluble builders, in particular selected from alkali metal aluminosilicate, crystalline alkali metal silicate with modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts ranging from 2.5% by weight to 60% by weight.
  • An agent which comprises the combination of active substances on which the invention is based preferably contains from 20% by weight to 55% by weight of water-soluble and / or water-insoluble, organic and / or inorganic builders.
  • the water-soluble organic builder substances include, in particular, those from the class of the polycarboxylic acids, in particular citric acid and sugar acids, as well as the polymeric (poly) carboxylic acids, in particular those by oxidation of Polysaccharides accessible polycarboxylates of the international patent application WO 93/16110, polymeric acrylic acids, methacrylic acids, maleic acid and copolymers thereof, which may also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality.
  • the molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5000 and 200,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on the free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000.
  • Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight.
  • the first acidic monomer 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 or its salt can be a derivative of a C 4 -C 8 -dicarboxylic acid, preferably a C 4 -C 8 -dicarboxylic acid, with maleic acid being particularly preferred.
  • the third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol.
  • vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example C 1 -C 4 carboxylic acids, with vinyl alcohol.
  • Preferred terpolymers contain 60 wt .-% to 95 wt .-%, in particular 70 wt .-% to 90 wt .-% of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% of vinyl alcohol and / or vinyl acetate.
  • the second acidic monomer 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 , is substituted.
  • Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10% by weight. to 30 wt .-%, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid or Methallylsulfonat and as a third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt. % of a carbohydrate.
  • This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred, sucrose being particularly preferred.
  • the use of the third monomer presumably incorporates predetermined breaking points in the polymer which are responsible for the good biodegradability of the polymer.
  • These terpolymers can be prepared in particular by processes which are described in German Patent DE 42 21 381 and German Patent Application DE 43 00 772, and generally have a molecular weight between 1000 and 200,000, preferably between 200 and 50,000 and in particular between 3000 and 10000 on.
  • polycarboxylic acids can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions.
  • All the polycarboxylic acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • Such organic builders are preferred. in amounts up to 40 wt .-%, in particular up to 25 wt .-% and particularly preferably of 1 wt .-%. contain up to 5 wt .-%. Quantities near the upper limit mentioned are preferably in pasty or liquid, in particular hydrous, used agents in which the invention underlying drug combination is included.
  • Amounts near the above upper limit are preferably used in solid, particulate agents.
  • suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m.
  • Their calcium binding capacity which can be determined according to the specifications of the German patent DE 24 12 837, is generally in the range of 100 to 200 mg CaO per gram.
  • Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline or amorphous alkali silicates which may be present alone or in a mixture with one another.
  • the alkali metal silicates useful as builders in the compositions according to the invention preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form.
  • Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of 1: 2 to 1: 2.8.
  • Amorphous silicates with a molar ratio of 1: 2 to 1: 2, 11 are available from departmentsohnst under the name 3Na in powder form and 3NaG in granulated form.
  • the crystalline silicates are crystalline layer silicates with the general formula Na 2 Si x O 2x + 1 yH 2 O used in the x, the so-called module is a number from 1.9 to 4 and y is a number from 0 to 20, preferred Values for x are 2, 3 or 4.
  • Crystalline layered silicates that fall under this general formula become For example, in the European patent application EP 0 164 514. Such a crystalline sheet silicate is under the name SKS-6 of Hoechst AG in the trade.
  • Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
  • both ⁇ - and 6-sodium disilicates are preferred, whereby ⁇ -sodium disilicate can be obtained, for example, by the process described in international patent application WO 91/08171.
  • 6-Sodium silicates with a modulus between 1.9 and 3.2 can be prepared according to Japanese Patent Applications JP 04/238809 or JP 04/260 610.
  • Crystalline sodium silicates with a modulus ranging from 1.9 to 3.5, as prepared by the methods of European patents EP 0 164 552 and / or EP 0 294 753 are used in a further preferred embodiment of the washing or cleaning agents according to the invention.
  • the content of alkali silicates which can be used as builder is preferably 1% by weight to 50% by weight and in particular 5% by weight to 35% by weight, based on anhydrous active substance. If alkali metal aluminosilicate, in particular zeolite, is present as an additional builder substance, the content of alkali silicate is preferably 1% by weight to 15% by weight and in particular 2% by weight to 8% by weight, based on anhydrous active substance.
  • the weight ratio of aluminosilicate to silicate, in each case based on anhydrous active substances, is then preferably 4: 1 to 10: 1.
  • the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.
  • inorganic builder in addition to the mentioned inorganic builder, other water-soluble or water-insoluble inorganic substances can be used in the agents according to the invention. Suitable in this context are the alkali metal carbonates, alkali metal bicarbonates and alkali metal sulfates and mixtures thereof. Such additional inorganic material may be present in amounts up to 70% by weight, but is preferably absent entirely.
  • the agents may contain other ingredients customary in detergents and cleaners.
  • These optional ingredients include, in particular, enzymes, enzyme stabilizers, bleaches, bleach activators, complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids, grayness inhibitors, for example cellulose ethers, dye transfer inhibitors, for example polyvinylpyrrolidone or polyvinylpyridine N-oxide, foam inhibitors, for example organopolysiloxanes or Paraffins, solvents and optical brighteners, for example stilbene disulfonic acid derivatives.
  • enzymes enzyme stabilizers
  • bleaches bleach activators
  • complexing agents for heavy metals for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids
  • grayness inhibitors for example cellulose ethers
  • dye transfer inhibitors for example polyvinylpyrroli
  • compositions according to the invention up to 1% by weight, in particular 0.01% by weight to 0.5% by weight, of optical brighteners, in particular compounds from the class of the substituted 4,4'-bis (2, 4,6-triamino-s-triazinyl) -stilbene-2,2'-disulfonic acids, up to 5 wt .-%, in particular 0.1 wt .-% to 2 wt .-% complexing agent for heavy metals, especially Aminoalkylenphosphonklaren and their Salts, up to 3 wt .-%, in particular 0.5 wt .-% to 2 wt .-% graying inhibitors and up to 2 wt .-%, in particular 0.1 wt .-% to 1 wt .-% foam inhibitors , Wherein said parts by weight each refer to total means.
  • optical brighteners in particular compounds from the class of the substituted 4,4'-bis (2, 4,6-triamino-s-
  • Solvents which are used in particular for liquid agents according to the invention are, in addition to water, preferably those which are water-miscible. These include the lower alcohols, for example ethanol, propanol, isopropanol, and the isomeric butanols, glycerol, lower glycols, for example ethylene and propylene glycol, and the ethers derivable from the mentioned classes of compounds.
  • the soil release-rich polyesters are usually dissolved or in suspended form.
  • present enzymes are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase or mixtures thereof.
  • proteases derived from microorganisms such as bacteria or fungi, come into question. It can be obtained in a known manner by fermentation processes from suitable microorganisms, for example, in the German patents DE 19 40 488, DE 20 44 161, DE 22 01 803 and DE 21 21 397, US Pat. Nos. 3,632,957 and US 4,264,738, European Patent Application EP 006 638 and international patent application WO 91/02792.
  • Proteases are commercially available, for example, under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym® or Maxapem®.
  • the lipase which can be used can be prepared from Humicola lanuginosa, as described, for example, in European patent applications EP 258 068, EP 305 216 and EP 341 947, from Bacillus species, as described, for example, in international patent application WO 91/16422 or European patent application EP 384 717 , from Pseudomonas species, as for example in the European patent applications EP 468 102, EP 385 401, EP 375 102, EP 334 462, EP 331 376, EP 330 641, EP 214 761, EP 218 272 or EP 204 284 or the international Patent application WO 90/10695, from Fusarium species, as described for example in the European patent application EP 130,064, from Rhizopus
  • Suitable lipases are, for example, under the name Lipolase®, Lipozym®, Lipomax®, Amano® lipase, Toyo-jozo® lipase, Meito® lipase and Diosynth® lipase are commercially available.
  • Suitable amylases are commercially available, for example, under the names Maxamyl® and Termamyl®.
  • the usable cellulase may be a recoverable from bacteria or fungi enzyme, which has a pH optimum, preferably in the weakly acidic to slightly alkaline range of 6 to 9.5.
  • Such cellulases are known, for example, from German Offenlegungsschriften DE 31 17 250, DE 32 07 825, DE 32 07 847, DE 33 22 950 or European patent applications EP 265 832, EP 269 977, EP 270 974, EP 273 125 and EP 339 550 known.
  • the customary enzyme stabilizers which may be present, in particular in liquid agents of the invention, include amino alcohols, for example mono-, di-, triethanol- and -propanolamine and mixtures thereof, lower carboxylic acids, for example boric acid known from European patent applications EP 376 705 and EP 378 261 or alkali borates, boric acid-carboxylic acid combinations, as known for example from European Patent Application EP 451 921, boric acid esters, such as, for example, from the international patent application WO 93/11215 or the European patent application EP 511 456 known boronic acid derivatives, such as from the European patent application EP Calcium salts, for example the known from European Patent EP 28 865 Ca-formic acid combination, magnesium salts, as known for example from European Patent Application EP 378 262, and / or sulfur-containing reducing agents, as in For example, from the European patent applications EP 080 748 or EP 080 223 known.
  • lower carboxylic acids for example boric acid known from European patent applications EP 376 7
  • Suitable foam inhibitors include long-chain soaps, especially behenic soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which moreover can contain microfine, optionally silanated or otherwise hydrophobicized silica.
  • foam inhibitors preferably bound to granular, water-soluble carrier substances, as described, for example, in German Offenlegungsschrift DE 34 36 194, European patent applications EP 262 588, EP 301 414, EP 309 931 or European patent EP 150 386.
  • an agent according to the invention may contain graying inhibitors.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the graying of the fibers.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • soluble starch preparations and other than the above-mentioned starch products can be used, for example partially hydrolyzed starch. Na-carboxymethylcellulose, methylhydroxyethylcellulose and mixtures thereof are preferably used.
  • a further embodiment of an agent according to the invention contains peroxygen-based bleaching agents, in particular in amounts ranging from 5% by weight to 70% by weight, and optionally bleach activator, in particular in amounts ranging from 2% by weight to 10% by weight.
  • the bleaches in question are the perfluoro compounds usually used in detergents, such as hydrogen peroxide, perborate, which may be present as tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally present as alkali metal salts, in particular as sodium salts.
  • Such bleaching agents are in detergents which contain a combination of active substances according to the invention, preferably in amounts of up to 25 wt .-%, in particular up to 15 wt .-% and particularly preferably from 5 wt .-% to 15 wt .-%, in each case on total means, available.
  • the optional component of the bleach activators includes the commonly used N- or O-acyl compounds, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulphurylamides and cyanurates, moreover carboxylic anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl-phenolsulphonate, and acylated sugar derivatives, in particular pentaacetylglucose.
  • N- or O-acyl compounds for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N
  • the bleach activators may have been coated or granulated in a known manner with coating substances in order to avoid the interaction with the per compounds, with the aid of carboxymethylcellulose granulated tetraacetylethylenediamine having average particle sizes of 0.01 mm to 0.8 mm, as for example according to in European Patent EP 37,026 can be prepared, and / or granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, as described by the method described in German Patent DD 255,884 can be prepared, is particularly preferred.
  • Such bleach activators are preferably contained in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the total agent.
  • the agent according to the invention is present as a powder and, in addition to the active ingredient combination according to the invention, contains 20% by weight to 55% by weight of inorganic builder, up to 15% by weight, in particular 2% by weight to 12% by weight.
  • % water-soluble organic builder 2.5% by weight to 20% by weight synthetic anionic surfactant, 0.5% by weight to 20% by weight nonionic surfactant, up to 25% by weight, in particular 1% by weight % to 15 wt .-% bleach, up to 8 wt .-%, in particular 0.5 wt .-% to 6 wt .-% bleach activator and up to 20 wt .-%, in particular 0.1 wt .-% to 15% by weight of inorganic salts, especially alkali carbonate and / or sulfate.
  • such a pulverulent composition in particular for use as a mild detergent, contains from 20% by weight to 55% by weight of inorganic builder, up to 15% by weight, in particular from 2% by weight to 12% by weight.
  • % water-soluble organic builder 4 wt .-% to 24 wt .-% nonionic surfactant, up to 15 wt .-%, in particular 1 wt .-% to 10 wt .-% synthetic anionic surfactant, up to 65 wt .-%, in particular 1 wt .-% to 30 wt. % inorganic salts, in particular alkali carbonate and / or sulfate, and neither bleach nor bleach activator.
  • Another preferred embodiment comprises a liquid agent containing from 5% to 35% by weight of water-soluble organic builder, up to 15% by weight, especially from 0.1% to 5% by weight of water-insoluble inorganic builder , up to 15% by weight, in particular 0.5% by weight to 10% by weight of synthetic anionic surfactant, 1% by weight to 25% by weight of nonionic surfactant, up to 15% by weight, in particular 4 Wt .-% to 12 wt .-% soap and up to 30 wt .-%, in particular 1 wt .-% to 25 wt .-% water and / or water-miscible solvent.
  • SRP surfactant-soil release polymer
  • aqueous solutions of 1.0 g / l or 0.5 g / l of the respective surfactants and 0.06 g / l of a soil release polymer were prepared and prewashed with these solutions polyester WFK 30 A test fabric (laundry research institute Krefeld).
  • the pretreated fabrics were dried and soiled with used motor oil. After an exposure time of 1 hour, the test cloths were washed with the same surfactant / soil release polymer solutions. Subsequently, the remissions of the test tissues were measured.
  • test fabrics with the surfactant solutions without the addition of a soil release polymer or with the soil release polymer without presence washed a surfactant and determined the remissions.
  • Soil release polymers prepared as indicated below, used in the amount indicated in each case in the table.
  • Soil Release Polymer ® Repel-O-Tex SRP 4 from Rhone-Poulenc, used in the amount indicated in each case in the table.
  • the Soil Release Polymer I according to Example 1 was incorporated into a liquid detergent formulation which contained liquid as an anionic surfactant Hostapur SAS 60 or Hostapur OS and, for comparison, Marlon A 350.
  • Polyester fabric WFK 30 A was pre-washed comparatively with the detergents, dried, with Soiled engine oil and washed after a contact time of one hour, each with the same detergents as in the pre-wash.
  • the detergent concentration was 6 g / l.
  • the dirt removal was determined by measuring the remission.
  • the washing tests were carried out without the addition of the soil release polymer.
  • the washing conditions were the same as in Example 1. Table 5 Composition of liquid detergents in% by weight.
  • the Soil Release Polymer I according to Example 1 was incorporated into a washing powder containing as anionic surfactant Hostapur SAS 60 and as a comparison Marlon A 350. Subsequently, with these, as described in Example 2, washing tests were carried out on polyester fabric WFK 30A. The washing powder concentration was 6 g / l. For comparison, the washing tests were also carried out without the addition of this soil release polymer.
  • Table 7 Composition of washing powders in% by weight washing powder Formulation I Formulation II Marlon A 350 9.6 Hostapur SAS 60 8.0 Genapol LA 070 5.1 5.1 Soap 3.6 3.6 Zeolite A 32.1 32.1 SKS-6 3.4 3.4 soda 11.7 11.7 sodium sulphate 23.4 23.4 Na salt of a copolymer of acrylic and maleic acid 5.1 5.1 carboxymethylcellulose 1.3 1.3 EDTA 0.2 0.2 Water, foam inhibitor ad 100 ad 100 Enzymes (protease, amylase) 0.9 0.9 Soil release polymer 1.0 1.0 washing powder Remission (%) Formulation I without SRP 26.4 Formulation I with SRP 31.2 Formulation II without SRP 26.5 Formulation II with SRP 36.2
  • the Soil Release Polymer I (SRP I) according to Example 1 was incorporated into a second washing powder containing as anionic surfactant Hostapur SAS 93-G and as a comparison Marlon ARL. This was followed by washing tests on polyester fabric WFK 30 A, as described in Example 2. The washing powder concentration was 6 g / l. For comparison, the washing tests were also carried out without the addition of this soil release polymer.
  • Table 9 Composition of washing powders in% by weight washing powder Formulation III Formulation IV Marion ARL 10 Hostapur SAS 93-G 8.6 Genapol OA 040 4 4 Genapol OA 080 4 4 sodium 11 11 sodium sulphate 7 8.4 Zeolite A 24 24 citric acid 5 5 Sokalan CP 5 6 6 percarbonate 20 20 TAED 5 5 foam inhibitor 1 1 Enzymes (protease, amylase) 2 2 Soil release polymer 1 1 washing powder Remission (%) Formulation III without SRP 27.2 Formulation III with SRP 35.1 Formulation IV without SRP 27.2 Formulation IV with SRP 41.8
  • Marlon® A 350 linear C 10 -C 12 -alkylbenzenesulfonate, Huels AG Na salt, 50% Sulfopon® 1218 GF C 12 -C 18 fatty alcohol sulfate, 90% Henkel KGaA Hostapur® SAS 30 / Clariant GmbH secondary C 13 -C 17 n-alkanesulfonate sodium salt, 30% strength Hostapur® SAS 60 ...
  • n-alkanesulfonate sodium salt 60% Hostapur® OS liquid C 14 -C 16 alpha-olefin sulfonate sodium salt, Clariant GmbH 42% Repel-O-Tex® SRP 4 / Ethylene glycol, polyethylene glycol Terephthal Acid Rhone-Poulenc Copolymer to 70%, balance sodium sulfate and sodium aluminum silicate Genapol® OA 040 C 14 -C 15 oxo alcohol ethoxylate with Clariant GmbH 3 EO Genapol® OA 080 C 14 -C 15 oxo alcohol ethoxylate with 8EO, Clariant GmbH 100% Dequest® 2066 25% aqueous solution of heptasodium Monsanto salts of diethylenetriaminepenta- (methylenephosphonic acid) Genapol® LA 070 / C 12/14 fatty alcohol ethoxylate with 7EO, Clariant GmbH 100% SKS-6 / Clariant GmbH crystalline.

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Families Citing this family (54)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3910530B2 (ja) * 2002-12-16 2007-04-25 花王株式会社 汚れ放出剤
DE10351321A1 (de) * 2003-02-10 2004-08-26 Henkel Kgaa Verstärkung der Reinigungsleistung von Waschmitteln durch eine Kombination von Cellulosderivaten
JP2006517245A (ja) * 2003-02-10 2006-07-20 ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチエン 発泡調節剤としてのセルロース誘導体の使用
ATE350447T1 (de) * 2003-02-10 2007-01-15 Henkel Kgaa Erhöhung der wasseraufnahmefähigkeit von textilien
DE502004001801D1 (de) * 2003-02-10 2006-11-30 Henkel Kgaa Bleichmittelhaltiges waschmittel mit baumwollaktivem schmutzablösevermögendem cellulosederivat
JP4519122B2 (ja) * 2003-02-10 2010-08-04 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン 水溶性ビルダー系および汚れ解離性セルロース誘導体を含んでなる漂白剤含有洗濯または洗浄剤
DE10351325A1 (de) * 2003-02-10 2004-08-26 Henkel Kgaa Wasch- oder Reinigungsmittel mit wasserlöslichem Buildersystem und schmutzablösevermögendem Cellulosederivat
DE502004003950D1 (de) * 2003-02-10 2007-07-12 Henkel Kgaa Verstärkung der reinigungsleistung von waschmitteln durch cellulosederivat und hygroskopisches polymer
DE102004053970A1 (de) * 2004-11-09 2005-09-15 Clariant Gmbh Flüssigwaschmittel enthaltend anionische und kationische Tenside
DE102004053969A1 (de) * 2004-11-09 2005-09-15 Clariant Gmbh Flüssigwaschmittel enthaltend sekundäres Alkansulfonat und kationische Tenside
DE102005027604A1 (de) * 2005-06-15 2006-12-28 Clariant Produkte (Deutschland) Gmbh Reinigungsmittel für harte Oberflächen
EP1798232A1 (en) 2005-12-08 2007-06-20 Hybrigenics S.A. Inhibitors of cysteine proteases, the pharmaceutical compositions thereof and their therapeutic applications
US7846888B2 (en) * 2006-02-07 2010-12-07 Battelle Energy Alliance, Llc Long lasting decontamination foam
US7875613B2 (en) * 2006-10-30 2011-01-25 Hybrigenics Sa Tetracyclic inhibitors of cysteine proteases, the pharmaceutical compositions thereof and their therapeutic applications
DE102007013217A1 (de) 2007-03-15 2008-09-18 Clariant International Ltd. Anionische Soil Release Polymere
JP5342757B2 (ja) * 2007-07-26 2013-11-13 ライオン株式会社 液体漂白剤組成物
DE102007061861A1 (de) * 2007-12-19 2009-06-25 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmittel mit verbesserter Reinigungsleistung
DE102008015396A1 (de) * 2008-03-20 2009-09-24 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmittel mit Seife und polyesterbasiertem Soil-Release-Polymer
US8241624B2 (en) * 2008-04-18 2012-08-14 Ecolab Usa Inc. Method of disinfecting packages with composition containing peracid and catalase
US8226939B2 (en) 2008-04-18 2012-07-24 Ecolab Usa Inc. Antimicrobial peracid compositions with selected catalase enzymes and methods of use in aseptic packaging
EP2135931B1 (en) 2008-06-16 2012-12-05 The Procter & Gamble Company Use of soil release polymer in fabric treatment compositions
US8900328B2 (en) * 2009-03-16 2014-12-02 The Procter & Gamble Company Cleaning method
WO2011079459A1 (en) * 2009-12-31 2011-07-07 Rhodia (China) Co., Ltd. Combination of polymer and surfactant for improved laundry
WO2011120799A1 (en) 2010-04-01 2011-10-06 Unilever Plc Structuring detergent liquids with hydrogenated castor oil
BR112013019383B1 (pt) 2011-01-27 2021-04-06 Unilever Ip Holdings B.V. Polímero linear de liberação de sujeira e líquido detergente alcalino
WO2012104157A1 (en) 2011-01-31 2012-08-09 Unilever Plc Soil release polymers
WO2012104156A1 (en) 2011-01-31 2012-08-09 Unilever Plc Soil release polymers
EP2495300A1 (en) 2011-03-04 2012-09-05 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Structuring detergent liquids with hydrogenated castor oil
ES2421162T3 (es) 2011-04-04 2013-08-29 Unilever Nv Procedimiento de lavado de telas
EP2732015B1 (de) * 2011-07-12 2015-09-09 WeylChem Switzerland AG Verwendung einer kombination von sekundärem paraffinsulfonat und amylase zur erhöhung des reinigungsvermögens von flüssigen waschmitteln
US20140193887A1 (en) * 2011-07-12 2014-07-10 Clariant International Ltd. Use of Secondary Paraffin Sulfonates for Increasing the Cleaning Capacity of Enzymes
CN104011192B (zh) * 2011-12-20 2017-08-25 荷兰联合利华有限公司 包含去污聚合物的各向同性液体洗涤剂
DE102012204270A1 (de) * 2012-03-19 2013-09-19 Henkel Ag & Co. Kgaa Flüssiges Waschmittel mit erhöhter Reinigungsleistung
WO2013139702A1 (en) 2012-03-21 2013-09-26 Unilever Plc Laundry detergent particles
DE102012016444A1 (de) * 2012-08-18 2014-02-20 Clariant International Ltd. Polyester
WO2014046290A1 (ja) 2012-09-24 2014-03-27 味の素株式会社 スルホン酸塩型界面活性剤および／または硫酸塩型アニオン界面活性剤、ならびに複素環化合物を含む洗浄剤組成物
US9499772B2 (en) 2013-03-13 2016-11-22 Battelle Energy Alliance, Llc Methods of decontaminating surfaces and related compositions
DE102014218952A1 (de) 2014-09-19 2016-03-24 Henkel Ag & Co. Kgaa Mittel für die Textilbehandlung, enthaltend mindestens einen anionischen, aromatischen Polyester und mindestens einen nichtionischen, aromatischen Polyester
WO2016155993A1 (en) 2015-04-02 2016-10-06 Unilever Plc Composition
US9890350B2 (en) * 2015-10-28 2018-02-13 Ecolab Usa Inc. Methods of using a soil release polymer in a neutral or low alkaline prewash
WO2017102402A1 (en) 2015-12-14 2017-06-22 Unilever N.V. Isotropic detergent composition comprising weight-efficient polymers
WO2017133879A1 (en) 2016-02-04 2017-08-10 Unilever Plc Detergent liquid
EP3469130A1 (en) 2016-06-09 2019-04-17 Unilever PLC Laundry products
WO2017211697A1 (en) 2016-06-09 2017-12-14 Unilever Plc Laundry products
EP3272850A1 (en) 2016-07-19 2018-01-24 Henkel AG & Co. KGaA Easy ironing/anti-wrinkle/less crease benefit of fabric treatment compositions with the help of soil release polymers
WO2018127390A1 (en) 2017-01-06 2018-07-12 Unilever N.V. Stain removing composition
EP3635166A1 (en) 2017-06-09 2020-04-15 Unilever PLC, a company registered in England and Wales under company no. 41424 Laundry liquid dispensing system
WO2019038187A1 (en) 2017-08-24 2019-02-28 Unilever Plc IMPROVEMENTS RELATING TO THE CLEANING OF FABRICS
WO2019038186A1 (en) 2017-08-24 2019-02-28 Unilever Plc IMPROVEMENTS RELATING TO THE CLEANING OF FABRICS
WO2019063402A1 (en) 2017-09-29 2019-04-04 Unilever Plc LAUNDRY PRODUCTS
TR202005218U5 (tr) 2017-10-05 2020-08-21 Unilever Nv Çamaşır yıkama ürünleri.
WO2019111935A1 (ja) * 2017-12-06 2019-06-13 花王株式会社 繊維製品用洗浄剤組成物
CA3122650C (en) 2018-12-11 2023-04-11 Nouryon Chemicals International B.V. Polyester demulsifier
CN116018396B (zh) * 2020-08-28 2024-11-12 联合利华知识产权控股有限公司 洗涤剂组合物

Family Cites Families (84)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2016962A (en) 1932-09-27 1935-10-08 Du Pont Process for producing glucamines and related products
US1985424A (en) 1933-03-23 1934-12-25 Ici Ltd Alkylene-oxide derivatives of polyhydroxyalkyl-alkylamides
US2703798A (en) 1950-05-25 1955-03-08 Commercial Solvents Corp Detergents from nu-monoalkyl-glucamines
US3332880A (en) 1965-01-04 1967-07-25 Procter & Gamble Detergent composition
GB1154730A (en) 1965-10-08 1969-06-11 Ici Ltd Improvements in the Laundering of Synthetic Polymeric Textile Materials
US3547828A (en) 1968-09-03 1970-12-15 Rohm & Haas Alkyl oligosaccharides and their mixtures with alkyl glucosides and alkanols
GB1230463A (enExample) 1968-09-13 1971-05-05
GB1377092A (en) 1971-01-13 1974-12-11 Unilever Ltd Detergent compositions
FR2122026A5 (enExample) 1971-01-15 1972-08-25 Anvar
CA989557A (en) 1971-10-28 1976-05-25 The Procter And Gamble Company Compositions and process for imparting renewable soil release finish to polyester-containing fabrics
US3962152A (en) * 1974-06-25 1976-06-08 The Procter & Gamble Company Detergent compositions having improved soil release properties
US4125370A (en) 1976-06-24 1978-11-14 The Procter & Gamble Company Laundry method imparting soil release properties to laundered fabrics
US4116885A (en) 1977-09-23 1978-09-26 The Procter & Gamble Company Anionic surfactant-containing detergent compositions having soil-release properties
US4266031A (en) 1978-07-04 1981-05-05 Novo Industri A/S Protease product of reduced allergenicity
US4264738A (en) 1979-08-01 1981-04-28 Stepanov Valentin M Process for purification of proteolytic enzymes
US4287082A (en) 1980-02-22 1981-09-01 The Procter & Gamble Company Homogeneous enzyme-containing liquid detergent compositions containing saturated acids
DE3011998C2 (de) 1980-03-28 1982-06-16 Henkel KGaA, 4000 Düsseldorf Verfahren zur Herstellung eines lagerstabilen, leichtlöslichen Granulates mit einem Gehalt an Bleichaktivatoren
DK187280A (da) 1980-04-30 1981-10-31 Novo Industri As Ruhedsreducerende middel til et fuldvaskemiddel fuldvaskemiddel og fuldvaskemetode
CA1190695A (en) 1981-05-14 1985-07-16 George J. Stockburger Anionic textile treating compositions
EP0080748B1 (en) 1981-11-13 1985-07-10 Unilever N.V. Enzymatic liquid cleaning composition
US4462922A (en) 1981-11-19 1984-07-31 Lever Brothers Company Enzymatic liquid detergent composition
US4411831A (en) * 1981-12-02 1983-10-25 Purex Industries, Inc. Stable liquid anionic detergent compositions having soil, release properties
JPS591598A (ja) 1982-06-25 1984-01-06 花王株式会社 洗浄剤組成物
DE3324258A1 (de) 1982-07-09 1984-01-12 Colgate-Palmolive Co., 10022 New York, N.Y. Nichtionogene waschmittelzusammensetzung mit verbesserter schmutzauswaschbarkeit
JPS59156282A (ja) 1983-02-25 1984-09-05 Daikin Ind Ltd 新規耐熱性リパーゼおよびその製造法
DE3400008A1 (de) 1984-01-02 1985-07-11 Henkel KGaA, 4000 Düsseldorf Zur verwendung in tensidhaltigen mitteln geeignetes schaumregulierungsmittel
DE3413571A1 (de) 1984-04-11 1985-10-24 Hoechst Ag, 6230 Frankfurt Verwendung von kristallinen schichtfoermigen natriumsilikaten zur wasserenthaertung und verfahren zur wasserenthaertung
DE3417649A1 (de) 1984-05-12 1985-11-14 Hoechst Ag, 6230 Frankfurt Verfahren zur herstellung von kristallinen natriumsilikaten
US4636468A (en) 1984-06-25 1987-01-13 Genencor, Inc. Lipolytic enzyme derived from a aspergillus microorganism having an accelerating effect on cheese flavor development
ATE73150T1 (de) 1984-12-21 1992-03-15 Procter & Gamble Blockpolyester und aehnliche verbindungen, verwendbar als verschmutzungsentferner in waschmittelzusammensetzungen.
DK154572C (da) 1985-08-07 1989-04-24 Novo Industri As Enzymatisk detergentadditiv, detergent og fremgangsmaade til vask af tekstiler
US5278066A (en) 1985-08-09 1994-01-11 Gist-Brocades Nv Molecular cloning and expression of gene encoding lipolytic enzyme
US4933287A (en) 1985-08-09 1990-06-12 Gist-Brocades N.V. Novel lipolytic enzymes and their use in detergent compositions
US4713194A (en) 1986-04-15 1987-12-15 The Procter & Gamble Company Block polyester and like compounds having branched hydrophilic capping groups useful as soil release agents in detergent compositions
US4711730A (en) 1986-04-15 1987-12-08 The Procter & Gamble Company Capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters useful as soil release agents
GB8617255D0 (en) 1986-07-15 1986-08-20 Procter & Gamble Ltd Laundry compositions
US4810414A (en) 1986-08-29 1989-03-07 Novo Industri A/S Enzymatic detergent additive
DE3633519A1 (de) 1986-10-02 1988-04-14 Henkel Kgaa Verfahren zur herstellung von rieselfaehigen, stabilen schauminhibitor-konzentraten durch kompaktierende granulation
ES2060590T3 (es) 1986-10-28 1994-12-01 Kao Corp Celulasas alcalinas y microorganismos para su produccion.
JP2530181B2 (ja) 1986-10-31 1996-09-04 花王株式会社 アルカリセルラ―ゼ遺伝子を含むｄｎａ断片並びに該ｄｎａ断片を組み込んだ組換えプラスミド及び組換え微生物
US5108457A (en) 1986-11-19 1992-04-28 The Clorox Company Enzymatic peracid bleaching system with modified enzyme
SG28337G (en) 1986-11-27 1995-09-18 Kao Corp Alkaline cellulases and microorganisms capable of producing same
US4943532A (en) 1986-12-05 1990-07-24 Kao Corporation Alkali-resistant cellulases and microorganisms capable of producing same
GB8629936D0 (en) 1986-12-15 1987-01-28 Procter & Gamble Laundry compositions
US4721580A (en) 1987-01-07 1988-01-26 The Procter & Gamble Company Anionic end-capped oligomeric esters as soil release agents in detergent compositions
DE3723826A1 (de) 1987-07-18 1989-01-26 Henkel Kgaa Verfahren zur herstellung von alkylglykosiden
DE3725030A1 (de) 1987-07-29 1989-02-09 Henkel Kgaa Oberflaechenaktive hydroxysulfonate
DE3732947A1 (de) 1987-09-30 1989-04-13 Henkel Kgaa Zur verwendung in wasch- und reinigungsmitteln geeignetes schaumregulierungsmittel
US5240851A (en) 1988-02-22 1993-08-31 Fina Research, S.A. Lipase-producing Pseudomonas aeruginosa strain
BE1001436A3 (fr) 1988-02-22 1989-10-31 Synfina Sa Nouvelle lipase et compositions detergentes en contenant.
JP3079276B2 (ja) 1988-02-28 2000-08-21 天野製薬株式会社 組換え体ｄｎａ、それを含むシュードモナス属菌及びそれを用いたリパーゼの製造法
JP2652871B2 (ja) 1988-04-25 1997-09-10 花王株式会社 アルカリセルラーゼおよびその製造法
GB8810954D0 (en) 1988-05-09 1988-06-15 Unilever Plc Enzymatic detergent & bleaching composition
DE3827534A1 (de) 1988-08-13 1990-02-22 Henkel Kgaa Verfahren zur herstellung von alkylglucosidverbindungen aus oligo- und/oder polysacchariden
DE68925765T2 (de) 1988-08-26 1996-10-02 Procter & Gamble Schmutzabweisende Mittel mit von Allylgruppen abgeleiteten sulphonierten Endgruppen
US5576425A (en) 1988-10-05 1996-11-19 Henkel Kommanditgesellschaft Auf Aktien Process for the direct production of alkyl glycosides
US5275753A (en) 1989-01-10 1994-01-04 The Procter & Gamble Company Stabilized alkaline liquid detergent compositions containing enzyme and peroxygen bleach
US5093256A (en) 1989-02-22 1992-03-03 Shen Gwo Jenn Essentially purified, thermostable and alkalophilic lipase from bacillus sp. a30-1 atcc 53841
US5166069A (en) 1989-02-22 1992-11-24 Michigan Biotechnology Institute Bacillus sp. A30-1 ATCC no. 53841
US5063160A (en) 1989-03-16 1991-11-05 Olin Corporation Identification, characterization, and method of production of a novel microbial lipase
DE3914131A1 (de) 1989-04-28 1990-10-31 Henkel Kgaa Verwendung von calcinierten hydrotalciten als katalysatoren fuer die ethoxylierung bzw. propoxylierung von fettsaeureestern
US4950417A (en) 1989-05-01 1990-08-21 Miles Inc. Detergent formulations containing alkaline lipase derived from Pseudomonas plantarii
ES2144990T3 (es) 1989-08-25 2000-07-01 Henkel Of America Inc Enzima proteolitica alcalina y metodo de produccion.
US5236682A (en) 1989-10-25 1993-08-17 Hoechst Aktiengesellschaft Process for producing crystalline sodium silicates having a layered structure
US5196133A (en) 1989-10-31 1993-03-23 The Procter & Gamble Company Granular detergent compositions containing peroxyacid bleach and sulfobenzoyl end-capped ester oligomers useful as soil-release agents
US5182043A (en) 1989-10-31 1993-01-26 The Procter & Gamble Company Sulfobenzoyl end-capped ester oligomers useful as soil release agents in granular detergent compositions
US5256168A (en) * 1989-10-31 1993-10-26 The Procter & Gamble Company Sulfobenzoyl end-capped ester oligomers useful as soil release agents in granular detergent compositions
YU221490A (sh) 1989-12-02 1993-10-20 Henkel Kg. Postupak za hidrotermalnu izradu kristalnog natrijum disilikata
DE4000705A1 (de) 1990-01-12 1991-07-18 Hoechst Ag Verfahren zur herstellung von kristallinen natriumsilikaten
WO1991016422A1 (de) 1990-04-14 1991-10-31 Kali-Chemie Aktiengesellschaft Alkalische bacillus-lipasen, hierfür codierende dna-sequenzen sowie bacilli, die diese lipasen produzieren
WO1992004433A1 (en) 1990-09-07 1992-03-19 The Procter & Gamble Company Improved soil release agents for granular laundry detergents
EP0558515B1 (en) 1990-10-12 1997-07-09 The Procter & Gamble Company Process for preparing n-alkyl polyhydroxy amines and fatty acid amides therefrom in hydroxy solvents
DE4107230C2 (de) 1991-03-07 1995-04-06 Hoechst Ag Verfahren zur Herstellung von Natriumsilikaten
US5422030A (en) 1991-04-30 1995-06-06 The Procter & Gamble Company Liquid detergents with aromatic borate ester to inhibit proteolytic enzyme
DE69204472T2 (de) 1991-12-04 1996-05-02 Procter & Gamble Fluessige waschmittel mit zitronensaeure, cellulase und bor-diol-komplex um proteolytisches enzym zu inhibieren.
DE4142711A1 (de) 1991-12-21 1993-06-24 Hoechst Ag Verfahren zur herstellung von kristallinen natriumdisilikaten
DE4221381C1 (de) 1992-07-02 1994-02-10 Stockhausen Chem Fab Gmbh Pfropf-Copolymerisate von ungesättigten Monomeren und Zuckern, Verfahren zu ihrer Herstellung und ihre Verwendung
DE4203923A1 (de) 1992-02-11 1993-08-12 Henkel Kgaa Verfahren zur herstellung von polycarboxylaten auf polysaccharid-basis
ATE149563T1 (de) 1992-08-14 1997-03-15 Procter & Gamble Alpha-aminoborsäurehaltige flüssige waschmittel
US5415807A (en) * 1993-07-08 1995-05-16 The Procter & Gamble Company Sulfonated poly-ethoxy/propoxy end-capped ester oligomers suitable as soil release agents in detergent compositions
DE4400632C1 (de) 1994-01-12 1995-03-23 Henkel Kgaa Tensidgemische und diese enthaltende Mittel
DE4436151A1 (de) 1994-08-16 1996-05-02 Henkel Kgaa Verfahren zur Herstellung eines Flüssigwaschmittels mit Bleiche
DE4440956A1 (de) 1994-11-17 1996-05-23 Henkel Kgaa Schmutzabweisendes Waschmittel mit bestimmter Tensidkombination
US5922663A (en) 1996-10-04 1999-07-13 Rhodia Inc. Enhancement of soil release with gemini surfactants

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AU8624998A (en) 1999-01-04
ES2283066T3 (es) 2007-10-16
JP2002504948A (ja) 2002-02-12
JP4237269B2 (ja) 2009-03-11
AR016073A1 (es) 2001-06-20
WO1998058044A1 (de) 1998-12-23
DE19725508A1 (de) 1998-12-24
US6514927B2 (en) 2003-02-04
US20020042354A1 (en) 2002-04-11
EP0991743A1 (de) 2000-04-12
DE59813922D1 (de) 2007-04-12

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