EP0991743B1 - Detergent et produit de nettoyage - Google Patents

Detergent et produit de nettoyage 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)
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EP0991743A1 (fr
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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Claims (3)

  1. Produits détergents et nettoyants, contenant une combinaison de matières actives, constituée d'un polymère antisalissure et d'un alcanesulfonate et/ou d'un α-oléfinesulfonate, caractérisés en ce que le polymère d'enlèvement des salissures est un oligoester, pouvant être obtenu à partir d'acide téréphtalique, d'acide isophtalique, d'acide sulfoisophtalique et/ou de leurs esters méthyliques, d'acides dicarboxyliques aliphatiques et/ou de leurs anhydrides, d'acides dicarboxyliques aliphatiques substitués, de propylèneglycol, de polyéthylèneglycols, d'alkylpolyéthylèneglycols, d'esters de l'acide benzoïque du polyéthylèneglycol, d'esters de l'acide sulfobenzoïque du polyéthylèneglycol, et éventuellement d'alcanolamines.
  2. Produits détergents et nettoyants selon la revendication 1, caractérisés en ce que le rapport en poids du polymère à pouvoir d'enlèvement des salissures à la somme de l'alcanesulfonate et/ou de l'α-oléfine-sulfonate est de 1:25 à 1:2.
  3. Produits détergents et nettoyants selon la revendication 1, caractérisés en ce qu'ils contiennent 5 à 50 % en poids de la combinaison de matières actives.
EP98937453A 1997-06-17 1998-06-08 Detergent et produit de nettoyage Expired - Lifetime EP0991743B1 (fr)

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DE19725508A DE19725508A1 (de) 1997-06-17 1997-06-17 Wasch- und Reinigungsmittel
DE19725508 1997-06-17
PCT/EP1998/003423 WO1998058044A1 (fr) 1997-06-17 1998-06-08 Detergent

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

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