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EP1888732A1 - Renforcement du pouvoir detersif de detergents par l'intermediaire d'un polymere - Google Patents

Renforcement du pouvoir detersif de detergents par l'intermediaire d'un polymere

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Publication number
EP1888732A1
EP1888732A1 EP06742985A EP06742985A EP1888732A1 EP 1888732 A1 EP1888732 A1 EP 1888732A1 EP 06742985 A EP06742985 A EP 06742985A EP 06742985 A EP06742985 A EP 06742985A EP 1888732 A1 EP1888732 A1 EP 1888732A1
Authority
EP
European Patent Office
Prior art keywords
acid
polymer
weight
soil release
detergents
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP06742985A
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German (de)
English (en)
Other versions
EP1888732B1 (fr
Inventor
Josef Penninger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions

Definitions

  • the present patent application relates to enhancing the detergency of laundry detergents in the washing of textiles through the use of a particular soil release polymer.
  • Detergents contain in addition to the indispensable for the washing process ingredients such as surfactants and builder materials usually further ingredients that can be summarized by the term washing aids and include as different drug groups such as foam regulators, grayness inhibitors, bleach, bleach activators and dye transfer inhibitors.
  • Such adjuvants also include substances which impart soil repellency properties to the laundry fiber and, 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.
  • soil release agents are often referred to as “soil release” agents or because of their ability to impart soil repellency to the treated surface, such as the fiber, as “soil repellents".
  • European Patent Application EP 0 213 729 discloses the reduced redeposition when using detergents containing a combination of soap and nonionic surfactant with alkyl hydroxyalkyl cellulose.
  • European Patent Application EP 0 213 730 discloses textile treatment compositions which contain cationic surfactants and nonionic cellulose ethers having HLB values of from 3.1 to 3.8.
  • US Pat. No. 4,000,093 discloses detergents containing from 0.1% to 3% by weight of alkyl cellulose, hydroxyalkyl cellulose or alkyl hydroxyalkyl cellulose and from 5% to 50% by weight.
  • surfactant wherein the surfactant component consists essentially of C 10 - to C ⁇ -alkyl sulfate and up to 5 wt .-% C] 4 alkyl sulfate and less than 5 wt .-% alkyl sulfate having alkyl radicals of Ci 5 and higher.
  • 4,174,305 discloses detergents containing from 0.1% to 3% by weight of alkyl cellulose, hydroxyalkyl cellulose, or Alkyl-hydroxyalkyl cellulose and 5 wt .-% to 50 wt .-% surfactant, wherein the surfactant component consists essentially of Ci 0 - to Ci 2 -alkylbenzenesulfonate and less than 5 wt .-% alkylbenzenesulfonate with alkyl radicals of Cn and higher having.
  • European patent application EP 0 634 481 relates to a detergent containing alkali metal carbonate and one or more nonionic cellulose derivatives.
  • EP 0 271 312 relates to soil release agents, among these cellulose alkyl ethers and cellulose hydroxyalkyl ethers (having DS 1.5 to 2.7 and molecular weights of 2,000 to 100,000) such as methylcellulose and ethylcellulose, which contain peroxygen bleach in a weight ratio (Based on the active oxygen content of the bleaching agent) of 10: 1 to 1: 10 to be used.
  • European Patent EP 0 948 591 B1 discloses a detergent in liquid or granular form which imparts textile appearance advantages such as pilling / lint reduction, anti-color fading, improved abrasion resistance and / or increased softness to fabrics and textiles washed therewith, and to US Pat 80 wt .-% of surfactant, 1 to 80 wt .-% organic or inorganic builder, 0.1 to 80 wt .-% of a hydrophobically modified nonionic cellulose ether having a molecular weight of 10,000 to 2,000,000, wherein the modification in the Presence of optionally oligomerized (degree of oligomerization up to 20) ethyleneoxy or 2-propyleneoxy ether units and Cg -24 alkyl substituents and the alkyl substituents in amounts of 0.1-5 wt .-%, based on the cellulose ether material, is present have to be.
  • German Offenlegungsschrift DT 16 17 141 describes a washing process using polyethylene terephthalate-polyoxyethylene glycol copolymers.
  • the German Offenlegungsschrift DT 22 00 911 relates to detergents which contain nonionic surfactant and a copolymer of polyoxyethylene glycol and polyethylene terephthalate.
  • acidic textile finishing agents which contain a copolymer of a dibasic carboxylic acid and an alkylene or Cycloalkylenpolyglykol and optionally an alkylene or cycloalkylene glycol.
  • 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 50:50 to 90:10, and their use in detergents are in the German patent DE 28 57,292.
  • Polymers having a molecular weight of 15,000 to 50,000 of ethylene terephthalate and polyethylene oxide terephthalate, wherein the polyethylene glycol units have molecular weights of 1000 to 10,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 2: 1 to 6: 1, can according to the German Offenlegungsschrift DE 33 24 258 are used in detergents.
  • 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 oxyethylene groups and terephthalic acid units, also contains substituted ethylene units and also glycerol units.
  • European patent EP 241 985 discloses polyesters which, in addition to oxyethylene groups and terephthalic acid units, contain 1,2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene groups and also glycerol units and with Ci- to C 4 -alkyl groups are end group-capped.
  • European Patent EP 253 567 relates to soil release polymers having a molecular weight of 900 to 9000 of 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.
  • Detergents are known from German Patent DE 28 46 984 which contain, as a soil release polymer, a reaction product of a polyester with a prepolymer containing terminal isocyanate groups, obtained from a diisocyanate and a hydrophilic nonionic macrodiol.
  • the invention therefore relates to the use of a polymer obtainable from the monomers styrene, methacrylic acid, hydroxyethyl methacrylate and methyl methacrylate, for enhancing the cleaning performance of detergents in the washing of textiles.
  • Particularly preferred polymers are block polymers, ie those in which first a monomer, in particular styrene, is grafted on, and then with the others Carbonchingre phenomenon- or carboxylate-containing monomers, together or in succession, is reacted polymerizing.
  • Polymers which are particularly suitable according to the invention have a molecular weight of not more than 10,000 D, in particular from 3,000 D to 8,000 D. The determination of the molecular weight can be carried out using conventional chromatographic methods using known standards.
  • the use according to the invention can be carried out as part of a washing process in such a way that the polymer is added separately to a detergent-containing liquor, or the polymer is introduced into the liquor as a constituent of the detergent.
  • Another object of the invention is therefore a detergent containing a polymer described above.
  • the use according to the invention in the context of a laundry aftertreatment process can be carried out in such a way that the polymer is added separately to the rinse liquor or is it incorporated as a constituent of the laundry aftertreatment agent, in particular a fabric softener.
  • said detergent may also contain, but may be free of, the polymer to be used according to the invention.
  • Another object of the invention is a method for washing textiles, in which a detergent and the aforementioned soil release polymer are used.
  • This method can be carried out manually or preferably by means of a conventional household washing machine. It is possible to use the detergent and the polymer essential to the invention simultaneously or successively. The simultaneous application can be particularly advantageous by the use of a detergent containing the polymer perform.
  • Detergents containing the polymer to be used according to the invention may contain all the usual ingredients of such agents which do not undesirably interact with it.
  • the soil release polymer is preferably incorporated in detergent in amounts of from 0.1% by weight to 2% by weight, in particular from 0.4% by weight to 1% by weight.
  • Another aspect of the invention relates to enhancing the cleaning performance of detergents in the washing of textiles made of cotton or containing cotton.
  • the polymer used according to the invention has a positive effect on the action of certain other detergent ingredients and, conversely, that the effect of the polymer used according to the invention is enhanced by certain other detergent ingredients.
  • these effects occur in particular with enzymatic active compounds, in particular proteases and lipases, with water-insoluble inorganic builders, with water-soluble inorganic and organic builders, in particular based on oxidized carbohydrates, with peroxygen-based bleaching agents, especially with alkali percarbonate, with synthetic anionic surfactants of the sulfate and sulfonate type and in grayness inhibitors, for example other, in particular anionic cellulose ethers such as carboxymethylcellulose, which is why the use of at least one of said further ingredient together with the polymer to be used according to the invention is preferred.
  • such an agent contains nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation products of fatty alkylamines, vicinal diols, fatty acid alkyl esters and / or Fatty acid amides and mixtures thereof, in particular in an amount in the range of 2 wt .-% to 25 wt .-%.
  • Such agents comprises the presence of sulfate and / or sulfonate synthetic anionic surfactant, in particular fatty alkyl sulfate, fatty alkyl ether sulfate, sulfo fatty acid ester and / or sulfo fatty acid salt, in particular in an amount in the range from 2% to 25% by weight.
  • the anionic surfactant is preferably selected from the alkyl or alkenyl sulfates and / or the alkyl or alkenyl ether sulfates in which the alkyl or alkenyl group has 8 to 22, in particular 12 to 18, carbon atoms.
  • Suitable nonionic surfactants include the alkoxylates, in particular the ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched-chain alcohols having 10 to 22 C atoms, preferably 12 to 18 C atoms.
  • the degree of alkoxylation of the alcohols is generally between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides.
  • Particularly suitable are the derivatives of fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can be used for the preparation of usable alkoxylates.
  • alkoxylates in particular the ethoxylates, primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof.
  • suitable alkoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the said alcohols with respect to the alkyl part usable.
  • the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters such as may be prepared according to the process disclosed in International Patent Application WO 90/13533, and fatty acid polyhydroxyamides, as prepared according to the processes of US Pat. Nos.
  • alkylpolyglycosides which are suitable for incorporation into the compositions according to the invention are compounds of the general formula (G) n -OR 12 in which R 12 is an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and n is a number between 1 and 10 mean.
  • R 12 is an alkyl or alkenyl radical having 8 to 22 C atoms
  • G is a glycose unit
  • n is a number between 1 and 10 mean.
  • Such compounds and their preparation are described, for example, in European patent applications EP 92 355, EP 301 298, EP 357 969 and EP 362 671 or US Pat. No. 3,547,828.
  • the glycoside component (G) n are oligomers or polymers of naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, Include arabinose, xylose and 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 n assumes as the value to be determined analytically generally broken numerical values; he is lying at values 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 R 12 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.
  • Nonionic surfactant is included in compositions containing a polymer used in the invention, preferably in amounts of 1 wt .-% to 30 wt .-%, in particular from 1 wt .-% to 25 wt .-%, with amounts in the upper part of this Area are more likely to be found in liquid detergents and particulate detergent preferably contain rather lower amounts of up to 5 wt .-%.
  • compositions may instead or additionally contain further surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type, such as, for example, alkylbenzenesulfonates, 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.
  • Suitable synthetic anionic surfactants which are particularly suitable for use in such compositions are the alkyl and / or alkenyl sulfates having 8 to 22 C atoms which carry an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as counter cation.
  • 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 present in the compositions in amounts of from 0.1% by weight to 15% by weight, in particular from 0.5% by weight to 10% by weight.
  • the sulfate-type surfactants which can be used also include the sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates.
  • ether sulfates preferably contain from 2 to 30, in particular from 4 to 10, ethylene glycol groups per molecule.
  • 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, as well as the formal saponification resulting from these sulfo fatty acids.
  • soaps which may be 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. Soap mixtures are preferred, to 50 wt .-% to 100 wt .-% of saturated Ci acid soaps 2 -Cig-fatty acid and are composed to 50 wt .-% to oleic acid soap.
  • soap is included in amounts of from 0.1% to 5% by weight. However, especially in liquid compositions containing a polymer used according to the invention, higher amounts of soap, as a rule up to 20% by weight, can also be present.
  • an agent which comprises a polymer to be used 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 in the range of From 2.5% to 60% by weight.
  • An agent containing a polymer to be used according to the invention 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 polycarboxylic acids, in particular citric acid and sugar acids, and also the polymeric (poly) carboxylic acids, in particular the polycarboxylates of international patent application WO 93/16110 obtainable by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids . Maleic acids and copolymers of these, 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 acid or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50 wt .-%.
  • the third monomer is derived from a monoethylenically unsaturated C 3 -Cg 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, 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 of 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 Maleinate 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 may 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 40 wt .-% to 60 wt .-%, in particular 45 to 55 wt .-% of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10 wt .-% to 30 wt .-%, preferably 15 % By weight to 25% by weight of methallylsulfonic acid or methallylsulfonate and as the third monomer 15% by weight to 40% by weight, preferably 20% by weight to 40% by weight 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.
  • 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 builder substances are preferably present in amounts of up to 40% by weight, in particular up to 25% by weight and particularly preferably from 1% by weight to 5% by weight. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular hydrous, agents.
  • Crystalline or amorphous alkali metal aluminosilicates in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are particularly suitable as water-insoluble, water-dispersible inorganic builder materials.
  • the detergent-grade crystalline aluminosilicates especially zeolite NaA and optionally NaX, are preferred. 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.
  • Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates.
  • the alkali silicates useful as builders in the compositions preferably have a molar ratio of alkali 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.
  • Such amorphous alkali silicates are commercially available, for example, under the name Portil®.
  • Those with a molar ratio of Na 2 O: SiO 2 of 1: 1.9 to 1: 2.8 can be prepared by the process of European Patent Application EP 0 425 427. They are preferably added in the course of the production as a solid and not in the form of a solution.
  • the crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula of Na 2 Si x O 2x +] 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 and preferred values for x are 2, 3 or 4.
  • Crystalline layered silicates which fall under this general formula are described, for example, in European Patent Application EP 0 164 514.
  • Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
  • both .beta.- and ⁇ -sodium are preferred, with beta-sodium disilicate being obtainable, for example, by the method described in International Patent Application WO 91/08171.
  • ⁇ -Sodium silicates with a modulus between 1.9 and 3.2 can be prepared according to Japanese patent applications JP 04/238 809 or JP 04/260 610.
  • Crystalline sodium silicates with a modulus ranging from 1.9 to 3.5 are used in a further preferred embodiment of detergents or cleaners containing a polymer used according to the invention.
  • Their content of alkali metal silicates is preferably 1 wt .-% to 50 wt .-% and in particular 5 wt .-% to 35 wt .-%, based on anhydrous active substance.
  • alkali metal aluminosilicate in particular zeolite
  • 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 is preferably 1: 2 to 2: 1 and especially 1: 1 to 2: 1.
  • inorganic builder In addition to the above-mentioned inorganic builder, other water-soluble or water-insoluble inorganic substances may be used in the agents containing a polymer to be used in the present 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.
  • 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, dye fixing agents, color 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.
  • compositions which contain a combination used according to the invention up to 1% by weight, in particular from 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, in particular Aminoalkylenphosphonkla and their salts, up to 3 wt .-%, in particular 0.5 wt .-% to 2 wt .-% grayness inhibitors and up to 2 wt .-%, in particular 0.1 wt .-% to 1 wt .-% foam inhibitors, wherein said weight fractions refer to the total agent.
  • optical brighteners in particular compounds from the class of the substituted 4,4 ' -Bis
  • Solvents which are used in particular for liquid agents 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, such as ethylene and propylene glycol, and the derivable from the aforementioned classes of compounds ether.
  • the polymer used according to the invention or the constituents of the combination used according to the invention are generally 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 German Offenlegungsschriften DE 19 40 488, DE 20 44 161, DE 21 01 803 and DE 21 21 397, US Pat. Nos. 3,623,957 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 species
  • Suitable lipases are commercially available, for example, under the names Lipolase®, Lipozym®, Lipomax®, Amano®-Lipase, Toyo-Jozo®-Lipase, Meito®-Lipase and Diosynth®-Lipase.
  • Suitable amylases are commercially available, for example, under the names Maxamyl®, Termamyl®, Duramyl® and Purafect® OxAm.
  • 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 and International Patent Applications WO 95/02675 and WO 97/14804 and commercially available under the names Celluzyme®, Carezyme® and Ecostone®.
  • the customary enzyme stabilizers present in particular, if appropriate, in liquid agents include amino alcohols, for example mono-, di-, triethanol- and -propanolamine and mixtures thereof, lower carboxylic acids, as known, for example, from European patent applications EP 376 705 and EP 378 261, Boric acid or alkali metal borates, boric acid-carboxylic acid combinations, as known for example from European patent application EP 451 921, boric acid esters, such as from the international patent application WO 93/11215 or European patent application EP 511 456 known boronic acid derivatives, such as from the European patent application EP 583 536 known, calcium salts, for example, 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, such as de n European patent applications EP 080 748 or EP 080 223.
  • amino alcohols for example mono-, di-, triethanol- and -propanol
  • Suitable foam inhibitors include long-chain soaps, in particular heel 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 are preferably added to granular, water-soluble carrier substances. punched as described, for example, in German Offenlegungsschrift DE 34 36 194, the European patent applications EP 262 588, EP 301 414, EP 309 931 or the European patent EP 150 386.
  • a further embodiment of such an agent which contains a polymer to be used according to the invention contains peroxygen-based bleaches, in particular in amounts ranging from 5% to 70% by weight, and optionally bleach activator, in particular in amounts in the range of 2% by weight % to 10% by weight.
  • bleaches which are suitable are the per compounds generally used in detergents, such as hydrogen peroxide, perborate, which may be in the form of a 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 containing a polymer used in 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 .-%, each based on total agent, present, in particular percarbonate is used.
  • the optionally present component of the bleach activators comprises the conventionally 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, also carboxylic anhydrides, especially phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl-phenolsulfonat, and acylated sugar derivatives, in particular pentaacetylglucose, and cationic nitrile derivatives such as trimethylammoniumacetonitrile salts.
  • N- or O-acyl compounds for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine
  • 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, granulated l, 5-diacetyl-2,4-dioxohexahydro-l, 3,5-triazine, as can be prepared by the process described in German Patent DD 255,884 , and / or according to the methods described in International Patent Applications WO 00/50553, WO 00/50556, WO 02/12425, WO 02/12426 or WO 02/26927 particulate formally prepared trialkylammonium acetonitrile 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,
  • polyester-active soil release polymer of dicarboxylic acid and diol which may also be a polymeric diol or a mixture of monomeric and polymeric diol, to enhance the cleaning performance of detergents in the washing of textiles.
  • polyester-active soil release polymers which can be used in addition to the polymer essential to the invention include copolyesters of dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol.
  • dicarboxylic acids for example adipic acid, phthalic acid or terephthalic acid
  • diols for example ethylene glycol or propylene glycol
  • polydiols for example polyethylene glycol or polypropylene glycol.
  • Preferred soil release polymers 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 1 '-) a OH, also known as polymeric diol H- (O- (CHR 1 i-) a ) b OH may be present.
  • Ph is an o-, m- or p-phenylene radical which may carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof
  • R 1 ' 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 of 4 to 200, especially 12 to 140.
  • the molecular weight or the average molecular weight or the maximum molecular weight distribution of preferred soil release polyester is in the range of 250 to 100,000, especially 500 to 50,000
  • the acid underlying the radical 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 selected.
  • 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. If desired, instead of the monomer HOOC-Ph-COOH, small proportions, in particular not more than 10 mol%, based on the proportion of Ph with the meaning given above, of other acids which have at least two carboxyl groups may be present in the soil release-capable polyester.
  • 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 1 '-) a OH include those in which R 11 is hydrogen and a is a number from 2 to 6, and those in which a is 2 and R 11 are hydrogen and the alkyl radicals with 1 to 10, in particular 1 to 3 C-atoms is selected.
  • diols those of the formula HO-CH 2 -CHR 1 '-OH, in which R 11 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 synthesized 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.
  • valeric acid caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleinic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroseic acid, oleic acid, linoleic acid, linolaidic acid, linolenic acid, levostearic acid , Arachidic acid, gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, which carry 1 to 5 substituents with a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms may, for example, tert-butylbenz
  • the end groups can also be based on hydroxymonocarboxylic acids having 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, the hydrogenation product of which includes hydroxystearic acid and also o-, m- and p-hydroxybenzoic acid.
  • the hydroxy-monocarboxylic acids can 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 soil release polymers are preferably water-soluble, the term "water-soluble” being understood to mean a solubility of at least 0.01 g, preferably at least 0.1 g, of the polymer per liter of water at room temperature and pH 8.
  • Preferably used polymers have these conditions However, a solubility of at least 1 g per liter, in particular at least 10 g per liter.
  • Preferred laundry aftertreatment compositions containing a polymer to be used according to the invention have, as a laundry softening agent, a so-called esterquat, that is to say a quaternized ester of carboxylic acid and aminoalcohol.
  • esterquat that is to say a quaternized ester of carboxylic acid and aminoalcohol.
  • German Patent DE 43 08 794 moreover discloses a process for preparing solid ester quats, in which the quaternization of triethanolamine esters is carried out in the presence of suitable dispersants, preferably fatty alcohols.
  • suitable dispersants preferably fatty alcohols.
  • Reviews on this topic are, for example, by R. Puchta et al. in Tens.Surf.Det, 30, 186 (1993), M.Brock in Tens.Surf.Det. 30, 394 (1993), R. Lagerman et al. in J.Am.Oil.Chem.Soc, 7JL, 97 (1994) and I.Shapiro in Cosm.Toil. 109, 77 (1994).
  • Ester quats preferred in the compositions are quaternized fatty acid triethanolamine ester salts which follow formula (I),
  • R 1 CO for an acyl radical having 6 to 22 carbon atoms
  • R 2 and R 3 are independently hydrogen or R 1 CO
  • R 4 is an alkyl radical having 1 to 4 carbon atoms or a (CH 2 CH 2 O) q H Group
  • m, n and p in total are 0 or numbers from 1 to 12
  • q is numbers from 1 to 12
  • X is a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.
  • esterquats which can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachidic acid, behenic acid and erucic acid and their technical mixtures, such as They occur, for example, in the pressure splitting of natural fats and oils.
  • the fatty acids and the triethanolamine can generally be used in a molar ratio of 1.1: 1 to 3: 1.
  • an employment ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1 has proven to be particularly advantageous.
  • the Esterquats preferably used represent technical mixtures of mono-, di- and triesters with an average degree of esterification of 1, 5 to 1, 9 and are derived from technical C 16/18 - tallow or palm oil fatty acid (iodine 0 to 40) from , Quaternized Fettkladretriethanolaminestersalze of formula (I), in which R 1 CO for an acyl radical with 16 bis 18 carbon atoms, R 2 is R 1 CO, R 3 is hydrogen, R 4 is a methyl group, m, n and p is 0 and X is methyl sulfate, have proven to be particularly advantageous.
  • formula (I) in which R 1 CO for an acyl radical with 16 bis 18 carbon atoms, R 2 is R 1 CO, R 3 is hydrogen, R 4 is a methyl group, m, n and p is 0 and X is methyl sulfate, have proven to be particularly advantageous.
  • quaternized ester salts of carboxylic acids with diethanolalkylamines of the formula (II) are also suitable as esterquats.
  • R 1 CO for an acyl radical having 6 to 22 carbon atoms
  • R 2 is hydrogen or R 1 CO
  • R 4 and R 5 are independently alkyl radicals having 1 to 4 carbon atoms
  • X is a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.
  • R 6 O- (CH 2 CH 2 O) 01 OCR 1 [R 4 -N + -CH 2 CHCH 2 O- (CH 2 CH 2 O) n R 2 ]
  • X " (III) 1> in the R 1 CO for an acyl radical having 6 to 22 carbon atoms
  • R 2 is hydrogen or R 1 CO
  • R 4 , R 6 and R 7 are independently alkyl radicals having 1 to 4 carbon atoms, m and n in total for O or numbers from 1 to 12
  • X represents a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.
  • ester quats arrive in Form 50 to 90 weight percent alcoholic solutions on the market, which can also be easily diluted with water, with ethanol, propanol and isopropanol are the usual alcoholic solvents.
  • Esterquats are preferably used in amounts of from 5% by weight to 25% by weight, in particular from 8% by weight to 20% by weight, in each case based on the total laundry aftertreatment agent.
  • the laundry aftertreatment agents used in the present invention may additionally contain detergent ingredients listed above, unless they unduly interact negatively with the esterquat. It is preferably a liquid, water-containing agent which is accessible in a simple manner by mixing the ingredients.
  • an agent into which a polymer to be used according to the invention is incorporated is particulate and contains up to 25% by weight, in particular 5% by weight to 20% by weight, of bleaching agent, in particular alkali percarbonate, up to 15% Wt .-%, in particular 1 wt .-% to 10 wt .-% bleach activator, 20 wt .-% to 55 wt .-% inorganic builder, up to 10 wt .-%, in particular 2 wt .-% to 8 wt % of water-soluble organic builder, 10% by weight to 25% by weight of synthetic anionic surfactant, 1% by weight to 5% by weight of nonionic surfactant and up to 25% by weight, in particular 0.1% by weight .-% to 25 wt .-% of inorganic salts, in particular alkali carbonate and / or bicarbonate.
  • bleaching agent in particular alkali percarbonate
  • up to 15% Wt .-% in particular 1
  • an agent into which a polymer to be used according to the invention is incorporated is liquid and contains 10% by weight to 25% by weight, in particular 12% by weight to 22.5% by weight, of nonionic surfactant , 2 wt .-% to 10 wt .-%, in particular 2.5 wt .-% to 8 wt .-% synthetic anionic surfactant, 3 wt .-% to 15 wt .-%, in particular 4.5 wt .-% up to 12.5% by weight of soap, 0.5% by weight to 5% by weight, in particular 1% by weight to 4% by weight of organic builder, in particular polycarboxylate such as citrate, up to 1, 5 wt .-%, in particular 0.1 wt .-% to 1 wt .-% complexing agent for heavy metals, such as phosphonate, and optionally enzyme, enzyme stabilizer, color and / or fragrance and water and / or water-miscible solvent.
  • heavy metals such
  • Solid agents are preferably prepared by mixing a particle containing the soil release polymer with other detergent ingredients present in solid form.
  • a spray-drying step to prepare the particle which contains soil release-capable polymer.
  • a compacting compounding step for producing this particle and optionally also for producing the finished product.
  • Styrene, methacrylic acid, hydroxyethyl methacrylate and methyl methacrylate were radically polymerized.
  • the soiled tissues were measured with a Minolta CR 200 and then aged for 7 days at RT. Thereafter, the soiled cloths were stapled on towels and washed under the conditions given above. The fabrics were dried and measured again with a Minolta CR 200.

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  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
EP06742985A 2005-06-08 2006-05-19 Renforcement du pouvoir detersif de detergents par l'intermediaire d'un polymere Not-in-force EP1888732B1 (fr)

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DE102012024440A1 (de) * 2012-12-14 2014-06-18 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Die Primärwaschkraft verbessernde polymere Wirkstoffe
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JP2008545857A (ja) 2008-12-18
EP1888732B1 (fr) 2010-03-24
DE502006006513D1 (de) 2010-05-06
DE102005026544A1 (de) 2006-12-14
WO2006131197A1 (fr) 2006-12-14
JP5113043B2 (ja) 2013-01-09
US20080301883A1 (en) 2008-12-11
US8034123B2 (en) 2011-10-11
PL1888732T3 (pl) 2010-08-31
ATE461991T1 (de) 2010-04-15
ES2341672T3 (es) 2010-06-24

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