EP1592764B1 - Augmentation de la capacite d'absorption d'eau de textiles - Google Patents

Augmentation de la capacite d'absorption d'eau de textiles Download PDF

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Publication number
EP1592764B1
EP1592764B1 EP04707139A EP04707139A EP1592764B1 EP 1592764 B1 EP1592764 B1 EP 1592764B1 EP 04707139 A EP04707139 A EP 04707139A EP 04707139 A EP04707139 A EP 04707139A EP 1592764 B1 EP1592764 B1 EP 1592764B1
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EP
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Prior art keywords
acid
cellulose derivative
weight
soil release
groups
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EP04707139A
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German (de)
English (en)
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EP1592764A1 (fr
Inventor
Josef Penninger
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority claimed from DE10351320A external-priority patent/DE10351320A1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D3/0026—Low foaming or foam regulating compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D06M15/05—Cellulose or derivatives thereof
    • D06M15/09—Cellulose ethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material

Definitions

  • the present patent application relates to the use of soil release cellulose derivative for increasing the water absorbency of textiles of synthetic material.
  • JP-A-59015573 discloses the use of hydroxypropylmethycellulose for the treatment of synthetic textiles.
  • FR-A-14 19 645 discloses that polyamide fabric treated with a mixture of the reaction product of certain cellulose ethers with crosslinking agent or resinous precondensation products has improved water absorbency.
  • the invention therefore provides the use of soil release cellulose derivative obtainable by alkylation and hydroxyalkylation of cellulose to increase the water absorbency of textiles of synthetic material.
  • Preferred cellulose derivatives are those which are alkylated with C 1 to C 10 groups, in particular C 1 to C 3 groups, and additionally carry C 2 to C 10 hydroxyalkyl groups, in particular C 2 to C 3 hydroxyalkyl groups.
  • appropriate alkylating agents for example alkyl halides or alkyl sulfates, and subsequent reaction with corresponding alkylene oxides, such as, for example, ethylene oxide and / or propylene oxide.
  • a mean of 0.5 to 2.5, in particular 1 to 2, alkyl groups and 0.02 to 0.5, in particular 0.05 to 0.3, hydroxyalkyl groups per anhydroglycosemonomer unit are contained in the cellulose derivative.
  • the average molar mass of the cellulose derivatives used according to the invention is preferably in the range from 10,000 D to 150,000 D, in particular from 40,000 D to 120,000 D and particularly preferably in the range from 80,000 D to 110,000 D.
  • the determination of the degree of polymerization or of the molecular weight of the soil release-capable cellulose derivative is based on the determination of the limiting viscosity number of sufficiently dilute aqueous solutions by means of an Ubbelohde capillary viscometer (capillary 0c). Using a constant [H. Staudinger and F. Reinecke, “On Molecular Weight Determination on Cellulose Ethers", Liebigs Annalen der Chemie 535, 47 (1938)] and a Correction Factor [F.
  • Rodriguez and LAGoettler, "The Flow of Moderately Concentrated Polymer Solutions in Water", Transactions of the Society of Rheology VIII, 3 17 (1964)] can be calculated from the degree of polymerization and, taking into account the degrees of substitution (DS and MS), the corresponding molecular weight.
  • the use according to the invention is preferably carried out as part of a washing and / or laundry aftertreatment step in which the soil release-capable cellulose derivative is used.
  • Another object of the invention is therefore a process for increasing the water absorbency of textiles made of synthetic material by washing and / or after-treatment of the textile in the presence of soil release cellulose derivative, which is obtainable by alkylation and hydroxyalkylation of cellulose.
  • the cellulose derivatives used according to the invention can be prepared in a simple manner and are ecologically and toxicologically harmless. They lead to one Significantly higher water absorbency of textiles of synthetic material when they are treated with them, which leads to an improvement of the cleaning result, in particular the fat separation, in the next wash and also in further washing of the textile thus treated. Alternatively, significant amounts of surfactants can be saved while maintaining fat removal capability.
  • the textiles to be treated according to the invention consist of or contain polyester, polyamide, polyacrylonitrile, elastane or mixtures thereof.
  • so-called cotton blends are to be understood that contain cotton and synthetic material in the blended fabric.
  • the use according to the invention can be carried out as part of a washing process in such a way that one adds the cellulose derivative of a detergent-containing liquor or preferably introduces the cellulose derivative as a constituent of a detergent in the liquor.
  • a laundry aftertreatment process can be carried out in such a way that the cellulose derivative of the rinse liquor is added separately, which is used after washing done using a detergent, or it is incorporated as a component of the laundry aftertreatment agent, in particular a softener.
  • said detergent may also contain, but may be free of, a cellulose derivative to be used in accordance with the invention.
  • compositions containing a cellulose derivative to be used according to the invention may contain all other conventional constituents of such agents which do not undesirably interact with the cellulose derivative.
  • the cellulose derivative in amounts of from 0.1 wt .-% to 5 wt .-%, in particular 0.5 wt .-% to 2.5 wt .-% is incorporated in detergent.
  • the cellulose derivative used according to the invention has the effect of certain other detergent ingredients positively influenced and that, conversely, the effect of the cellulose derivative used in the invention is enhanced by certain other detergent ingredients.
  • these effects occur in particular with enzymatic agents, in particular proteases and lipases, with water-insoluble inorganic builders, with water-soluble inorganic and organic builders, especially based on oxidized carbohydrates, with peroxygen bleaching agents, especially with alkali percarbonate, with synthetic anionic surfactants of the sulfate and sulfonate type and at Grayness inhibitors, for example other, in particular anionic cellulose ethers such as carboxymethylcellulose, and fabric softening active ingredients, in particular esterquats, which is why the use of at least one of said further ingredients together with the combination to be used according to the invention is preferred.
  • such agent comprises nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, especially 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 usually between 1 and 20, preferably between 3 and 10.
  • 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 as can 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 in 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, arabinose, Include 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 Oligomermaschinesgrad.
  • the degree of oligomerization n assumes as the value to be determined analytically generally broken numerical values; 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 part R 12 of the glycosides preferably also comes from readily available derivatives of renewable raw materials, in particular from fatty alcohols, although also whose branched-chain isomers, in particular so-called oxoalcohols, can be used for the preparation of useful glycosides. Accordingly, 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 cellulose derivative used in the invention, preferably in amounts of from 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
  • Such alkyl and / or alkenyl sulfates are in the compositions containing a urethane-based polymer according to the invention, preferably in amounts of 0.1 wt .-% to 15 wt .-%, in particular from 0.5 wt .-% to 10 wt .-% included.
  • Sulfur-type surfactants which can be used also include the sulfated alkoxylation products of the alcohols mentioned, known as ether sulfates. Such ether sulfates preferably contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule.
  • Suitable sulfonate anionic surfactants include the ⁇ -sulfoesters obtainable by reaction of fatty acid esters with sulfur trioxide and subsequent neutralization, especially those of fatty acids containing 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and linear alcohols of 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.
  • compositions may also contain betaines and / or cationic surfactants, which, if present, are preferably used in amounts of from 0.5% by weight to 7% by weight.
  • betaines and / or cationic surfactants which, if present, are preferably used in amounts of from 0.5% by weight to 7% by weight.
  • esterquats discussed below are particularly preferred.
  • 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.
  • higher amounts of soap as a rule up to 20% by weight, can also be present.
  • an agent containing a combination 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 which contains a cellulose derivative 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, as well as 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 thereof, which also polymerizes small amounts of polymerizable substances without carboxylic acid functionality can contain.
  • 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, 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 Maleinate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% of vinyl alcohol and / or vinyl acetate.
  • the second acid monomer or its salt may also be a derivative of an allylsulfonic acid which is substituted in position 2 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.
  • 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, from 10% by weight to 30% by weight. %, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid or Methallylsulfonat and as the 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 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 weight percent 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 water-insoluble, water-dispersible inorganic builder materials.
  • the detergent-grade crystalline aluminosilicates especially zeolite NaA and optionally NaX, are preferred.
  • Quantities near the upper limit mentioned are preferably in solid, particulate Funds used.
  • suitable aluminosilicates have no particles with a particle size greater than 30 mm and preferably consist of at least 80% by weight of particles having a size of less than 10 mm.
  • 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 metal silicates useful as builders in the compositions 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.
  • 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 Na 2 Si x O 2x + 1 ⁇ are used yH 2 O, in which x, the so-called module, 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 ⁇ - and ⁇ -sodium Na 2 Si 2 O 5 ⁇ yH 2 O
  • ⁇ -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.
  • compositions can be prepared from amorphous alkali metal silicates, practically anhydrous crystalline alkali metal silicates of the above general formula in which x is a number from 1.9 to 2.1, preparable as in the European patent applications EP 0 548 599, EP 0 502 325 and EP 0 425 428 can be used in agents which contain a cellulose derivative used according to the invention.
  • a crystalline sodium layer silicate having a modulus of 2 to 3, as can be prepared by the process of European patent application EP 0 436 835 from sand and soda.
  • Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are disclosed in another preferred embodiment of laundry detergents. or detergents which contain a cellulose derivative 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.
  • water-soluble or water-insoluble inorganic substances may be used in the compositions containing a cellulose derivative 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, 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
  • dye fixing agents for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopoly
  • agents 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 aminoalkylenephosphonic acids 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, respectively.
  • optical brighteners in particular compounds from the class of the substituted 4,4'- Bis- (2,4,6-tri
  • 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 said classes of compounds ether.
  • the cellulose derivative used in the invention is 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 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, such as in 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 international patent application WO 90/10695, from Fusarium Types, as described, for example, in European patent application EP 130 064, from Rhizopus species,
  • Suitable lipases are commercially available, for example, under the names Lipolase®, Lipozym®, Lipomax®, Lipex®, 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®.
  • customary enzyme stabilizers include amino alcohols, for example mono-, di-, triethanol- and -propanolamine and mixtures thereof, lower carboxylic acids, such as from the European patent applications EP 376 705 and EP 378 261 known boric acid or Alkali borates, boric acid-carboxylic acid combinations, as known for example from European patent application EP 451 921, boric acid esters, as known for example from international patent application WO 93/11215 or European patent application EP 511 456, boronic acid derivatives, as for example from European patent application EP 583 536 known, 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, such as from European patent applications EP 080 748 or EP 080 223.
  • lower carboxylic acids such as from the European patent applications EP 376 705 and EP 378 261 known boric acid or Alkali borates, boric
  • 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 are 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.
  • a further embodiment of such an agent which contains a cellulose derivative to be used according to the invention comprises 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 which contain a cellulose derivative used 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 .-%, respectively 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, and also carboxylic acid anhydrides , in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoylphenolsulfonat, and acylated sugar derivatives, in particular pentaacetylglucose, as well as cationic nitrile derivatives such as trimethylammoniumacetonitrile salts.
  • N- or O-acyl compounds for example polyacylated alkylenediamines, in particular tetraacety
  • 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 during storage, granulated with the aid of carboxymethylcellulose granulated tetraacetylethylenediamine with average grain sizes of 0.01 mm to 0.8 mm, as can be prepared, for example, according to the method described in European Patent EP 37,026, granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5 triazine, as may 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
  • soil release-modulating cellulose derivative together with a polyester-active soil release polymer of a dicarboxylic acid and an optionally 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 cellulose derivative of 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, wherein the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO- (CHR 11 -) a OH, also known as polymeric Diol H- (O- (CHR 11 -) a ) b OH may be present.
  • Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof
  • R 11 denotes hydrogen
  • 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 4 to 200, in particular from 12 to 140.
  • the molecular weight or the maximum molecular weight distribution of preferred soil release polyesters is in the range from 250 to 100,000, in particular from 500 to 50,000 underlying acid 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.
  • acids having at least two carboxyl groups may be included 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 11 -) 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 is hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 C-atoms is selected.
  • R 11 is hydrogen and a is a number from 2 to 6
  • R 11 is hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 C-atoms is selected.
  • those of the formula HO-CH 2 -CHR 11 -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, petroselaidic acid, oleic acid, linoleic acid, linolaidic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, Cerotic acid, melissic acid, benzoic acid, which may carry 1 to 5 substituents with a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms, for example tert-but
  • 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 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.
  • preferred polymers have a solubility of at least 1 g per liter, in particular at least 10 g per liter, under these conditions.
  • Preferred laundry aftertreatment compositions containing a cellulose derivative to be used according to the invention have, as a laundry softening active ingredient, 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., 71 , 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), in the 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 and X is a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.
  • 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
  • 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.
  • technical C 12/18 coconut fatty acids and in particular partially hydrogenated C 16/18 tallow or palm oil fatty acids and elaidic acid-rich C 16/18 fatty acid cuts are used.
  • 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 proved to be particularly advantageous.
  • the preferred esterquats used are 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 value 0 to 40) , Quaternized fatty acid triethanolamine ester salts of the formula (I) in which R 1 is CO for an acyl radical having 16 to 18 carbon atoms, R 2 is R 1 CO, R 3 is hydrogen R 4 is a methyl group, m, n is 0 and X is methyl sulfate stands have proved 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 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
  • X is a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.
  • esterquats of the formulas (II) and (III).
  • the esterquats are marketed in the form of 50 to 90 weight percent alcoholic solutions, which can also be easily diluted with water, with ethanol, propanol and isopropanol being 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 cellulose derivative 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 bleach, in particular alkali percarbonate, up to 15% by weight .-%, 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.
  • % water-soluble organic builder 10% to 25% by weight synthetic anionic surfactant, 1% to 5% by weight 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.
  • an agent into which a cellulose derivative 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 .-% to 12.5 wt .-% soap, 0.5 wt .-% to 5 wt .-%, in particular 1 wt .-% to 4 wt .-% 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
  • Solid agents are preferably prepared by mixing a particulate soil release-containing cellulose derivative with other detergent ingredients present in solid form. In this case, it is preferable to use a spray-drying step to produce the particle which contains the soil release-capable cellulose derivative. Alternatively, it is also possible to use a compacting compounding step for producing this particle and optionally also for producing the finished product.

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Claims (8)

  1. Utilisation d'un dérivé de cellulose capable de détacher les salissures, que l'on peut obtenir par alkylation et hydroxyalkylation de cellulose, et dans lequel sont contenus en moyenne de 0,5 à 2,5 groupes alkyle et de 0,02 à 0,5 groupe hydroxyalkyle par unité monomère anhydroglycose, pour accroître la capacité d'absorption d'eau des textiles en matériau synthétique.
  2. Utilisation selon la revendication 1, caractérisée en ce que le dérivé de cellulose capable de détecter les salissures est alkylé avec des groupes en C1 à C10, en particulier avec des groupes en C1 à C3, et porte en outre des groupes hydroxyalkyle en C2 à C10, en particulier des groupes hydroxyalkyle en C2 à C3.
  3. Utilisation selon la revendication 1 ou 2, caractérisée en ce que dans le dérivé de cellulose capable de détacher les salissures sont contenus en moyenne de 1 à 2 groupes alkyle et de 0,05 à 0,3 groupe hydroxyalkyle par unité monomère anhydroglycose.
  4. Utilisation selon l'une des revendications 1 à 3, caractérisée en ce que la masse molaire moyenne du dérivé de cellulose capable de détacher les salissures se situe dans un intervalle de 10 000 D à 150 000 D, en particulier de 40 000 D à 120 000 D.
  5. Utilisation selon l'une des revendications 1 à 4, caractérisée en ce qu'elle se déroule dans une étape de lavage et/ou de post-traitement de la lessive.
  6. Utilisation selon la revendication 5, caractérisée en ce qu'on emploie le dérivé de cellulose capable de détacher les salissures comme composant d'un produit de lavage ou de post-traitement de la lessive, qui contient, outre le dérivé de cellulose, au moins un autre constituant choisi parmi les matières actives enzymatiques, en particulier les protéases et les lipases, les builders inorganiques insolubles dans l'eau, les builders inorganiques et organiques solubles dans l'eau, en particulier à base d'hydrates de carbone oxydés, des agents de blanchiment à base de peroxygène, en particulier un percarbonate de métal alcalin, des agents tensioactifs anioniques de synthèse de type sulfate et sulfonate, des inhibiteurs de grisaillement, en particulier des éthers de cellulose anioniques, et des matières actives assouplissant la lessive, en particulier des esterquats.
  7. Utilisation selon l'une des revendications 1 à 6, caractérisée en ce que les textiles se composent de polyester, de polyamide,de polyacrylonitrile, d'élastane, ou de mélanges de ces corps, ou les contiennent.
  8. Procédé pour accroître la capacité d'absorption d'eau des textiles en matériau synthétique par lavage et/ou post-traitement du textile en présence d'un dérivé de cellulose capable de détacher les salissures, que l'on peut obtenir par alkylation et hydroxyalkylation de cellulose et dans lequel sont contenus en moyenne de 0,5 à 2,5 groupes alkyle et de 0,02 à 0,5 groupe hydroxyalkyle par unité monomère anhydroglycose.
EP04707139A 2003-02-10 2004-01-31 Augmentation de la capacite d'absorption d'eau de textiles Revoked EP1592764B1 (fr)

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DE10305306 2003-02-10
DE10305306 2003-02-10
DE10351320A DE10351320A1 (de) 2003-02-10 2003-10-31 Erhöhung der Wasseraufnahmefähigkeit von Textilien
DE10351320 2003-10-31
PCT/EP2004/000872 WO2004069975A1 (fr) 2003-02-10 2004-01-31 Augmentation de la capacite d'absorption d'eau de textiles

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US20060035806A1 (en) 2006-02-16
JP2006517264A (ja) 2006-07-20
JP4578465B2 (ja) 2010-11-10
DE502004002541D1 (de) 2007-02-15
ATE350447T1 (de) 2007-01-15
EP1592764A1 (fr) 2005-11-09
WO2004069975A1 (fr) 2004-08-19
ES2279344T3 (es) 2007-08-16

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