EP3487972B1 - Ester de propylène glycol utilisé comme composant d'entretien de textiles - Google Patents

Ester de propylène glycol utilisé comme composant d'entretien de textiles Download PDF

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Publication number
EP3487972B1
EP3487972B1 EP17737814.8A EP17737814A EP3487972B1 EP 3487972 B1 EP3487972 B1 EP 3487972B1 EP 17737814 A EP17737814 A EP 17737814A EP 3487972 B1 EP3487972 B1 EP 3487972B1
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Prior art keywords
laundry
weight
agents
carbon atoms
acid
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German (de)
English (en)
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EP3487972A1 (fr
Inventor
Doris Dahlmann
Martina Seiler
Martina Hutmacher
Frank Janssen
Christina RÖLEKE
Karin Kania
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • 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
    • C11D3/2093—Esters; Carbonates
    • 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
    • C11D3/001—Softening 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile

Definitions

  • the present invention relates to detergents, laundry aftertreatment or laundry care products, in particular liquid detergents, which contain propylene glycol esters and their use to minimize the tendency to wrinkle and to facilitate ironing of textiles, in particular textiles made of cellulosic material, and a household process for making ironing easier and/or wrinkle-reducing finishing of textiles.
  • Textiles made of cellulose such as cotton or regenerated cellulose fibers (e.g. Modal or Lyocel) have positive properties in terms of wearing comfort from the consumer’s point of view.
  • a major disadvantage of these textiles is the easy crease formation during wear, after washing and drying. This wrinkling tendency is based on the swelling of the cellulose fibers and their low elastic restoring forces ("bounce") after deformation.
  • the cellulosic materials from which the textiles to be treated are made include cotton, regenerated cellulosic fibers such as modal or lyocel, and blends of cotton or regenerated cellulosic fibers with other materials commonly used in clothing, such as polyester and polyamide.
  • compositions herein comprise at least one propylene glycol monoester
  • the propylene glycol ester of the present invention may be propylene glycol laurate such as the Migoto Type BP compound from Riken.
  • any other monoester of propylene glycol and fatty acids can also be used (e.g. propylene glycol isostearate, propylene glycol oleate and propylene glycol myristate).
  • these monoesters are described as auxiliaries in the hair care sector, in the skin care sector and in the body care sector.
  • X 1 is -OH and x2 wherein R 2 is an alkyl of 5-35 carbon atoms, preferably an alkyl of 11 carbon atoms.
  • alkenyl refers to a monovalent straight or branched chain group containing at least one carbon-carbon double bond.
  • the alkenyl groups can be optionally substituted.
  • alkyl refers to saturated, straight or branched chain hydrocarbon groups.
  • alkylene include methyl, ethyl, propyl, iso -propyl, n -butyl, tert -butyl, neo -pentyl and n -hexyl.
  • the alkyl groups can be optionally substituted.
  • At least one as used herein means 1 or more, i.e. 1, 2, 3, 4, 5, 6, 7, 8, 9 or more.
  • the information refers to the type of ingredient and not to the absolute number of molecules.
  • At least one propylene glycol ester thus means at least one type of propylene glycol ester, i.e. one type of propylene glycol ester or a mixture of several different propylene glycol esters can be used.
  • the information refers to all compounds of the type specified that are contained in the composition/mixture, i.e. the composition does not contain any other compounds of this type beyond the specified amount of the corresponding compounds.
  • the process can be carried out, for example, by bringing textiles made of cellulose-containing material into contact with an aqueous preparation which contains 0.01 to 30% by weight, preferably 0.1 to 4% by weight, of at least one propylene glycol ester according to the invention.
  • an aqueous preparation which contains 0.01 to 30% by weight, preferably 0.1 to 4% by weight, of at least one propylene glycol ester according to the invention.
  • the propylene glycol ester in an aqueous liquor is preferably used in the washing step, but can also be used in the rinsing step, for example.
  • the propylene glycol ester can be a component of detergents or laundry aftertreatment agents such as fabric softeners that are usually used in such washing processes.
  • the concentration of propylene glycol ester in aqueous treatment liquor is in particular in the range from 0.01 g/l to 2.7 g/l, particularly preferably 0.01 g/l to 0.4 g/l.
  • the propylene glycol ester can also be part of a laundry care product, which can be present in particular as a liquid spray product which, after dilution with water or preferably undiluted, is applied, in particular sprayed, to a textile made of cellulosic material, without a washing process having to follow or the application of a washing process must have immediately preceded it.
  • Detergents, laundry aftertreatment or laundry care products which contain the active ingredient to be used according to the invention or are used together with them or are used in the method according to the invention are preferably liquid and can also be present, for example, as a single dose (for example in the form of a sachet pack).
  • Examples of specific agents in which the propylene glycol esters can be used are liquid detergents and fabric softeners.
  • All of the detergents, laundry aftertreatment agents or laundry care agents mentioned above can contain customary other components of such agents which do not interact in an undesirable manner with the propylene glycol ester essential to the invention.
  • Such a composition preferably contains synthetic anionic surfactants of the sulfate or sulfonate type, in amounts of preferably not more than 35% by weight, in particular from 0.1% by weight to 25% by weight, based in each case on the composition as a whole.
  • Synthetic anionic surfactants which are particularly suitable for use in such agents are the alkyl and/or alkenyl sulfates having 8 to 22 carbon atoms which carry an alkali metal, ammonium or alkyl- or hydroxyalkyl-substituted ammonium ion as counter cation.
  • the derivatives of fatty alcohols with in particular 12 to 18 carbon atoms and their branched-chain analogues, the so-called oxo alcohols, are preferred.
  • the alkyl and alkenyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a customary sulfating agent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali, ammonium, or alkyl- or hydroxyalkyl-substituted ammonium bases.
  • a customary sulfating agent in particular sulfur trioxide or chlorosulfonic acid
  • Suitable anionic surfactants of the sulfonate type include the ⁇ -sulphoesters obtainable by reacting fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those derived from fatty acids having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and linear alcohols having 1 up to 6 carbon atoms, preferably 1 to 4 carbon atoms, deriving sulfonation products, and the sulfofatty acids resulting from these by formal hydrolysis.
  • the anionic surfactants that can be used also include the salts of sulfosuccinic acid esters, which are also known as alkyl sulfosuccinates or dialkyl sulfosuccinates are referred to, and represent the monoesters or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C8 to C18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain an ethoxylated fatty alcohol residue, which in itself represents a nonionic surfactant.
  • sulfosuccinates whose fatty alcohol radicals are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred.
  • Alkyl benzene sulfonate is a further synthetic anionic surfactant.
  • a further embodiment of the agent comprises the presence of 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 their Mixtures, especially in an amount ranging from 2% to 25% by weight.
  • 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 their Mixtures, especially in an amount ranging from 2% to
  • 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 carbon atoms, preferably 12 to 18 carbon 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.
  • the derivatives of fatty alcohols are particularly suitable, although their branched-chain isomers, in particular so-called oxo alcohols, can also be used for the preparation of useful alkoxylates.
  • the alkoxylates in particular the ethoxylates, of primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals, and mixtures thereof, can be used.
  • Corresponding alkoxylation products of alkylamines, vicinal diols and carboxamides which correspond to the alcohols mentioned with regard to the alkyl part can also be used.
  • the ethylene oxide and/or propylene oxide insertion products of fatty acid alkyl esters and fatty acid polyhydroxyamides also come into consideration.
  • alkyl polyglycosides suitable for incorporation into the agents 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 carbon atoms, G is a glycose unit and n is a number between 1 and 10 mean.
  • the glycoside component (G) n is an oligomer or polymer of naturally occurring aldose or ketose monomers, including in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, xylose and lyxose belong.
  • the oligomers consisting of such glycosidically linked monomers are characterized not only by the type of sugar they contain but also by their number, the so-called degree of oligomerization.
  • the degree of oligomerization n as a variable to be determined analytically, generally assumes fractional numerical values; it is between 1 and 10, in the case of the glycosides preferably used it is below one value of 1.5, in particular between 1.2 and 1.4.
  • the preferred monomer building block is glucose because it is readily available.
  • Nonionic surfactant is present in the compositions described preferably in amounts of 1% by weight to 30% by weight, in particular 1% by weight to 25% by weight, with amounts in the upper part of this range being more likely to be found in liquid compositions and particulate compositions preferably contain rather minor amounts of up to 5% by weight.
  • soaps with 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, being suitable.
  • those soap mixtures are preferred which are composed of 50% by weight 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 generally up to 20% by weight, can also be present.
  • the agents can also contain betaines and/or cationic surfactants, which—if present—are preferably used in amounts of 0.01% by weight to 7% by weight.
  • betaines and/or cationic surfactants which—if present—are preferably used in amounts of 0.01% by weight to 7% by weight.
  • ester quats are particularly preferred.
  • the detergents can contain bleaching agents based on peroxygen, especially in amounts ranging from 5% by weight to 70% by weight, and optionally bleach activator, especially in amounts ranging from 0.5% by weight to 10% by weight, contain.
  • the bleaches that come into consideration are preferably the peroxygen compounds usually used in detergents, such as percarboxylic acids, for example dodecanediperoic acid or phthaloylaminoperoxicaproic acid, hydrogen peroxide, alkali metal perborate, which can be in the form of tetrahydrate or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally present as alkali metal salts, in particular as sodium salts.
  • Bleaching agents of this type are present in detergents which contain a propylene glycol ester used according to the invention, preferably in amounts of up to 25% by weight, in particular up to 15% by weight and particularly preferably from 5% by weight to 15% by weight on entire Medium, available, with percarbonate being used in particular.
  • the optionally present component of the bleach activators includes the N- or O-acyl compounds commonly used, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides and cyanurates, and also carboxylic acid anhydrides , In particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl phenolsulfonate, and acylated sugar derivatives, in particular pentaacetyl glucose, and cationic nitrile derivatives such as trimethylammonium acetonitrile salts.
  • N- or O-acyl compounds commonly used, for example polyacylated alkylenediamines, in particular tetraacetylethylened
  • the bleach activators may have been coated and/or granulated in a known manner with encapsulating substances, granulated tetraacetylethylenediamine having an average grain size of 0.01 mm to 0.8 mm, granulated 1, 5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and/or trialkylammoniumacetonitrile formulated in particulate form is particularly preferred.
  • Such bleach activators are preferably present in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the detergent as a whole.
  • the composition contains water-soluble and/or water-insoluble builder, in particular selected from alkali metal aluminosilicate, crystalline alkali metal silicate with a modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts ranging from 2.5% by weight to 60 wt%.
  • water-soluble and/or water-insoluble builder in particular selected from alkali metal aluminosilicate, crystalline alkali metal silicate with a modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts ranging from 2.5% by weight to 60 wt%.
  • the water-soluble organic builder substances include in particular those from the class of polycarboxylic acids, in particular citric acid and sugar acids, and polymeric (poly)carboxylic acids, in particular the polycarboxylates accessible by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers of these, which also may contain small proportions of polymerizable substances without carboxylic acid functionality as polymerized units.
  • the relative molecular mass of the homopolymers of unsaturated carboxylic acids is generally between 5000 g/mol and 200,000 g/mol, and that of the copolymers between 2000 g/mol and 200,000 g/mol, preferably 50,000 g/mol to 120,000 g/mol, based on the free acid .
  • a particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 g/mol to 100,000 g/mol.
  • Suitable, although less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight.
  • Terpolymers which contain two carboxylic acids and/or their salts as monomers and vinyl alcohol and/or a vinyl alcohol derivative or a carbohydrate as the third monomer can also be used as water-soluble organic builder substances.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated Cs-Cs carboxylic acid and preferably from a C 3 -C 4 monocarboxylic acid, especially from (Meth)acrylic acid.
  • the second acidic monomer or its salt may be a derivative of a C 4 -C 8 dicarboxylic acid, with maleic acid being particularly preferred.
  • the third monomeric unit is formed by vinyl alcohol and/or preferably an esterified vinyl alcohol.
  • vinyl alcohol derivatives which represent an ester of short-chain carboxylic acids, for example of C 1 -C 4 -carboxylic acids, with vinyl alcohol.
  • Preferred terpolymers contain 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight, of (meth)acrylic acid and/or (meth)acrylate, particularly preferably acrylic acid and/or acrylate, and maleic acid and/or maleate and 5% to 40% by weight, preferably 10% to 30% by weight, of vinyl alcohol and/or vinyl acetate.
  • the second acidic monomer or its salt may also be a derivative of an allylsulfonic acid substituted in the 2-position with an alkyl radical, preferably a C 1 -C 4 alkyl radical, or an aromatic radical, preferably derived from benzene or benzene derivatives , is substituted.
  • Preferred terpolymers contain 40% by weight to 60% by weight, in particular 45 to 55% by weight, of (meth)acrylic acid and/or (meth)acrylate, particularly preferably acrylic acid and/or acrylate, 10% by weight to 30% by weight, preferably 15% by weight to 25% by weight, of methallyl sulfonic acid and/or methallyl sulfonate and, as a third monomer, 15% by weight to 40% by weight, preferably 20% by weight to 40% by weight.
  • % of a carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, with mono-, di- or oligosaccharides being preferred, and sucrose being particularly preferred.
  • the use of the third monomer incorporates predetermined breaking points in the polymer, which are responsible for the good biodegradability of the polymer.
  • These terpolymers generally have a relative molecular mass of between 1000 g/mol and 200000 g/mol, preferably between 2000 g/mol and 50000 g/mol and in particular between 3000 g/mol and 10000 g/mol. They can be used in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions, particularly for the production of liquid compositions. All of 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. Amounts close to the upper limit mentioned are preferably used in pasty or liquid, in particular aqueous, compositions.
  • crystalline or amorphous alkali metal aluminosilicates in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid compositions, in particular from 1% by weight to 5% by weight, are used as water-insoluble, water-dispersible inorganic builder materials. deployed.
  • the crystalline detergent grade aluminosilicates are preferred. Amounts close to the upper limit mentioned are preferably used in solid, particulate compositions.
  • suitable aluminosilicates do not have any particles with a particle size of more than 30 ⁇ m and preferably consist of at least 80% by weight of particles with a size of less than 10 ⁇ m.
  • Your calcium binding capacity according to the information in the German patent specification DE 24 12 837 can be determined is in the range from 100 to 200 mg CaO per gram.
  • Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali metal silicates which can be present alone or in a mixture with amorphous silicates.
  • the alkali metal silicates which can be used as builders in the agents 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 can be present in amorphous or crystalline form.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar Na 2 O:SiO 2 ratio of 1:2 to 1:2.8.
  • Amorphous alkali metal silicates of this type are commercially available, for example, under the name Portil® .
  • Crystalline phyllosilicates of the general formula Na 2 Si x O 2x+1 ⁇ yH 2 O are preferably used as crystalline silicates, which can be present alone or in a mixture with amorphous silicates, in which x, the so-called modulus, is a number of 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline layered silicates are those in which x has the value 2 or 3 in the general formula mentioned.
  • both ⁇ - and ⁇ -sodium disilicates are preferred.
  • Practically anhydrous crystalline alkali metal silicates of the abovementioned general formula, in which x is a number from 1.9 to 2.1, produced from amorphous alkali metal silicates can also be used in the compositions described herein.
  • a crystalline layered sodium silicate with a modulus of 2 to 3 is used, as can be produced from sand and soda. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of detergents.
  • alkali metal silicates are preferably 1% by weight to 50% by weight and in particular 5% by weight to 35% by weight, based on anhydrous active substance. If alkali metal aluminosilicate, in particular zeolite, is also present as an additional builder substance, the alkali metal silicate content 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, based in each case 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 in particular 1:1 to 2:1.
  • the agents can contain other components that are customary in detergents, laundry aftertreatment agents, laundry care agents, or cleaning agents.
  • These optional ingredients include, in particular, enzymes, enzyme stabilizers, complexing agents for heavy metals, builders, bleaches, builders, electrolytes, non-aqueous solvents, pH adjusters, odor absorbers, deodorizing substances, perfume, perfume carriers, fluorescent agents, dyes, hydrotropes, foam inhibitors, silicone oils, antiredeposition agents, Graying inhibitors, shrinkage inhibitors, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellent and impregnating agents, swelling and non-slip agents, softening components and UV absorbers.
  • solvents which can be used in particular in the case of liquid agents are preferably non-aqueous solvents which are water-miscible.
  • these include the lower alcohols, for example ethanol, propanol, isopropanol, and the isomeric butanols, glycerol, lower glycols, for example ethylene and propylene glycol, and the ethers which can be derived from the classes of compounds mentioned.
  • the washing or cleaning agent according to the invention also comprises at least one enzyme.
  • Optional enzymes are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase, pectinase and mixtures thereof.
  • Protease obtained from microorganisms such as bacteria or fungi is primarily considered. It can be obtained in a known manner from suitable microorganisms by fermentation processes. Proteases are commercially available, for example, under the names BLAP® , Savinase® , Esperase® , Maxatase® , Optimase® , Alcalase® , Durazym® or Maxapem® .
  • the lipase that can be used can be obtained, for example, from Humicola lanuginosa, from Bacillus species, from Pseudomonas species, from Fusarium species, from Rhizopus species or from Aspergillus 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 cellulase that can be used can be an enzyme that can be obtained from bacteria or fungi and has a pH optimum, preferably in the weakly acidic to weakly alkaline range of 6 to 9.5.
  • Such cellulases are commercially available under the names Celluzyme ® , Carezyme ® and Ecostone ® .
  • Suitable pectinases are, for example, under the names Gamanase® , Pektinex AR® , X- Pect® or Pectaway® from Novozymes, under the name Rohapect UF® , Rohapect TPL® , Rohapect PTE100® , Rohapect MPE® , Rohapect MA plus HC, Rohapect DA12L ® , Rohapect 10L ® , Rohapect B1L ® from AB Enzymes and available under the name Pyrolase ® from Diversa Corp., San Diego, CA, USA.
  • the agent according to the invention contains at least one enzyme selected from protease, amylase, cellulase, mannanase, lipase, pectate lyase as the enzyme.
  • the enzymes contained in the agent according to the invention can be adsorbed on carriers and/or embedded in encapsulating substances in order to protect them against premature inactivation.
  • the enzymes obtained can be added to agents according to the invention in any form established according to the prior art. These include, in particular, the solid preparations obtained by granulation, extrusion or lyophilization, advantageously as concentrated as possible, low in water and/or mixed with stabilizers.
  • the enzymes can also be encapsulated, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel, or in those from Core-shell type in which an enzyme-containing core is coated with a protective layer impermeable to water, air and/or chemicals.
  • Additional active substances for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can also be applied in superimposed layers.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • Such granules for example due to the application of polymeric film formers, produce little dust and are stable in storage due to the coating.
  • the proteases used are preferably alkaline serine proteases. They act as non-specific endopeptidases, which means that they hydrolyze any acid amide bonds that are inside peptides or proteins, thereby breaking down protein-containing soiling on the items to be cleaned. Their optimum pH is usually in the clearly alkaline range.
  • subtilisin-type proteases preferably used in detergents and cleaning agents are the subtilisins BPN' and Carlsberg, the protease PB92, the subtilisins 147 and 309, the protease from Bacillus lentus, in particular from Bacillus lentus DSM 5483, subtilisin DY and the the subtilases, but no longer the subtilisins in the narrower sense of the enzymes Thermitase, proteinase K and the proteases TW3 and TW7, as well as variants of the proteases mentioned which have an amino acid sequence which is altered compared to the starting protease.
  • Proteases are modified in a targeted or random manner using methods known from the prior art and are thus optimized, for example, for use in detergents and cleaning agents. These include point mutagenesis, deletion or insertion mutagenesis, or fusion with other proteins or protein parts. These modified protease variants can also be contained in the agents according to the invention.
  • the agent according to the invention can contain an amylase, more preferably an alpha-amylase.
  • Alpha amylases are among the technically important enzymes.
  • An alpha-amylase is an enzyme that catalyzes the hydrolysis of the internal ⁇ (1-4) glycosidic bonds of amylose but not the cleavage of terminal or ⁇ (1-6) glycosidic bonds.
  • Alpha amylases therefore represent a group of esterases (EC 3.2.1.1.).
  • Alpha-amylases catalyze the cleavage of starch, glycogen, and other oligo- and polysaccharides that contain an ⁇ (1-4) glycosidic linkage.
  • alpha-amylases act against starch residues in the laundry and catalyze their hydrolysis (endohydrolysis).
  • the alpha-amylases used in the detergents or cleaning agents known from the prior art are usually of microbial origin and usually come from bacteria or fungi, for example of the genera Bacillus, Pseudomonas, Acinetobacter, Micrococcus, Humicola, Trichoderma or Trichosporon, in particular Bacillus .
  • Alpha-amylases are usually produced by suitable microorganisms, for example by transgenic expression hosts of the genus Bacillus or by filamentous fungi, using biotechnological methods known per se.
  • the agents preferably additionally contain at least one cellulase.
  • a cellulase is an enzyme. Synonymous terms can be used for cellulases, in particular endoglucanase, endo-1,4-beta-glucanase, carboxymethyl cellulase, endo-1,4-beta-D-glucanase, beta-1,4-glucanase, beta-1,4-endoglucan hydrolase , celludextrinase or avicelase.
  • the decisive factor in determining whether an enzyme is a cellulase within the meaning of the invention is its ability to hydrolyze 1,4- ⁇ -D-glucosidic bonds in cellulose.
  • Cellulases which can be prepared according to the invention include, for example, the fungal cellulase preparation rich in endoglucanase (EG) or its further developments, which is offered by the company Novozymes under the trade name Celluzyme® .
  • the products Endolase ® and Carezyme ® which are also available from the company Novozymes, are based on the 50 kD EG or the 43 kD EG from Humicola insolens DSM 1800.
  • Other usable commercial products from this company are Cellusoft ® , Renozyme ® and Celluclean ® .
  • Other cellulases from the company AB Enzymes are Econase ® and Ecopulp ® .
  • suitable cellulases are from Bacillus sp. CBS 670.93 and CBS 669.93, wherein the Bacillus sp. CBS 670.93 is available from the Danisco/Genencor company under the tradename Puradax® .
  • Other usable commercial products from the company Danisco/Genencor are “Genencor detergent cellulase L” and IndiAge® Neutra.
  • Variants of these enzymes obtainable by point mutations can also be used according to the invention.
  • Particularly preferred cellulases are Thielavia terrestris cellulase variants described in International Laid-Open Specification WO 98/12307 are disclosed, cellulases from Melanocarpus, in particular Melanocarpus albomyces, which are disclosed in International Offenlegungsschrift WO 97/14804 are disclosed, EGIII-type cellulases from Trichoderma reesei, which are disclosed in European patent application EP 1 305 432 are disclosed or variants obtainable therefrom, in particular those disclosed in the European patent applications EP1240525 and EP1305432 , as well as cellulases disclosed in the International Laid-Open Specifications WO1992006165 , WO 96/29397 and WO 02/099091 . Reference is therefore expressly made to their respective disclosure or their relevant disclosure content is therefore expressly included in the present patent application.
  • the agents according to the invention additionally contain at least one lipase.
  • Lipase enzymes preferred according to the invention are selected from at least one enzyme from the group formed by triacylglycerol lipase (EC 3.1.1.3) and lipoprotein lipase (EC 3.1.1.34) and monoglyceride lipase (EC 3.1.1.23).
  • the area of use preferred according to the invention for the agents according to the invention is the cleaning of textiles. Because detergents and cleaning agents for textiles have predominantly alkaline pH values, lipases in particular are used for this purpose, which are active in an alkaline medium.
  • the lipase preferably contained in a composition according to the invention is naturally present in a microorganism of the species Thermomyces lanuginosus or Rhizopus oryzae or Mucor javanicus or is derived from the aforementioned naturally present lipases by mutagenesis.
  • preferred lipases are the lipase enzymes available from Amano Pharmaceuticals under the names Lipase M- AP10® , Lipase LE® and Lipase F® (also Lipase JV® ).
  • the lipase F ® is naturally present in Rhizopus oryzae.
  • the lipase M- AP10® is naturally present in Mucor javanicus.
  • compositions of a most preferred embodiment of the invention contain at least one lipase selected from at least one or more polypeptides having an amino acid sequence that is at least 90% (and more preferably at least 81%, 82%, 83%, 84%, 85% %, 86%, 87%, 88%, 89%, 90%, 90.5%, 91%, 91.5%, 92%, 92.5%, 93%, 93.5%, 94%, 94 .5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, 99.0%, 99.1%, 99.2% , 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9%) to the wild-type lipase from the strain DSM 4109
  • Thermomyces lanuginosus is identical. It is again preferred if, starting from said wild-type lipase from strain DSM 4109, at least the amino acid change N233R is present
  • a highly preferred lipase is commercially available under the trade name Lipex® from the company Novozymes (Denmark) and can be used advantageously in the cleaning compositions according to the invention.
  • the lipase Lipex® 100 L (ex Novozymes A/S, Denmark) is particularly preferred here.
  • Preferred compositions are characterized in that said lipase enzyme from Lipex ® 100 L is present in a total amount of from 0.01 to 1.0% by weight, in particular from 0.02 to 0.1% by weight, based on the total weight of the composition. %, is included.
  • the agents according to the invention can additionally contain at least one mannanase as an enzyme.
  • a mannanase contained in the composition according to the invention (in particular in a detergent and cleaning agent preferred according to the invention for textiles) catalyzes the hydrolysis of 1,4-beta-D-mannosidic bonds in mannans, galactomannans, glucomannans and galactoglucomannans as part of its mannanase activity.
  • said mannanase enzymes according to the invention are referred to as E.C. 3.2.1.78 classified.
  • compositions according to the invention contain, for example, the mannanase which is marketed under the name Mannaway® by the Novozymes company.
  • customary enzyme stabilizers that may be present, especially in liquid agents, include amino alcohols, for example mono-, di-, triethanolamine and -propanolamine and mixtures thereof, lower carboxylic acids, boric acid, alkali metal borates, boric acid-carboxylic acid combinations, boric acid esters, boronic acid derivatives, calcium salts, for example Ca-formic acid combination, magnesium salts, and/or sulphur-containing reducing agents.
  • Suitable foam inhibitors include long-chain soaps, in particular behenic soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, as well as microfine, optionally silanated or otherwise hydrophobic silica may contain.
  • foam inhibitors are preferably bound to granular, water-soluble carrier substances.
  • polyester-active soil release polymers 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.
  • the preferably used dirt-removing polyesters include those compounds that are formally accessible by esterification of two monomer parts, the first monomer being a dicarboxylic acid HOOC-Ph-COOH and the second monomer being a diol HO-(CHR 11 -) a OH, which can also be used as a 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 carbon atoms, sulfonic acid groups, carboxyl groups and mixtures thereof
  • R 11 is hydrogen, an alkyl radical having 1 to 22 carbon atoms and mixtures thereof
  • a is a number from 2 to 6
  • b is a number from 1 to 300.
  • the polyesters obtainable from these preferably contain both monomer diol units -O-(CHR 11 -) a O- and polymer diol units --( O-(CHR 11 -) a ) b O- before.
  • 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 in the polymer diol units is preferably in the range from 4 to 200, in particular from 12 to 140.
  • the molecular weight or the average molecular weight or the maximum of the molecular weight distribution of preferred soil-removing polyesters is in the range from 250 g/mol to 100,000 g/mol, in particular from 500 g/mol to 50000 g/mol.
  • the acid on which the radical Ph is based is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulphoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably present in salt form, in particular as an alkali metal or ammonium salt. Among these, the sodium and potassium salts are particularly preferred.
  • HOOC-Ph-COOH monomer 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 can be present in the soil-removing polyester.
  • these include, for example, alkylene and alkenylenedicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
  • Preferred diols HO-(CHR 11 -) a OH include those in which R 11 is hydrogen and a is from 2 to 6 and those in which a is 2 and R 11 is selected from hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 carbon atoms is selected.
  • R 11 is hydrogen and a is from 2 to 6
  • R 11 is selected from hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 carbon atoms is selected.
  • those of the formula HO-CH 2 -CHR 11 -OH, in which R 11 has the meaning given above 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.
  • polymeric diols is polyethylene glycol with an average molar mass in the range from 1000 g/mol to 6000 g/mol.
  • the polyesters can also be end-capped, suitable end groups being alkyl groups having 1 to 22 carbon atoms and esters of monocarboxylic acids.
  • the end groups bonded via ester bonds can be based on alkyl, alkenyl and aryl monocarboxylic acids having 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms.
  • alkyl, alkenyl and aryl monocarboxylic acids having 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms.
  • These include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleic 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, eleostearic acid, arachidic acid , Gadoleic acid, ar
  • the end groups can also be based on hydroxymonocarboxylic acids with 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 can in turn be connected to one another via their hydroxyl group and their carboxyl group and can therefore be present more than once in an end group.
  • the number of hydroxymonocarboxylic acid units per end group, i.e. their degree of oligomerization, is preferably in the range from 1 to 50, in particular from 1 to 10.
  • the soil-removing polymers are preferably water-soluble, the term "water-soluble" meaning 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.
  • polymers which are preferably used have a solubility of at least 1 g per liter, in particular at least 10 g per liter, under these conditions.
  • the laundry care agents used as aftertreatment agents in particular can contain additional softener components, preferably cationic surfactants.
  • additional softener components preferably cationic surfactants.
  • fabric-softening components are quaternary ammonium compounds, cationic polymers and emulsifiers, such as are used in hair care products and also in fabric conditioners.
  • Suitable examples are quaternary ammonium compounds of the formulas (II) and (III), where in (II) R and R 1 are an acyclic alkyl radical having 12 to 24 carbon atoms, R 2 is a saturated C 1 -C 4 alkyl or hydroxyalkyl radical, R 3 is either the same as R, R 1 or R 2 or is one aromatic residue.
  • X - represents either a halide, methosulfate, methophosphate, or phosphate ion, and mixtures thereof.
  • Examples of cationic compounds of the formula (II) are didecyldimethylammonium chloride, ditallowdimethylammonium chloride or dihexadecylammonium chloride.
  • esterquats are notable for their good biodegradability and are preferred in the context of the present invention.
  • R 4 is an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds
  • R 5 represents H, OH or O(CO)R 7
  • R 6 independently of R 5 represents H, OH or O(CO)R 8
  • R 7 and R 8 each independently represent an aliphatic alkyl radical having 12 bis 22 carbon atoms with 0, 1, 2 or 3 double bonds.
  • m, n and p can each independently have the value 1, 2 or 3.
  • X - can be either a halide, methosulfate, methophosphate or phosphate ion, and mixtures of these. Preference is given to compounds which contain the group O(CO)R 7 for R 5 and alkyl radicals having 16 to 18 carbon atoms for R 4 and R 7 . Compounds in which R 6 is also OH are particularly preferred.
  • Examples of compounds of the formula (III) are methyl-N-(2-hydroxyethyl)-N,N-di(tallowacyl-oxyethyl)ammonium methosulfate, bis(palmitoyl)-ethyl-hydroxyethyl-methyl-ammonium methosulfate or methyl -N,N-bis(acyloxyethyl)-N-(2-hydroxyethyl)ammonium methosulfate.
  • the agents contain the additional plasticizer components in amounts of up to 35% by weight, preferably from 0.01 to 25% by weight, particularly preferably from 0.01 to 15% by weight and in particular from 0.01% up to 10% by weight, in each case based on the total agent.
  • the agents may contain pearlescent agents.
  • Pearlescent agents give the textiles an additional shine and are therefore preferably used in mild detergents.
  • suitable pearlescent agents are: alkylene glycol esters; fatty acid alkanolamides; partial glycerides; esters of polybasic, optionally hydroxy-substituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms; Fatty substances, such as fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which have a total of at least 24 carbon atoms; Ring opening products of olefin epoxides having 12 to 22 carbon atoms with fatty alcohols having 12 to 22 carbon atoms, fatty acids and/or polyols having 2 to 15 carbon atoms and 2 to 10 hydroxyl groups, and mixtures thereof.
  • liquid agents can also contain thickeners.
  • thickeners particularly in the case of liquid detergents in gel form, has proven effective in increasing consumer acceptance.
  • Polymers derived from nature that can be used as thickeners are, for example, agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatine and casein, cellulose derivatives such as carboxymethylcellulose hydroxyethyl - and -propyl cellulose, and polymeric polysaccharide thickeners such as xanthan gum; fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes are also suitable.
  • the textile care agents according to the invention contain thickeners, preferably in amounts of up to 10% by weight, particularly preferably up to 5% by weight, in particular from 0.1 to 1% by weight, based in each case on the agent as a whole .
  • the agents can additionally contain odor absorbers and/or color transfer inhibitors.
  • the agents optionally contain 0.1% by weight to 2% by weight, preferably 0.2% by weight to 1% by weight, of color transfer inhibitor which, in a preferred embodiment of the invention, is a polymer of vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide or a copolymer of these.
  • polyvinylpyrrolidones with molecular weights of 15,000 to 50,000 and polyvinylpyrrolidones with molecular weights above 1,000,000, in particular from 1,500,000 to 4,000,000, N-vinylimidazole/N-vinylpyrrolidone copolymers, polyvinyloxazolidones, copolymers based on vinyl monomers can be used and carboxylic acid amides, polyesters and polyamides containing pyrrolidone groups, grafted polyamidoamines, polyamine-N-oxide polymers, polyvinyl alcohols and copolymers based on acrylamidoalkenylsulfonic acids.
  • enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance that supplies hydrogen peroxide in water.
  • a mediator compound for the peroxidase for example an acetosyringone, a phenol derivative or a phenotiazine or phenoxazine, is preferred in this case, it also being possible to use the above-mentioned polymeric dye transfer inhibitor active ingredients.
  • polyvinylpyrrolidone preferably has an average molar mass in the range from 10,000 to 60,000, in particular in the range from 25,000 to 50,000.
  • copolymers preference is given to those of vinylpyrrolidone and vinylimidazole in a molar ratio of 5:1 to 1:1 with an average molar mass in the range from 5,000 to 50,000, in particular from 10,000 to 20,000.
  • Preferred deodorizing substances are metal salts of an unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acid having at least 16 carbon atoms and/or a resin acid, with the exception of the alkali metal salts, and any mixtures thereof.
  • a particularly preferred unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acid having at least 16 carbon atoms is ricinoleic acid.
  • a particularly preferred resin acid is abietic acid.
  • Preferred metals are the transition metals and the lanthanides, in particular the transition metals from Groups VIIIa, Ib and IIb of the Periodic Table and lanthanum, cerium and neodymium, particularly preferably cobalt, nickel, copper and zinc, extremely preferably zinc.
  • the cobalt, nickel and copper salts and the zinc salts are similarly effective, the zinc salts are to be preferred for toxicological reasons.
  • One or more metal salts of ricinoleic acid and/or abietic acid, preferably zinc ricinoleate and/or zinc abietate, in particular zinc ricinoleate, are advantageous and therefore particularly preferred as deodorizing substances.
  • Cyclodextrins and mixtures of the aforementioned metal salts with cyclodextrin preferably in a weight ratio of from 1:10 to 10:1, particularly preferably from 1:5 to 5:1 and in particular from 1: 3 to 3:1.
  • cyclodextrin includes all known cyclodextrins, i.e. both unsubstituted cyclodextrins with 6 to 12 glucose units, in particular alpha-, beta- and gamma-cyclodextrins and their mixtures and/or their derivatives and/or their mixtures.
  • Liquid or pasty agents in the form of solutions containing customary solvents, in particular water are generally produced by simply mixing the ingredients, which can be added to an automatic mixer as such or as a solution.
  • Embodiments of the present invention include all solid, powdery, liquid, gel-like or pasty forms of administration of the agents described herein, which may also consist of several phases and may be in compressed or non-compressed form.
  • the agent can be in the form of a free-flowing powder, in particular with a bulk density of 300 g/l to 1200 g/l, in particular 500 g/l to 900 g/l or 600 g/l to 850 g/l.
  • the solid dosage forms of the agent also include extrudates, granules, tablets or pouches.
  • the agent can also be liquid, gel-like or pasty, for example in the form of a non-aqueous liquid detergent or dishwashing detergent or a non-aqueous paste or in the form of an aqueous liquid detergent or dishwashing detergent or an aqueous paste.
  • the agent can be in the form of a one-component system. Such funds consist of one phase.
  • a remedy can also consist of several phases. Such a remedy is therefore divided into several components.
  • the agents can have different states of aggregation.
  • the detergents or cleaning agents are liquid or gel-like agents.
  • the agents are present, preferably in liquid form, as a portion in a completely or partially water-soluble envelope. The portioning makes it easier for the consumer to dose.
  • the funds can be packed in foil bags, for example.
  • Pouch packaging made from water-soluble film eliminates the need for the consumer to tear open the packaging. In this way, a single portion measured for a wash cycle can be conveniently dosed by placing the bag directly in the washing machine or by throwing the bag into a certain amount of water, for example in a bucket, bowl or hand wash basin.
  • the film bag surrounding the wash portion dissolves without leaving any residue when a certain temperature is reached.
  • thermoforming process deep-drawing process
  • water-soluble envelopes do not necessarily have to consist of a film material, but can also be dimensionally stable containers that can be obtained, for example, by means of an injection molding process.
  • the filling material is injected into the capsule that is being formed, with the injection pressure of the filling liquid pressing the polymer strips into the cavities of the hemisphere.
  • a process for the production of water-soluble capsules in which first the filling and then the Sealing is based on the so-called Bottle-Pack ® process.
  • a tube-like preform is fed into a two-part cavity. The cavity is closed, with the lower tube section being sealed, the tube is then inflated to form the capsule shape in the cavity, filled and finally sealed.
  • the casing material used to produce the water-soluble portion is preferably a water-soluble polymeric thermoplastic, particularly preferably selected from the group (optionally partially acetalized) polyvinyl alcohol, polyvinyl alcohol copolymers, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and derivatives thereof, starch and derivatives thereof, blends and composites, inorganic salts and mixtures of the materials mentioned, preferably hydroxypropylmethylcellulose and/or polyvinyl alcohol blends.
  • Polyvinyl alcohols are commercially available, for example under the trademark Mowiol® (Clariant).
  • polyvinyl alcohols are, for example, Mowiol® 3-83, Mowiol® 4-88, Mowiol® 5-88, Mowiol® 8-88 and Clariant L648.
  • the water-soluble thermoplastic used to produce the portion can optionally also contain polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers and/or mixtures of the above polymers.
  • the water-soluble thermoplastic used comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol %, preferably 80 to 90 mol %, particularly preferably 81 to 89 mol % and in particular 82 to 88 mol %. It is further preferred that the water-soluble thermoplastic used comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol -1 , preferably from 11,000 to 90,000 gmol -1 , particularly preferably from 12,000 to 80,000 gmol -1 and in particular from 13,000 to 70,000 gmol -1 lies.
  • thermoplastics are used in amounts of at least 50% by weight, preferably at least 70% by weight, particularly preferably at least 80% by weight and in particular at least 90% by weight, in each case based on the weight the water-soluble polymeric thermoplastic.
  • Washing or cleaning processes ie in particular processes for cleaning textiles, are generally characterized in that active cleaning substances are applied to the items to be cleaned in one or more process steps and washed off after the exposure time, or that the items to be cleaned are otherwise treated with a detergent or cleaning agent or a solution of this agent.
  • temperatures of up to 95° C. or less, 90° C. or less, 60° C. or less, 50° C. or less, 40° C. or less are used in various embodiments of the invention , 30°C or less or 20°C or less. These temperature specifications relate to the temperatures used in the washing or cleaning steps.
  • the present invention is also aimed at the use of the agent according to the invention for minimizing the tendency to wrinkle and/or for facilitating the ironing of textiles; and to increase the softness of fabrics after laundering as described above.
  • the present invention is also directed to methods of finishing textiles to reduce the tendency to wrinkle and/or make them easier to iron, and methods of increasing the softness of textiles as described above, and a washing method as described above.
  • ingredients recipe 1 Recipe 2 (according to the invention) Standard (in % by weight) Standard with 1.0% propylene glycol ester (in % by weight) anionic surfactant 5.7 5.7 nonionic surfactant 3.3 3.3 Builders (citric acid and phosphonates) 0.43 0.43 caustic soda 0.6 0.6 palm kernel oil fatty acid 0.5 0.5 glycerin 0.5 0.5 sodium chloride 1.8 1.8 Enzymes (protease, amylase, cellulase, lipase) 0.4 0.4 boric acid 0.5 0.5 propylene glycol laurate; Migoto type BP (propylene glycol ester) - 1.0 Other additives (preservatives, defoamers, optical brighteners, dyes, perfume) 0.49 0.49 Water to 100
  • the Migoto type BP compound from Riken was used as the propylene glycol ester. Surprisingly, it has now been found that these compounds can improve the surface of textiles in detergents. The esters can be easily incorporated into the liquid detergent.
  • Fabric SAM Fabric 65% Polyester / 35% Cotton
  • Cotton Formulation 2 standard with 1% propylene glycol laurate

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Claims (9)

  1. Produit de lavage, de post-traitement du linge ou d'entretien du linge, en particulier produit de lavage liquide, caractérisé en ce que le produit contient, par rapport au poids total, 0,01 à 30 % en poids, de préférence 0,1 à 4 % en poids d'au moins un ester de propylèneglycol selon la formule (I) :
    Figure imgb0038
     où
    X1 est -OH et
    X2 est
    Figure imgb0039
    dans laquelle R2 est un groupe alkyle ayant de 5 à 35 atomes de carbone
    ou une groupe alcényle ayant de 5 á 35 atomes de carbone.
  2. Produit de lavage, de post-traitement du linge ou d'entretien du linge, en particulier produit de lavage liquide, selon la revendication 1, caractérisé en ce que R2 est un alkyle comportant 11 atomes de carbone.
  3. Produit de lavage, de post-traitement du linge ou d'entretien du linge, en particulier produit de lavage liquide selon l'une des revendications 1 à 2, caractérisé en ce que le produit contient en outre au moins un autre composant choisi dans le groupe constitué par les agents tensioactifs, les enzymes, les stabilisateurs d'enzymes, les complexants pour métaux lourds, les adjuvants, les agents de blanchiment, les adjuvants, les électrolytes, les solvants non aqueux, les régulateurs de pH, les absorbeurs d'odeurs, les substances désodorisantes, les parfums, les porteurs de parfums, les agents fluorescents, les colorants, les hydrotropes, les inhibiteurs de mousse, les huiles de silicone, les agents antidéposition, les inhibiteurs de grisaillement, les agents antirétrécissement, d'autres agents anti-froissement, les inhibiteurs de transfert de couleur, les agents antimicrobiens, les germicides, les produits contenant des agents de conservation, les inhibiteurs de corrosion, les agents antistatiques, les agents d'amertume, les auxiliaires de repassage, les agents de phobisation et d'imprégnation, les agents de gonflement et de fixation par glissement, les composants adoucissants ainsi que les absorbeurs d'UV.
  4. Utilisation d'un produit de lavage, de post-traitement du linge ou d'entretien du linge, en particulier d'un produit de lavage liquide, caractérisée en ce que le produit contient, par rapport au poids total, 0,01 à 30 % en poids, de préférence 0,1 à 4 % en poids d'au moins un ester de propylèneglycol selon la formule (I) :
    Figure imgb0040
     où
    X1 est -OH et
    X2 est
    Figure imgb0041
    dans laquelle R2 est un alkyle de 5 à 35 atomes de carbone ou un alcényle de 5 à 35 atomes de carbone,
    pour minimiser le froissement et/ou faciliter le repassage des textiles.
  5. Utilisation d'un produit de lavage, de post-traitement du linge ou d'entretien du linge, en particulier d'un produit de lavage liquide, caractérisée en ce que le produit contient, par rapport au poids total, 0,01 à 30 % en poids, de préférence 0,1 à 4 % en poids d'au moins un ester de propylèneglycol selon la formule (I) :
    Figure imgb0042
     où
    X1 est -OH et
    X2 est
    Figure imgb0043
    dans laquelle R2 est un alkyle de 5 à 35 atomes de carbone ou un alcényle de 5 à 35 atomes de carbone,
    pour augmenter la douceur des textiles après le lavage.
  6. Procédé d'apprêtage de textiles pour réduire le froissement et/ou faciliter le repassage, par mise en contact avec un agent de lavage, de post-traitement du linge ou d'entretien du linge, en particulier un agent de lavage liquide, caractérisé en ce que l'agent contient, par rapport au poids total, de 0,01 à 30 % en poids, de préférence de 0,1 à 4 % en poids d'au moins un ester de propylèneglycol selon la formule (I) :
    Figure imgb0044
    Figure imgb0045
     où
    X1 est -OH et
    X2 est
    Figure imgb0046
    dans laquelle R2 est un groupe alkyle ayant de 5 à 35 atomes de carbone ou un groupe alcényle ayant de 5 à 35 atomes de carbone,
    et le lavage ultérieur du textile en présence du produit de lavage, de post-traitement ou d'entretien du linge.
  7. Procédé pour augmenter la douceur de textiles par mise en contact avec un agent de lavage, de post-traitement du linge ou d'entretien du linge, en particulier un agent de lavage liquide, caractérisé en ce que l'agent contient, par rapport au poids total, de 0,01 à 30 % en poids, de préférence de 0,1 à 4 % en poids d'au moins un ester de propylèneglycol selon la formule (I) :
    Figure imgb0047
     où
    X1 est -OH et
    X2 est
    Figure imgb0048
    dans laquelle R2 est un groupe alkyle ayant de 5 à 35 atomes de carbone ou un groupe alcényle ayant de 5 à 35 atomes de carbone,
    et le lavage ultérieur du textile en présence du produit de lavage, de post-traitement ou d'entretien du linge.
  8. Procédé de lavage comprenant les étapes de procédé suivantes
    a) Fournir une solution de lavage ou de nettoyage comprenant un agent de lavage, de post-traitement ou d'entretien du linge, en particulier un détergent liquide, selon l'une quelconque des revendications 1 à 3, et
    b) Mise en contact d'un textile ou d'une surface dure avec la solution de lavage ou de nettoyage selon (a).
  9. Utilisation ou procédé selon l'une quelconque des revendications 4 à 7, caractérisé en ce que le produit de lavage, de post-traitement ou d'entretien du linge, en particulier la lessive liquide, est un produit de lavage, de post-traitement ou d'entretien du linge, en particulier une lessive liquide, selon l'une quelconque des revendications 1 à 3.
EP17737814.8A 2016-07-25 2017-07-12 Ester de propylène glycol utilisé comme composant d'entretien de textiles Active EP3487972B1 (fr)

Applications Claiming Priority (2)

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DE102016213567.8A DE102016213567A1 (de) 2016-07-25 2016-07-25 Propylenglykolester als textilpflegende Inhaltsstoffe
PCT/EP2017/067559 WO2018019593A1 (fr) 2016-07-25 2017-07-12 Ester de propylène glycol utilisé comme composant d'entretien de textiles

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EP3487972A1 EP3487972A1 (fr) 2019-05-29
EP3487972B1 true EP3487972B1 (fr) 2023-05-03

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Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT330930B (de) 1973-04-13 1976-07-26 Henkel & Cie Gmbh Verfahren zur herstellung von festen, schuttfahigen wasch- oder reinigungsmitteln mit einem gehalt an calcium bindenden substanzen
EP0877077B1 (fr) 1991-06-11 2010-05-26 Genencor International, Inc. Compositions de detergent contenant des compositions de cellulase manquant de constituants de type CBH I
NZ303162A (en) 1995-03-17 2000-01-28 Novo Nordisk As Enzyme preparations comprising an enzyme exhibiting endoglucanase activity appropriate for laundry compositions for textiles
DK0857216T3 (en) 1995-10-17 2014-12-15 Ab Enzymes Oy Cellulases, GENES ENCODING THEM AND USES THEREOF
CN100362100C (zh) 1996-09-17 2008-01-16 诺沃奇梅兹有限公司 纤维素酶变体
EP0845523A3 (fr) * 1996-11-28 1999-01-27 Givaudan-Roure (International) S.A. Ingrédient pour la prévention du problème de viscosité dans un adoucissant concentré parfumé pour le linge
WO2001046700A2 (fr) 1999-12-23 2001-06-28 Pharmacia & Upjohn Company Titrages et methodes diagnostiques et therapeutiques bases sur l'utilisation des canaux sodiques comme cibles de proteine beta-amyloide ou d'agregats de celle-ci
AU2001280920A1 (en) 2000-08-04 2002-02-18 Genencor International, Inc. Mutant trichoderma reesei egiii cellulases, dna encoding such egiii compositions and methods for obtaining same
MXPA03011194A (es) 2001-06-06 2004-02-26 Novozymes As Endo-beta-1,4-glucanasa.
GB0219281D0 (en) 2002-08-19 2002-09-25 Unilever Plc Fabric care composition
JP2005002179A (ja) * 2003-06-11 2005-01-06 Techno Guard Kk 油性成分用洗浄除去剤およびこれを使用した洗浄方法
JP5645808B2 (ja) * 2009-03-03 2014-12-24 日清オイリオグループ株式会社 化粧料、その製造方法、化粧料用組成物、及び前記化粧料用組成物を含む化粧料とその製造方法

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EP3487972A1 (fr) 2019-05-29
WO2018019593A1 (fr) 2018-02-01

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