EP2791310B1 - Waschmittelzusammensetzungen - Google Patents

Waschmittelzusammensetzungen Download PDF

Info

Publication number
EP2791310B1
EP2791310B1 EP12780495.3A EP12780495A EP2791310B1 EP 2791310 B1 EP2791310 B1 EP 2791310B1 EP 12780495 A EP12780495 A EP 12780495A EP 2791310 B1 EP2791310 B1 EP 2791310B1
Authority
EP
European Patent Office
Prior art keywords
cationic
polymer
composition according
polymers
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP12780495.3A
Other languages
English (en)
French (fr)
Other versions
EP2791310A1 (de
Inventor
Martin Charles Crossman
Belinda Fay DAWSON
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP12780495.3A priority Critical patent/EP2791310B1/de
Publication of EP2791310A1 publication Critical patent/EP2791310A1/de
Application granted granted Critical
Publication of EP2791310B1 publication Critical patent/EP2791310B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines

Definitions

  • This invention relates to a laundry composition. More particularly, the invention is directed to a softening in the wash laundry composition.
  • Alkyl ether carboxylates are known as anionic surfactants for laundry formulations. We have found that a formulation comprising an alkyl ether carboxylate along with a betaine surfactant displays synergistically better softening.
  • the invention is directed to a laundry detergent composition
  • a laundry detergent composition comprising:-
  • the nonionic surfactant comprises an alcohol ethoxylate.
  • betaine surfactant comprises amidobetaines, alkyl betaines, or mixtures thereof.
  • the alkyl ether carboxylic acid or carboxylate salt thereof is present at a level of from 1 to 10 wt.%, more preferably at a level of from 2 to 7.5 wt.%.
  • Preferred alkyl ether carboxylic acid or carboxylate salt are depicted by formula 1: wherein R denotes a saturated or unsaturated C 6 -C 22 alkyl chain; R 1 and R 2 are either both hydrogen; or R 1 is hydrogen and R 2 is CH 3 ; or R 1 is CH 3 and R 2 is hydrogen; R 3 is hydrogen, or a solubilising cation such as sodium, potassium, ammonium or substituted ammonium; and, n is a number from 2 to 20, preferably 3 to 12, more preferably 3 to 10, which denotes the number of repeat units.
  • Preferred alkyl ether carboxylic acids or carboxylate salts thereof have a C 8 -C 18 alkyl chain with between 2 to 20, more preferably between 3 to 12, even more preferably between 3 to 10 glycol repeat units, wherein the glycol repeat units are selected from ethylene glycol, propylene glycol or mixtures thereof.
  • the molecule of formula 1 may contain mixtures of polyethylene glycol (also known as ethylene oxide) and polypropylene glycol (also known as propylene oxide) repeat units
  • a preferred level of the cationic polymer is from 0.1 to 1 wt.%.
  • the cationic polymer is selected from the group consisting of: cationic polysaccharide polymers, and cationic non-saccharide polymers having cationic protonated amine or quaternary ammonium functionalities that are homo or copolymers derived from monomers containing an amino or quaternary nitrogen functional group polymerised from at least one of the following monomer classes: acrylate, methacrylate, acrylamide, methacrylamide; allyls (including diallyl and methallyl); ethylene imine; and/or vinyl monomer classes, and mixtures thereof.
  • the cationic polymer is selected from the group consisting of cationic cellulose polymers, cationic guar polymers, cationic diallyl quaternary ammonium-containing polymers and homo or copolymers of dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate or tert-butylaminoethyl (meth)acrylate in their quaternary or protonated amine form, and mixtures thereof.
  • Preferred cationic polysaccharide polymers are cationic guar and cationic cellulose polymers. Particularly preferred is hydroxy ether cellulose that is modified by incorporation of cationic groups (i.e. quaternised hydroxy ethyl cellulose).
  • the detergent composition is a liquid laundry detergent composition.
  • composition is a liquid, then preferably it has a pH of from 6.2 to 9, more preferably from pH 6.5 to 8.5, for example from pH 6.5 to 8.
  • the composition further comprises an ingredient selected from, shading dye, enzyme, an antiredeposition polymer, a dye transfer inhibiting polymer, builder, sequestrant, sunscreen and/or soil release polymer.
  • the invention provides the use of a composition comprising an alkyl ether carboxylate, a cationic polymer and a betaine to soften fabrics.
  • the term “comprising” means including, made up of, composed of, consisting and/or consisting essentially of.
  • the invention is directed to laundry compositions containing alkyl ether carboxylic acid or carboxylate salt thereof, a cationic polymer, a nonionic surfactant which comprises an alcohol ethoxylate, a betaine surfactant, and an anionic surfactant, comprising sodium and/or potassium alkyl C 9 to C 20 benzene sulfonate.
  • the composition displays improved stability over the prior art at pH levels of 6.2 to 9.
  • the invention can take any of a number of forms that are laundry compositions. Examples include powders, granules, bars, gels and liquids. Preferably the composition is in the form of a liquid laundry product. Preferably they are main wash products. It can take the form of a laundry composition for the main wash, which may be dilutable or non-dilutable.
  • the laundry composition may for example be an isotropic liquid, or a surfactant-structured liquid.
  • Particularly preferred forms of this invention include combination detergent/softener products to provide "softening in the wash".
  • the detergent composition is a liquid laundry detergent composition.
  • the liquid composition has a pH of from 6.2 to 9, more preferably from pH 6.5 to 8.5, for example from pH 6.5 to 8.
  • composition comprises 1 to 12 wt.% alkyl ether carboxylic acid or carboxylate salt thereof.
  • the amount of alkyl ether carboxylic acid (or salt thereof) is considered separate to and not included in the level of anionic surfactant present in the composition.
  • the alkyl ether carboxylate (or salt thereof) is itself considered an anionic surfactant, for the purposes of this invention, the amount of anionic surfactant present in the formulation does not include the amount of alkyl ether carboxylate (or salt thereof).
  • alkyl ether carboxylic acid/carboxylate is usually derived from a fatty alcohol which is alkoxylated, usually with ethylene glycol and/or propylene glycol, a carboxylic acid is then introduced to the material to form the alkyl ether carboxylic acid.
  • the alkyl ether carboxylic acid or carboxylate salt thereof is present at a level of from 1 to 10 wt.%, more preferably at a level of from 2 to 7.5 wt.%.
  • Preferred alkyl ether carboxylic acid or carboxylate salt are depicted by formula 1: wherein R denotes a saturated or unsaturated C 6 -C 22 alkyl chain; R 1 and R 2 are either both hydrogen (in which case the repeat unit is ethylene glycol known as (EO) for short); or R 1 is hydrogen and R 2 is CH 3 ; or R 1 is CH 3 and R 2 is hydrogen (in which case the repeat unit is propylene glycol, known as (PO) for short); R 3 is hydrogen (in which case it is an alkyl ether carboxylic acid), or a solubilising cation such as sodium, potassium, ammonium or substituted ammonium (in which case it is an alkyl ether carboxylate salt); and, n is a number from 2 to 20, preferably 3 to 12, more preferably 3 to 10, which denotes the number of repeat units.
  • R denotes a saturated or unsaturated C 6 -C 22 alkyl chain
  • R 1 and R 2 are either both hydrogen (
  • Preferred alkyl ether carboxylic acids or carboxylate salts thereof have a C 8 -C 18 alkyl chain with between 2 to 20, more preferably between 3 to 12, even more preferably between 3 to 10 glycol repeat units, wherein the glycol repeat units are selected from ethylene glycol, propylene glycol or mixtures thereof.
  • the molecule of formula 1 may contain mixtures of polyethylene glycol (also known as ethylene oxide) and polypropylene glycol (also known as propylene oxide) repeat units.
  • a preferred salt is sodium.
  • suitable materials are oleyl alkyl ether (8EO) carboxylic acid, or laureth-5 carboxylic acid (5EO), and the sodium salts thereof.
  • the composition comprises a betaine surfactant at a level of from 0.1 to 10 wt.%, preferably from 0.2 to 10 wt.%, for example from 0.3 to 5 wt.%.
  • Preferred betaine surfactants are amidobetaines, alkyl betaines, sulfobetaines, sulfatobetaines, or mixtures thereof. Most preferred betaine surfactants are amidobetaines, alkyl betaines, or mixtures thereof.
  • Preferred alkyl betaines have a formula of: CH 3 (CH 2 ) 6-20 CH 2 N + (CH 3 ) 2 CH 2 COO - More preferred materials have a formula of: CH 3 (CH 2 ) 8-14 CH 2 N + (CH 3 ) 2 CH 2 COO -
  • Further alkyl betaines include (dodecyldimethylammonium) acetate (also known as lauryl betaine, (tetradecyldimethylammonium) acetate (also known as myristyl betaine, (cocodimethylammonium) acetate (also known as coconut betaine; (oleyldimethylammonium) acetate (also known as oleyl betaine;
  • alkyl betaine material is Empigen (Trade Mark) BB surfactant, available from Sigma Aldrich.
  • amidobetaines are C 8 to C 18 alkyl amidoalkyl betaines; for example (cocoamidopropyldimethylammonium) acetate (also known as cocoamidopropyl betaine or CAPB).
  • Example sulfatobetaines are: 3-(dodecyldimethylammonium)-1-propane sulfate; and 2-(cocodimethylammonium)-1-ethane sulfate.
  • Example sulfobetaines are:3-(dodecyldimethylammonium)-2-hydroxy-1 -propane sulfonate; 3-(tetradecyldimethylammonium)-1-propane sulfonate; 3-(C 12 -C 14 alkyl-amidopropyldimethylammonium)-2-hydroxy-1-propane sulfonate; and 3-(cocodimethylammonium)-1-propane sulfonate.
  • the liquid detergent composition comprises nonionic surfactant, and anionic surfactant.
  • the anionic surfactant comprises sodium and/or potassium alkyl C 9 to C 20 benzene sulfonate.
  • the nonionic surfactant component preferably comprises alcohol ethoxylate.
  • the alcohol ethoxylates are formed from the reaction of primary or secondary alcohols with ethylene oxide.
  • ethylene oxide is reacted with ethylene oxide in the required molar amount to produce the alcohol ethoxylate.
  • Preferred alcohol ethoxylates have from 2 to 40, preferably from 3 to 30, more preferably from 5 to 20 ethylene oxide units attached to the aliphatic chain.
  • the surfactants may be chosen from the surfactants described in " Surface Active Agents” Vol. 1, by Schwartz & Perry , Interscience 1949, Vol. 2 by Schwartz, Perry & Berch , Interscience 1958, in the current edition of "McCutcheon's Emulsifiers and Detergents” published by Manufacturing Confectioners Company or in " Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981 .
  • the surfactants used are saturated.
  • Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
  • Specific nonionic detergent compounds are C 6 to C 22 alkyl phenol-ethylene oxide condensates, generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule, and the condensation products of aliphatic C 8 to C 18 primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO.
  • Suitable anionic detergent compounds which may be used can be water-soluble alkali metal salts of organic sulphates and sulfonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.
  • suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher C 8 to C 18 alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl C 9 to C 20 benzene sulfonates, particularly sodium linear secondary alkyl C 10 to C 15 benzene sulfonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum.
  • the anionic surfactant may also include soaps of C 6 -C 22 fatty acids.
  • the preferred anionic detergent compounds are sodium C 11 to C 15 alkyl benzene sulfonates and sodium C 12 to C 18 alkyl sulphates. Salts of sulfonates included as hydrotrobes can additionally be considered as anionic surfactants as defined herein. Also applicable are surfactants such as those described in EP-A-328 177 (Unilever), which show resistance to salting-out, the alkyl polyglycoside surfactants described in EP-A-070 074 , and alkyl monoglycosides.
  • the nonionic detergent is present in amounts of from 1 to 40 wt.%, preferably from 5 to 35 wt.%, more preferably from 6 to 20 wt.%.
  • the anionic surfactant is present in amounts of from 4 to 40 wt.%, preferably from 5 to 35 wt.%, more preferably from 6 to 20 wt.%.
  • the alkyl ether carboxylate (or salt thereof) is itself considered an anionic surfactant, for the purposes of this invention, the amount of anionic surfactant present in the formulation does not include the amount of alkyl ether carboxylate (or salt thereof).
  • the total amount of surfactant present in the liquid composition is preferably at least 5 wt.%, more preferably at least 10 wt.%, More preferably the total amount of surfactant is from 15 to 65 wt.%, preferably from 10 to 50 wt.%.
  • surfactants such as cationic surfactants may also be present in addition to the aforementioned nonionic and anionic surfactants.
  • This term refers to polymers having an overall positive charge.
  • the cationic polymer is selected from the group consisting of: cationic polysaccharide polymers, and cationic non-saccharide polymers having cationic protonated amine or quaternary ammonium functionalities that are homo or copolymers derived from monomers containing an amino or quaternary nitrogen functional group polymerised from at least one of the following monomer classes: acrylate, methacrylate, acrylamide, methacrylamide; allyls (including diallyl and methallyl); ethylene imine; and/or vinyl monomer classes, and mixtures thereof.
  • the cationic polymer is selected from the group consisting of cationic cellulose polymers, cationic guar polymers, cationic diallyl quaternary ammonium-containing polymers and homo or copolymers of dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate or tert-butylaminoethyl (meth)acrylate in their quaternary or protonated amine form, and mixtures thereof.
  • the cationic polymer is a cationic polysaccharide polymer.
  • the cationic polysaccharide polymer is a cationic guar or cationic cellulose polymer.
  • the cationic polymer is a cationic cellulose polymer, for example, quaternised hydroxy ethyl cellulose.
  • the composition may include a single cationic polymer or a mixture of cationic polymers from the same or different classes, i.e. the composition may contain a cationic polysaccharide polymer and a cationic non-polysaccharide polymer.
  • cationic polysaccharide polymer refers to polymers having a polysaccharide backbone and an overall positive charge.
  • Polysaccharides are polymers made up from monosaccharide monomers joined together by glycosidic bonds.
  • the cationic polysaccharide-based polymers present in the compositions of the invention have a modified polysaccharide backbone, modified in that additional chemical groups have been reacted with some of the free hydroxyl groups of the polysaccharide backbone to give an overall positive charge to the modified cellulosic monomer unit.
  • a preferred class of cationic polysaccharide polymers suitable for this invention are those that have a polysaccharide backbone modified to incorporate a quaternary ammonium salt.
  • the quaternary ammonium salt is linked to the polysaccharide backbone by a hydroxyethyl or hydroxypropyl group.
  • the charged nitrogen of the quaternary ammonium salt has one or more alkyl group substituents.
  • Preferred cationic polysaccharide-based polymers have a guar based, or cellulosic based backbone. Cellulose based cationic polymers are most preferred. Guar is a galactomannan having a ⁇ -1,4 linked mannose backbone with branchpoints to ⁇ -1,6 linked galactose units.
  • Suitable cationic guar gum derivatives such as guar hydroxypropyltrimonium chloride, specific examples of which include the Jaguar series commercially available from Rhone-Poulenc Incorporated and the N-Hance series commercially available from Aqualon Division of Hercules, Inc.
  • guar 2-hydroxy-3-(trimethylammonium) propyl ether salt is guar 2-hydroxy-3-(trimethylammonium) propyl ether salt.
  • Cellulose is a polysaccharide with glucose as its monomer, specifically it is a straight chain polymer of D-glucopyranose units linked via ⁇ -1,4 glycosidic bonds and is a linear, non-branched polymer.
  • Example cationic cellulose polymers are salts of hydroxyethyl cellulose reacted with trimethyl ammonium substituted epoxide, referred to in the field under the International Nomenclature for Cosmetic Ingredients as Polyquatemium 10 and is commercially available from the Amerchol Corporation, a subsidiary of The Dow Chemical Company, marketed as the Polymer LR, JR, and KG series of polymers.
  • Other suitable types of cationic celluloses include the polymeric quaternary ammonium salts of hydroxyethyl cellulose reacted with lauryl dimethyl ammonium-substituted epoxide referred to in the field under the International Nomenclature for Cosmetic Ingredients as Polyquatemium 24. These materials are available from Amerchol Corporation marketed as Polymer LM-200.
  • Typical examples of preferred cationic cellulosic polymers include cocodimethylammonium hydroxypropyl oxyethyl cellulose, lauryldimethylammonium hydroxypropyl oxyethyl cellulose, stearyldimethylammonium hydroxypropyl oxyethyl cellulose, and stearyldimethylammonium hydroxyethyl cellulose; cellulose 2-hydroxyethyl 2-hydroxy 3-(trimethyl ammonio) propyl ether salt, polyquaternium-4, polyquaternium-10, polyquaternium-24 and polyquaternium-67 or mixtures thereof.
  • the cationic cellulosic polymer is a quaternised hydroxy ether cellulose cationic polymer. These are commonly known as polyquaternium-10. Suitable commercial cationic cellulosic polymer products for use according to the present invention are marketed by the Amerchol Corporation under the trade name UCARE.
  • Non-polysaccharide based cationic polymers may also be used.
  • Suitable cationic non-saccharide polymers include those having cationic protonated amine or quaternary ammonium functionalities that are homo or copolymers derived from monomers containing an amino or quaternary nitrogen functional group polymerised from at least one of the following monomer classes: acrylate, methacrylate, acrylamide, methacrylamide; allyls (including diallyl and methallyl); ethylene imine; and/or vinyl monomer classes, and mixtures thereof.
  • Preferred cationic non-saccharide polymers include cationic diallyl quaternary ammonium-containing polymers and homo or copolymers of dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate or tert-butylaminoethyl (meth)acrylate in their quaternary or protonated amine form, and mixtures thereof.
  • Suitable cationic polymers for use in the compositions include copolymers of 1-vinyl-2-pyrrolidone and 1-vinyl-3-methylimidazolium salt (known as Polyquatemium-16); copolymers of 1-vinyl-2-pyrrolidone and dimethylaminoethyl methacrylate (known as Polyquaternium-11); cationic diallyl quaternary ammonium-containing polymers, including, for example, dimethyldiallylammonium chloride homopolymer, copolymers of acrylamide and dimethyldiallylammonium chloride (known as Polyquatemium 6 and Polyquatemium 7 respectively); amphoteric copolymers of acrylic acid including copolymers of acrylic acid and dimethyldiallylammonium chloride (known as Polyquatemium 22), terpolymers of acrylic acid with dimethyldiallylammonium chloride and acrylamide (known as Polyquatemium 39), and terpolymers of acrylic acid with methacrylamidopropy
  • the counterion of the cationic polymer is freely chosen from the halides: chloride, bromide, and iodide; or from hydroxide, phosphate, sulphate, hydrosulphate, ethyl sulphate, methyl sulphate, formate, and acetate.
  • the species responsible for providing a softening benefit in these formulations is a polymer/surfactant complex, especially a cationic polymer/AEC complex.
  • the cationic polymer is present at a level of from 0.1 to 1.5 wt.%, preferably from 0.1 to 1 wt.%, more preferably from 0.2 to 1 wt.%.
  • the aforementioned cationic polymers can be synthesised in, and are commercially available in, a number of different molecular weights.
  • the molecular weight of the cationic polymer is from 10,000 to 2,000,000 Daltons, more preferably from 10,000 to 500,000 Daltons.
  • the detergent composition may optionally comprise one or more of the following optional ingredients, shading dye, enzyme, antiredeposition polymer, dye transfer inhibiting polymer, builder, sequestrant, sunscreen and/or soil release polymer.
  • the detergent compositions may also optionally contain relatively low levels of organic detergent builder or sequestrant material.
  • organic detergent builder or sequestrant material examples include the alkali metal, citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates.
  • Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, ethylene diamine tetra-acetic acid, diethylenetriaminepentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid, and citric acid.
  • DEQUESTTM organic phosphonate type sequestering agents sold by Monsanto and alkanehydroxy phosphonates.
  • suitable organic builders include the higher molecular weight polymers and copolymers known to have builder properties.
  • such materials include appropriate polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic acid copolymers and their salts, such as those sold by BASF under the name SOKALANTM.
  • SOKALANTM Another suitable builder is sodium carbonate.
  • the builder materials may comprise from about 0.5% to 20 wt%, preferably from 1 wt% to 10 wt%, of the composition.
  • the preferred builder level is less than 10 wt% and preferably less than 5 wt% of the composition.
  • the laundry detergent formulation is a non-phosphate built laundry detergent formulation, i.e., contains less than 1 wt.% of phosphate.
  • Shading dyes deposit to fabric during the wash or rinse step of the washing process providing a visible hue to the fabric. Shading of white garments may be done with any colour depending on consumer preference. Blue and Violet are particularly preferred shades and consequently preferred dyes or mixtures of dyes are ones that give a blue or violet shade on white fabrics. The shading dyes used are preferably blue or violet.
  • the shading dye chromophore is preferably selected from the group comprising: mono-azo, bis-azo, triphenylmethane, triphenodioxazine, phthalocyanin, naptholactam, azine and anthraquinone. Most preferably mono-azo, bis-azo, azine and anthraquinone.
  • the dye bears at least one sulfonate group.
  • Preferred shading dyes are selected from direct dyes, acid dyes, hydrophobic dyes, cationic dyes and reactive dyes.
  • the shading dye is present is present in the liquid composition in range from 0.0001 to 0.01 wt %.
  • the composition preferably comprises a fluorescent agent (optical brightener).
  • fluorescent agents are well known and many such fluorescent agents are available commercially. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts.
  • the total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2 wt.%, more preferably 0.01 to 0.1 wt.%.
  • Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g.
  • Preferred fluorescers are: sodium 2-(4-styryl-3-sulfophenyl)-2H-napthol[1,2-d]trazole, disodium 4,4'-bis ⁇ [(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1,3,5-triazin-2-yl)]amino ⁇ stilbene-2-2' disulfonate, disodium 4,4'-bis ⁇ [(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino ⁇ stilbene-2-2' disulfonate, and disodium 4,4'-bis(2-sulfoslyryl)biphenyl.
  • the composition comprises a perfume.
  • the perfume is preferably in the range from 0.001 to 3 wt.%, most preferably 0.1 to 1 wt.%.
  • CTFA Cosmetic, Toiletry and Fragrance Association
  • Many suitable examples of perfumes are provided in the CTFA (Cosmetic, Toiletry and Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co.
  • compositions of the present invention it is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components.
  • top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955 ]).
  • Preferred top-notes are selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.
  • the laundry treatment composition does not contain a peroxygen bleach, e.g., sodium percarbonate, sodium perborate, and peracid.
  • a peroxygen bleach e.g., sodium percarbonate, sodium perborate, and peracid.
  • the composition may comprise one or more polymers.
  • Polymers can assist in the cleaning process by helping to retail soil in solution or suspension and/or preventing the transfer of dyes. Polymers can also assist in the soil removal process. Dye transfer, anti-redeposition and soil-release polymers are described in further detail below.
  • the composition may comprise one or more polymers.
  • polymers are carboxymethylcellulose, hydroxyethyl cellulose, hydroxpropyl cellulose, poly(ethylene glycol), poly(vinyl alcohol), ethoxylated polyamines, polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
  • Modern detergent compositions typically employ polymers as so-called 'dye-transfer inhibitors'. These prevent migration of dyes, especially during long soak times.
  • dye-transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese pthalocyanine, peroxidases, and mixtures thereof, and are usually present at a level of from 0.01 to 10 wt.% based on total amount in the laundry composition.
  • Anti-redeposition polymers are designed to suspend or disperse soil.
  • antiredeposition polymers are ethoxylated and or propoxylated polyethylene imine or polycarboxylate materials, for example, Acrylic acid based homo or copolymers available under the trade mark ACUSOL from Dow Chemical, Alcosperse from Akzonobel or Sokolan from BASF.
  • suitable soil release polymers include graft copolymers of poly(vinyl ester), e.g., C 1 -C 6 vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones.
  • Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).
  • Further suitable soil release polymers of a different type include the commercially available material ZELCON 5126 (from DuPont) and MILEASE T (from ICI). If present, the soil release polymer may be included at a level of from from 0.01 to 10 wt.% based on total amount in the laundry composition.
  • Further examples of soil release polymers are terephthalic acid / glycol copolymers sold under the tradenames Texcare, Repel-o-tex, Gerol, Marloquest, Cirrasol.
  • the liquid detergent composition may optionally include a hydrotrope, which can prevent liquid crystal formation.
  • a hydrotrope which can prevent liquid crystal formation.
  • the addition of the hydrotrope thus aids the clarity/transparency of the composition.
  • Suitable hydrotropes include but are not limited to propylene glycol, ethanol, urea, salts of benzene sulfonate, toluene sulfonate, xylene sulfonate or cumene sulfonate.
  • Suitable salts include but are not limited to sodium, potassium, ammonium, monoethanolamine, triethanolamine. Salts of sulfonates can also be considered as anionic surfactants as defined herein.
  • the hydrotrope is selected from the group consisting of propylene glycol, xylene sulfonate, ethanol, and urea to provide optimum performance.
  • the amount of the hydrotrope is generally in the range of from 0 to 30%, preferably from 0.5 to 30%, more preferably from 0.5 to 30%, most preferably from 1 to 15%.
  • Enzymes can also be present in the formulation.
  • Preferred enzymes include protease, lipase, pectate lyase, amylase, cutinase, cellulase, mannanase. If present the enzymes may be stabilized with a known enzyme stabilizer for example boric acid.
  • Water and hydrotropes are mixed together at ambient temperature (approximately 22°C) for 2-3 minutes at a shear rate of 130 rpm using a Janke & Kunkel IKA RW20 overhead mixer. Salts and alkalis are added and mixed for 5 minutes prior to addition of surfactants and any alkyl ether carboxylic acid and/or fatty acid. The temperature of the mix rises to around 50-60°C at this point. After allowing to cool to ⁇ 30C, the LR400 solution, and any remaining components such as perfume, preservatives, opacifier and dyes are added. Formulations tested for softness are listed in table 1.
  • Formulation A is a comparative that includes betaine on its own without the alkyl ether carboxylate (AEC).
  • Formulation B is also comparative and includes AEC on its own without the betaine.
  • Formulation 1 is according to the invention and includes the combination of AEC and the betaine surfactant.
  • An internal control was also used in comparison. This internal control provides some fabric softening and was a liquid detergent comprising a nonionic surfactant, anionic surfactant, fatty acid and cationic polymer.
  • Formulations A, B and 1 were tested for fabric softening against the internal control and water to give 5 test products used as main wash products for identical bundles of fabrics.
  • the main wash was carried out using local water (6° French Hardness; 60mg of CaCO 3 per litre of water).
  • the protocol used involved washing 10 pieces (20cm x 20cm) of terry towelling along with polycotton ballast measured to a 2.5kg total load. This was added to a Miele front loading washing machine. 35ml of formulated detergent (or the internal control, or water) was added into a dosing ball then placed on top of the load in the drum of the washing machine.
  • the machine was programmed to a standard 40°C cotton cycle.
  • the towelling swatches were line dried in between cycles. This process was repeated 5 times. The towels were then given to the panel for assessment.
  • the laundered fabric was then assessed by a trained panel of 12 people.
  • the panellists were asked to score the garments for softness, in comparison to the internal control.
  • the internal control was given a score of 100.
  • the average softness scores are shown in table 2. A higher score indicates better softening. Water alone gave a poor value for softening.
  • Formulation A surfactant base + betaine gave a softening score that was lower than the internal control. This indicates that the presence of betaine in the surfactant base has a negative impact on softening in comparison to the internal control.
  • Formulation B the surfactant base + AEC gave a softening score that was higher than the internal control, indicating some softening benefit in comparison to the internal control. However, for formulation 1, the combination of AEC + betaine gave a softening score that was much higher than either one of formulations A or B.
  • formulations comprising a combination of alkyl ether carboxylic acid and betaine surfactant produced a synergistic softening benefit.
  • Table 4 Ingredient I %.wt II %.wt III %.wt IV %.wt V %.wt VI %wt LAS ACID 8 10 15 5 10 14 SLES 4 5 - 3 2 - NEODOL 25-7E 10 10 10 18 12 14 Empigen BB (betaine) 2.5 0.25 1 - 5 1 CAPB (betaine) - - - 2 - - MARLOWET 4560 (Alkyl Ether Carboxylate) 3 6 3 5 5 5 4 PRIFAC 5908 3 - 3 1 1 2 PROPYLENE GLYCOL 9 9 9 9 9 9 9 9 GLYCEROL - 5 - 4 5 5 TRIETHANOLAMINE 3 3 6 6 6 4 TINOPAL CBS-X 0.1 - 0.1 0.1 0.1 0.1 0.1 0.1 LR400 (Cationic polymer) 1 0.45 - 0.5 - - Jaguar C500 (Cationic polymer) - - - - - - 0.5

Claims (14)

  1. Waschmittelzusammensetzung, umfassend:
    (a) 1 bis 40 Gew.-% nichtionisches Tensid, umfassend ein Alkoholethoxylat,
    (b) 4 bis 40 Gew.-% anionisches Tensid, umfassend Natrium- und/oder Kalium-alkyl-C9- bis C20-benzolsulfonat,
    (c) 1 bis 12 Gew.-% Alkylethercarbonsäure oder Carboxylatsalz davon,
    (d) 0,1 bis 10 Gew.-% Betain-Tensid und
    (e) 0,1 bis 1,5 Gew.-% kationisches Polymer.
  2. Zusammensetzung nach Anspruch 1, wobei das Betain-Tensid Amidobetaine, Alkylbetaine oder Mischungen davon umfasst.
  3. Zusammensetzung nach irgendeinem vorhergehenden Anspruch, wobei die Alkylethercarbonsäure oder das Carboxylatsalz davon in einer Konzentration von 1 bis 10 Gew.-%, vorzugsweise in einer Konzentration von 2 bis 7,5 Gew.-%, vorliegen.
  4. Zusammensetzung nach irgendeinem vorhergehenden Anspruch, wobei die Alkylethercarbonsäure oder das Carboxylatsalz davon durch
    Figure imgb0004
     dargestellt ist, worin
    R eine gesättigte oder ungesättigte C6-C22-Alkylkette bedeutet,
    R1 und R2 entweder beide Wasserstoff sind oder R1 Wasserstoff ist und R2 CH3 ist oder R1 CH3 ist und R2 Wasserstoff ist,
    R3 Wasserstoff oder ein löslichmachendes Kation, wie Natrium, Kalium, Ammonium oder substituiertes Ammonium, ist und
    n eine Zahl von 2 bis 20, vorzugsweise 3 bis 12, ist, was die Anzahl der Wiederholungseinheiten bedeutet.
  5. Zusammensetzung nach irgendeinem vorhergehenden Anspruch, wobei die Alkylethercarbonsäure oder das Carboxylatsalz eine C8-C18-Alkylkette mit 2 bis 12 Glycol-Wiederholungseinheiten aufweist, worin die Glycol-Wiederholungseinheiten unter Ethylenglycol, Propylenglycol oder Mischungen davon ausgewählt sind.
  6. Zusammensetzung nach irgendeinem vorhergehenden Anspruch, wobei das kationische Polymer in einer Konzentration von 0,1 bis 1 Gew.-% vorliegt.
  7. Zusammensetzung nach irgendeinem vorhergehenden Anspruch, wobei das kationische Polymer aus der Gruppe ausgewählt ist, bestehend aus kationischen Polysaccharidpolymeren und kationischen Nicht-Saccharidpolymeren mit kationisch protonierten Amin- oder quaternären Ammonium-Funktionalitäten, die Homo- oder Copolymere darstellen, die von Monomeren abgeleitet sind, die eine Amino- oder quaternäre Stickstoff-funktionelle Gruppe enthalten, polymerisiert anhand mindestens einer der folgenden Monomerklassen: Acrylat, Methacrylat, Acrylamid, Methacrylamid, Allylverbindungen (einschließlich Diallyl und Methallyl), Ethylenimin und/oder Vinylmonomer-Klassen und Mischungen davon.
  8. Zusammensetzung nach irgendeinem der Ansprüche 1 bis 6, wobei das kationische Polymer aus der Gruppe ausgewählt ist, bestehend aus kationischen Cellulosepolymeren, kationischen Guarpolymeren, kationischen Diallylpolymeren mit einem Gehalt an quaternärem Ammonium und Homo- oder Copolymeren von Dimethylaminoethyl(meth)acrylat, Diethylaminoethyl(meth)acrylat oder tert-Butylaminoethyl(meth)acrylat in ihrer quaternären oder protonierten Aminform und Mischungen davon.
  9. Zusammensetzung nach irgendeinem der Ansprüche 1 bis 6, wobei das kationische Polymer ein kationisches Polysaccharidpolymer darstellt.
  10. Zusammensetzung nach Anspruch 9, wobei das kationische Polysaccharidpolymer ein kationisches Cellulosepolymer, vorzugsweise eine quaternisierte Hydroxyethylcellulose, darstellt.
  11. Zusammensetzung nach irgendeinem vorhergehenden Anspruch in Form eines flüssigen Waschmittels.
  12. Zusammensetzung nach irgendeinem vorhergehenden Anspruch mit einem pH von 6,2 bis 9, vorzugsweise einem pH von 6,5 bis 8,5, höchst bevorzugt einem pH von 6,5 bis 8.
  13. Zusammensetzung nach irgendeinem vorhergehenden Anspruch, wobei die Zusammensetzung des Weiteren einen Bestandteil enthält, der unter einem Nuancierfarbstoff, einem Enzym, einem Antiwiederablagerungspolymer, einem den Farbstoffübertrag inhibierenden Polymer, Builder, Komplexbildner, Sonnenschutz und/oder Soil-Release-Polymer ausgewählt ist.
  14. Verwendung einer Zusammensetzung, umfassend ein Alkylethercarboxylat, ein kationisches Polymer und ein Betain, um Textilien weich zu machen.
EP12780495.3A 2011-12-12 2012-10-31 Waschmittelzusammensetzungen Active EP2791310B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP12780495.3A EP2791310B1 (de) 2011-12-12 2012-10-31 Waschmittelzusammensetzungen

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP11192983 2011-12-12
EP12780495.3A EP2791310B1 (de) 2011-12-12 2012-10-31 Waschmittelzusammensetzungen
PCT/EP2012/071588 WO2013087286A1 (en) 2011-12-12 2012-10-31 Laundry compositions

Publications (2)

Publication Number Publication Date
EP2791310A1 EP2791310A1 (de) 2014-10-22
EP2791310B1 true EP2791310B1 (de) 2017-01-18

Family

ID=47115969

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12780495.3A Active EP2791310B1 (de) 2011-12-12 2012-10-31 Waschmittelzusammensetzungen

Country Status (7)

Country Link
EP (1) EP2791310B1 (de)
CN (1) CN103975050B (de)
AR (1) AR089149A1 (de)
BR (1) BR112014014072B1 (de)
ES (1) ES2622374T3 (de)
WO (1) WO2013087286A1 (de)
ZA (1) ZA201403694B (de)

Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014154234A1 (en) 2013-03-25 2014-10-02 Rhodia Operations Fabric softener
CN107592883B (zh) * 2015-05-08 2020-03-10 荷兰联合利华有限公司 洗衣洗涤剂组合物
EP3303535B1 (de) * 2015-05-27 2018-10-03 Unilever PLC Waschmittelzusammensetzung
CN107835851B (zh) 2015-06-02 2020-03-20 荷兰联合利华有限公司 洗衣洗涤剂组合物
EP3307862B1 (de) * 2015-06-11 2019-04-03 Unilever PLC Waschmittelzusammensetzung
TR201906232T4 (tr) * 2015-06-11 2019-05-21 Unilever Nv Çamaşır için deterjan bileşimi.
BR112018006212B1 (pt) 2015-10-01 2022-04-12 Unilever Ip Holdings B.V. Composição de detergente em pó formada por carbonato sem fosfato e método de tratamento doméstico de um tecido
CN108138084B (zh) * 2015-10-01 2021-04-27 荷兰联合利华有限公司 液体洗衣洗涤剂组合物
WO2017142012A1 (ja) * 2016-02-16 2017-08-24 ライオン株式会社 洗浄剤組成物
WO2017162378A1 (en) 2016-03-21 2017-09-28 Unilever Plc Laundry detergent composition
JP7066629B2 (ja) 2016-04-06 2022-05-13 ザ プロクター アンド ギャンブル カンパニー 自己構造化界面活性剤系を含有する安定な液体洗剤組成物
WO2017173589A1 (en) 2016-04-06 2017-10-12 The Procter & Gamble Company A stable liquid detergent composition containing a self-structuring surfactant system
WO2017173590A1 (en) * 2016-04-06 2017-10-12 The Procter & Gamble Company A stable liquid detergent composition containing a self-structuring surfactant system
CN108779416B (zh) * 2016-04-08 2021-01-05 荷兰联合利华有限公司 洗衣洗涤剂组合物
CN109790491B (zh) 2016-09-27 2021-02-23 荷兰联合利华有限公司 家用洗衣方法
BR112019011999B1 (pt) 2016-12-15 2022-11-08 Unilever Ip Holdings B.V Composição de detergente líquida aquosa para lavagem de roupas e método doméstico de tratamento de um tecido
EP3401384A1 (de) 2017-05-10 2018-11-14 Unilever PLC Flüssige waschmittelzusammensetzung
JP2020084023A (ja) * 2018-11-26 2020-06-04 花王株式会社 衣料用液体洗剤製品
DE102020200041A1 (de) * 2020-01-06 2021-07-08 Henkel Ag & Co. Kgaa Farbübertragungsinhibierung beim Waschen
US11447722B2 (en) * 2020-01-30 2022-09-20 Henkel Ag & Co. Kgaa Detergent composition for textile softening and anti-redeposition
EP4196562A1 (de) * 2020-08-12 2023-06-21 Unilever IP Holdings B.V. Verfahren zur herstellung einer flüssigen waschmittelzusammensetzung
WO2022033986A1 (en) * 2020-08-12 2022-02-17 Unilever Ip Holdings B.V. Laundry detergent composition
EP4196560A1 (de) * 2020-08-12 2023-06-21 Unilever IP Holdings B.V. Waschmittelzusammensetzung
EP4196565B1 (de) * 2020-08-12 2024-04-17 Unilever IP Holdings B.V. Waschmittel
IT202200006389A1 (it) * 2022-03-31 2023-10-01 Lamberti Spa Composizioni per la cura dei capelli e della pelle
WO2024050339A1 (en) 2022-09-02 2024-03-07 Danisco Us Inc. Mannanase variants and methods of use
WO2024050346A1 (en) 2022-09-02 2024-03-07 Danisco Us Inc. Detergent compositions and methods related thereto
WO2024050343A1 (en) 2022-09-02 2024-03-07 Danisco Us Inc. Subtilisin variants and methods related thereto

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GR76189B (de) 1981-07-13 1984-08-03 Procter & Gamble
GB8803036D0 (en) 1988-02-10 1988-03-09 Unilever Plc Liquid detergents
DE4409189C2 (de) * 1994-03-17 1996-08-14 Chem Y Tensid-Zusammensetzung, insbesondere zur Verwendung in Körperreinigungsmitteln
GB9613941D0 (en) * 1996-07-03 1996-09-04 Procter & Gamble Cleansing compositions
DE19721589A1 (de) * 1997-05-23 1998-11-26 Henkel Kgaa Textilweichmacherkonzentratre
US20020173435A1 (en) * 2000-08-18 2002-11-21 Librizzi Joseph J. Viscous, mild, and effective cleansing compositions
ES2324417T3 (es) * 2005-06-20 2009-08-06 Kao Chemicals Gmbh Agente potenciador de espuma.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
EP2791310A1 (de) 2014-10-22
ZA201403694B (en) 2015-12-23
BR112014014072A2 (pt) 2017-06-13
CN103975050B (zh) 2017-02-22
AR089149A1 (es) 2014-07-30
WO2013087286A1 (en) 2013-06-20
BR112014014072B1 (pt) 2022-05-10
ES2622374T3 (es) 2017-07-06
CN103975050A (zh) 2014-08-06

Similar Documents

Publication Publication Date Title
EP2791310B1 (de) Waschmittelzusammensetzungen
EP2791308B1 (de) Waschmittelzusammensetzungen
EP3074495B1 (de) Waschmittel
EP2922936B1 (de) Waschmittelzusammensetzungen
EP2909295B1 (de) Waschmittel
EP3074496B1 (de) Waschmittel
EP3074497B1 (de) Waschmittel
EP2366008B1 (de) Waschmittelzusammensetzungen
WO2013087285A1 (en) Laundry compositions and uses
EP2922938B1 (de) Waschmittelzusammensetzungen
CN107075422B (zh) 洗衣组合物成分
EP2922937B1 (de) Bestandteil zur verwendung in einer waschmittelzusammensetzung
BR112016011675B1 (pt) Composição detergente líquida de lavagem e uso da composição

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20140603

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RIC1 Information provided on ipc code assigned before grant

Ipc: C11D 1/90 20060101ALI20160809BHEP

Ipc: C11D 1/06 20060101ALI20160809BHEP

Ipc: C11D 3/22 20060101ALI20160809BHEP

Ipc: C11D 3/37 20060101ALI20160809BHEP

Ipc: C11D 1/22 20060101ALI20160809BHEP

Ipc: C11D 1/72 20060101ALI20160809BHEP

Ipc: C11D 1/94 20060101AFI20160809BHEP

INTG Intention to grant announced

Effective date: 20160902

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 862930

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170215

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602012028032

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20170118

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 862930

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170118

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170118

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2622374

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20170706

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170419

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170118

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170418

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170518

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170118

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170118

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170118

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170118

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170118

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170118

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170118

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170518

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170418

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602012028032

Country of ref document: DE

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170118

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170118

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170118

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170118

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170118

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170118

26N No opposition filed

Effective date: 20171019

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170118

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170118

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171031

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171031

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171031

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20171031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171031

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171031

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171031

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20181221

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20121031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170118

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170118

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170118

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 602012028032

Country of ref document: DE

Owner name: UNILEVER GLOBAL IP LIMITED, WIRRAL, GB

Free format text: FORMER OWNER: UNILEVER N.V., ROTTERDAM, NL

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20220127 AND 20220202

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230428

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20231020

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20231030

Year of fee payment: 12

Ref country code: FR

Payment date: 20231025

Year of fee payment: 12

Ref country code: DE

Payment date: 20231020

Year of fee payment: 12