EP4263770A1 - Laundry detergent composition containing dye fixative and stabilizing agent - Google Patents

Laundry detergent composition containing dye fixative and stabilizing agent

Info

Publication number
EP4263770A1
EP4263770A1 EP20966231.1A EP20966231A EP4263770A1 EP 4263770 A1 EP4263770 A1 EP 4263770A1 EP 20966231 A EP20966231 A EP 20966231A EP 4263770 A1 EP4263770 A1 EP 4263770A1
Authority
EP
European Patent Office
Prior art keywords
composition
weight
laundry detergent
surfactant system
detergent composition
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.)
Pending
Application number
EP20966231.1A
Other languages
German (de)
French (fr)
Inventor
Ming Tang
Dongpeng WANG
Jiahe KANG
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.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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 Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP4263770A1 publication Critical patent/EP4263770A1/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0021Dye-stain or dye-transfer inhibiting compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/044Hydroxides or bases
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/046Salts
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2003Alcohols; Phenols
    • C11D3/2006Monohydric alcohols
    • C11D3/201Monohydric alcohols linear
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2079Monocarboxylic acids-salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2086Hydroxy carboxylic acids-salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2093Esters; Carbonates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/33Amino carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/34Organic compounds containing sulfur
    • C11D3/3418Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719Polyamides or polyimides
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723Polyamines or polyalkyleneimines
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38618Protease or amylase in liquid compositions only
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40Dyes ; Pigments
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40Dyes ; Pigments
    • C11D3/42Brightening agents ; Blueing agents
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29Sulfates of polyoxyalkylene ethers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/662Carbohydrates or derivatives
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/75Amino oxides

Definitions

  • the present invention relates to a laundry detergent composition containing a dye fixative and a stabilizing agent.
  • Colored textiles may fade over several wash cycles due to the release of the dyes from the textiles, especially in the case of dark-colored textiles made of cotton and mixed cotton fabrics.
  • color bleeding might occur, i.e., a differently colored or white textile might be stained with the dye released from dyed textiles as a result relatively high dye concentration in the wash liquor if they were washed at the same time.
  • Color fading or color bleeding would result in a rapid deterioration of the appearance of colored textiles.
  • laundry detergent compositions that are capable of preventing color fading and/or color bleeding.
  • dye fixatives are employed in detergent compositions.
  • Such dye fixatives are usually cationic polymers which could bind negative-charged dyes on the textiles or in the washing liquor so as to prevent the detachment of dyes from colored textiles or redeposition of dyes onto white textiles or textiles with a different dye.
  • the introduction of such dye fixatives into a liquid detergent composition might compromise the stability of the liquid detergent composition, i.e., the dye fixatives have a tendency to separate from the aqueous phase and/or flocculation.
  • the present invention in one aspect relates to a laundry detergent composition, comprising:
  • reaction products of polyamines with cyanamides and acids such as organic and/or inorganic acids
  • the composition is a liquid composition comprising:
  • HCO hydrogenated castor oil
  • MCC microcrystalline cellulose
  • a nonionic surfactant system comprising C10-C16 ethoxylated alcohol having a weight average degree of ethoxylation ranging from 5to 15, preferably 6 to 12, and more preferably 7 to 10;
  • an anionic surfactant system comprising C10-C16 LAS and C10-C16 alkyl ethoxy sulfates in which preferably, the C10-C16 LAS is present in an amount ranging from 10%to 90%, by weight of the anionic surfactant system;
  • weight ratio of the nonionic surfactant system to the anionic surfactant system is between 1.5 and 8.
  • composition is an unit dose composition comprising:
  • said dye fixative is selected from the group consisting of reaction products of dimethylamine with epichlorohydrin;
  • anionic surfactant system comprising C 10 -C 16 LAS and C 10 -C 16 alkyl ethoxy sulfates in which said C 10 -C 16 LAS is present in an amount ranging from 40%to 90%, by weight of the anionic surfactant system;
  • weight ratio of the nonionic surfactant system to the anionic surfactant system is between 1.5 and 8.
  • the present invention relates to a method of protecting color in a colored fabric comprising contacting the colored fabric with the laundry detergent composition as mentioned hereinabove.
  • the protection of the color is achieved by fixing dyes in the colored fabric and/or preventing color fading or color bleeding from the colored fabric.
  • the present invention relates to a method of preventing color fading or color bleeding of a colored fabric comprising contacting the colored fabric with the laundry detergent composition as mentioned hereinabove.
  • the present invention relates to a method of fixing dyes in a colored fabric comprising contacting the colored fabric with the laundry detergent composition as mentioned hereinabove.
  • the terms “comprise” , “comprises” , “comprising” , “include” , “includes” , “including” , “contain” , “contains” , and “containing” are meant to be non-limiting, i.e., other steps and other ingredients which do not affect the end of result can be added.
  • the above terms encompass the terms “consisting of” and “consisting essentially of” .
  • composition is “substantially free” of a specific ingredient, it is meant that the composition comprises less than a trace amount, alternatively less than 0.1%, alternatively less than 0.01%, alternatively less than 0.001%, by weight of the composition, of the specific ingredient.
  • laundry detergent composition means a composition for cleaning soiled materials, including fabrics. Such compositions may be used as a pre-laundering treatment, a post-laundering treatment, or may be added during the rinse or wash cycle of the laundering operation.
  • the laundry detergent composition compositions may have a form selected from liquid, powder, unit dose such as single-compartment or multi-compartment unit dose, pouch, tablet, gel, paste, bar, or flake.
  • the laundry detergent composition is a liquid or a unit dose composition.
  • liquid laundry detergent composition herein refers to compositions that are in a form selected from the group consisting of pourable liquid, gel, cream, and combinations thereof.
  • the liquid laundry detergent composition may be either aqueous or non-aqueous, and may be anisotropic, isotropic, or combinations thereof.
  • unit dose laundry detergent composition herein refers to a water-soluble pouch containing a certain volume of liquid wrapped with a water-soluble film.
  • main surfactant refers to a surfactant that is present in a composition at an amount that is greater than any other surfactant contained by such composition.
  • main anionic surfactant refers to an anionic surfactant that is present in a composition at an amount that is greater than any other anionic surfactant contained by such composition
  • major surfactant refers to a surfactant that is present in a composition at an amount that is at least 50%by weight of the total surfactant content in such composition.
  • major anionic surfactant refers to an anionic surfactant that is present in a composition at an amount that is at least 50%by weight of the total anionic surfactant content in such composition.
  • alkyl means a hydrocarbyl moiety which is branched or unbranched, substituted or unsubstituted. Included in the term “alkyl” is the alkyl portion of acyl groups.
  • washing solution refers to the typical amount of aqueous solution used for one cycle of laundry washing, preferably from 1 L to 50 L, alternatively from 1 L to 20 L for hand washing and from 20 L to 50 L for machine washing.
  • oiled fabric is used non-specifically and may refer to any type of natural or artificial fibers, including natural, artificial, and synthetic fibers, such as, but not limited to, cotton, linen, wool, polyester, nylon, silk, acrylic, and the like, as well as various blends and combinations.
  • the dye fixatives of the present invention are cationic polymers. Without being bound by any theory, it is believed that such dye fixatives with positive charges can bind dyes with negative charges through charge interactions and then prevent the dyes out of the textiles or prevent the redeposition of the dyes onto a different colored textiles.
  • the dye fixatives may be selected from the group consisting of reaction products of: i) polyamines with cyanamides and organic and/or inorganic acids, ii) cyanamides with aldehydes and ammonium salts, iii) cyanamides with aldehydes and amines, or iv) amines with epichlorohydrin.
  • the dye fixative may be selected from the group consisting of reaction products of amines with epichlorohydrin in which the amines are primary, secondary or tertiary amines. More preferably, the dye fixative may be selected from the group consisting of reaction products of dimethylamine with epichlorohydrin. Most preferably, the dye fixative may be poly (2-hydroxypropyldimethylammonium chloride) , also called poly (dimethylamine-co-epichlorohydrin) , for example the polymer commercially available under the trade name of TEXCARE DFC 6 from Clariant (CAS#: 25988-97-0) .
  • amines comprises monoamines and polyamines.
  • the monoamines used herein may be primary, secondary and tertiary amines. They may be aliphatic amines, for example dialkylamines, especially dimethylamine, alicyclic amines, for example cyclohexylamine, and aromatic amines, for example aniline.
  • the amines used herein may also simultaneously have aliphatic, alicyclic and aromatic substituents.
  • heterocyclic compounds for example pyridine.
  • polyamines herein includes, for example diamines, triamines, tetraamines, etc, and also the analogous N-alkylpolyamines and N, N-dialkylpolyamines. Examples thereof are ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, diethylenetriamine, triethylenetetraamine and higher polyamines. Particularly preferred polyamines may be ethylenediamine, diethylenetriamine and dimethylaminopropylamine.
  • the ammonium salts are salts of ammonia, especially ammonium chloride or the abovementioned amines or polyamines with different inorganic or organic acids, or else quaternary ammonium salts.
  • the cyanamides may be cyanamide or dicyandiamide.
  • Aldehydes used herein may include, for example, aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde; dialdehydes, for example glyoxal; unsaturated aldehydes, for example acrolein, crotonaldehyde and aromatic aldehydes, for example benzaldehyde.
  • Particularly preferred aldehydes may be aliphatic aldehydes such as formaldehyde.
  • the dye fixatives used herein may also be homo-and copolymers based on diallyldimethylammonium chloride (DADMAC) .
  • DADMAC diallyldimethylammonium chloride
  • Copolymers based on DADMAC contain, as further components, other vinylic monomers, for example vinylimidazole, vinylpyrrolidone, vinyl alcohol, vinyl acetate, (meth) acrylic acid/ester, acrylamide, styrene, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid (AMPS) , etc.
  • Homopolymers based on DADMAC are obtainable under the trade names 3954, Dodigen 4033 and Genamin PDAC (from Clariant) .
  • the dye fixative suitable for use in the present disclosure can be selected from the group consisting of reaction products of amines with epichlorohydrin in which the amines are primary, secondary or tertiary amines. More preferably, the dye fixative suitable for use in the present invention can be selected from the group consisting of reaction products of dimethylamine with epichlorohydrin. Most preferably, the dye fixative may be poly (2-hydroxypropyldimethylammonium chloride) .
  • the dye fixative is poly (2-hydroxypropyldimethylammonium chloride) of formula (I) :
  • n is an integer from 5 to 1000.
  • the dye fixative in the composition according to the present disclosure may be present in an amount ranging from 0.02%to 5%, preferably from 0.05%to 2%, more preferably from 0.1%to 1.5%, most preferably from 0.15%to 0.9%, for example 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%or any ranges therebetween, by weight of the composition.;
  • the stabilizing agent suitable for use in the present invention may be a crystalline, hydroxyl-containing stabilizing agent.
  • the stabilizing agent may be selected from the group consisting of microcrystalline cellulose (MCC) or derivatives thereof, castor oil or derivatives thereof, hydrogenated castor oil (HCO) or derivatives thereof, and any combinations thereof. More preferably, the stabilizing agent may be microcrystalline cellulose or derivatives thereof and/or hydrogenated castor oil or derivatives thereof.
  • MCC is a naturally occurring polymer. It is composed of glucose units connected by a 1-4 beta glycosidic bond. These linear cellulose chains are bundled together as microfibril spiralled together in plant cell walls. It has been used in food applications and pharmaceutical tablets.
  • Castor oils may include glycerides, especially triglycerides, comprising C 10 to C 22 alkyl or alkenyl moieties which incorporate a hydroxyl group. Hydrogenation of castor oil to make HCO converts double bonds, which may be present in the starting oil as ricinoleyl moieties, to convert ricinoleyl moieties to saturated hydroxyalkyl moieties, e.g., hydroxystearyl.
  • the HCO herein may, in some embodiments, be selected from: trihydroxystearin; dihydroxystearin; and mixtures thereof.
  • the HCO may be processed in any suitable starting form, including, but not limited those selected from solid, molten and mixtures thereof.
  • the stabilizing agent is incorporated into the liquid detergent composition through the use of external structuring system (s) (ESS) comprising the stabilizing agent.
  • ESS external structuring system
  • the ESS suitable for use in the present invention may comprise: (a) the stabilizing agent; (b) alkanolamine e.g. monoethanolamine (MEA) ; (c) anionic surfactant such as: linear alkyl benzene sulphonate (LAS) ; and (d) additional components.
  • HCO is typically present in the ESS of the present invention at a level of from about 2%to about 10%, from about 3%to about 8%, or from about 4%to about 6%by weight of the structuring system.
  • the corresponding percentage of hydrogenated castor oil delivered into a finished laundry detergent product is below about 1.0%, typically from 0.1%to 0.8%.
  • Useful HCO may have the following characteristics: a melting point of from about 40 °C to about 100 °C, or from about 65 °C to about 95 °C; and/or Iodine value ranges of from 0 to about 5, from 0 to about 4, or from 0 to about 2.6.
  • the melting point of HCO can be measured using either ASTM D3418 or ISO 11357; both tests utilize DSC: Differential Scanning Calorimetry.
  • HCO of use in the present invention includes those that are commercially available.
  • Non-limiting examples of commercially available HCO of use in the present invention include: from Rheox, Inc.
  • the source of the castor oil for hydrogenation to form HCO can be of any suitable origin, such as from Brazil or India.
  • castor oil is hydrogenated using a precious metal, e.g., palladium catalyst, and the hydrogenation temperature and pressure are controlled to optimize hydrogenation of the double bonds of the native castor oil while avoiding unacceptable levels of dehydroxylation.
  • the stabilizing agent in the composition according to the present disclosure may be present in an amount ranging from 0.01%to 9%, preferably from 0.02%to 8%, more preferably from 0.03%to 5%, yet more preferably from 0.05%to 3%, most preferably from 0.06%to 2%, for example, 0.1%, 0.2%, 0.3%, 0.5%, 0.7%, 1%, 2%or any ranges therebetween, by weight of the composition.
  • the amine oxide suitable for use in the present invention may be selected from the group consisting of C 6 -C 20 alkyldimethyl amine oxides (AO) and combinations thereof.
  • the amine oxide is characterized by the following structure:
  • R 1 is a C 6-20 alkyl, a C 6-20 hydroxyalkyl, or a C 6-20 alkyl phenyl group
  • each R 2 is a C 2-5 alkylene, or a C 2-5 hydroxyalkylene group
  • x is from 0 to about 3
  • each R 3 is a C 1-3 alkyl, a C 1-3 hydroxyalkyl, or a polyethylene oxide containing from about 1 to about 3 ethoxylene (EO) units.
  • the amine oxide may be a C 8-18 alkyldimethyl amine oxide, preferably a C 10-16 alkyldimethyl amine oxide.
  • the amine oxide is selected from the group consisting of dodecyldimethyl amine oxide, tetradecyldimethyl amino oxide, and a combination thereof. More preferably, the amine oxide contains dodecyldimethyl amino oxide having the following formula (III) :
  • Such a compound is also referred to as lauryldimethyl amine oxide or dodecydimethyl amine-N-oxide (DDAO) . It is commercially available from Huntsman under the tradename LO.
  • the amine oxide in the composition according to the present disclosure may be present in an amount ranging from 0.01%to 10%, preferably from 0.02%to 8%, more preferably from 0.1%to 3%, most preferably from 0.15%to 2%, for example 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%or any ranges therebetween, by weight of the composition.
  • the laundry detergent composition of the present invention may comprise an anionic surfactant system.
  • the laundry detergent composition of the present invention may comprise from 0.1%to 50%by weight of the composition, of an anionic surfactant system.
  • the anionic surfactant system may comprise an anionic surfactant selected from the group consisting of C 6 -C 20 linear alkylbenzene sulfonates (LAS) , C 6 -C 20 alkyl sulfates (AS) , C 6 -C 20 alkyl alkoxy sulfates (AAS) , C 6 -C 20 methyl ester sulfonates (MES) , C 6 -C 20 alkyl ether carboxylates (AEC) , and any combinations thereof.
  • an anionic surfactant selected from the group consisting of C 6 -C 20 linear alkylbenzene sulfonates (LAS) , C 6 -C 20 alkyl sulfates (AS) , C 6 -C 20 alkyl alkoxy sulfates (AAS) , C 6 -C 20 methyl ester sulfonates (MES) , C 6 -C 20 alkyl ether carboxylates (A
  • the anionic surfactant system may comprise a C 6 -C 20 LAS and optionally an additional anionic surfactant such as a C 6 -C 20 AS and/or a C 6 -C 20 AAS.
  • LAS is C 10 -C 16 LAS, preferably C 12 -C 14 LAS.
  • the LAS is normally prepared by sulfonation (using SO 2 or SO 3 ) of alkylbenzenes followed by neutralization.
  • Suitable alkylbenzene feedstocks can be made from olefins, paraffins or mixtures thereof using any suitable alkylation scheme, including sulfuric and HF-based processes.
  • the precise alkylation catalyst it is possible to widely vary the position of covalent attachment of benzene to an aliphatic hydrocarbon chain. Accordingly, the LAS herein can vary widely in 2-phenyl isomer and/or internal isomer content.
  • C 6 -C 20 LAS may be present in an amount ranging from 1%to 100%, preferably from 10%to 99%, more preferably from 20%to 95%, most preferably from 30%to 90%, for example 40%, 50%, 60%, 70%, 80%, 90%or any ranges therebetween, by weight of the anionic surfactant.
  • the level of LAS is preferably higher than that of any other anionic surfactant contained by such composition, i.e., the LAS is the main anionic surfactant in such composition.
  • the anionic surfactant suitable for use in the present disclosure may further comprise C 6 -C 20 alkyl sulfates (AS) , C 6 -C 20 alkyl alkoxy sulfates (AAS) , C 6 -C 20 methyl ester sulfonates (MES) , C 6 -C 20 alkyl ether carboxylates (AEC) , or any combinations thereof.
  • the laundry detergent composition may contain a C 6 -C 20 alkyl alkoxy sulfates (AA x S) , wherein x is about 1-30, preferably about 1-15, more preferably about 1-10, most preferably x is about 1-3.
  • the alkyl chain in such AA x S can be either linear or branched, with mid-chain branched AA x S surfactants being particularly preferred.
  • a preferred group of AA x S include C 12 -C 14 alkyl alkoxy sulfates with x of about 1-3.
  • the amount of AA x S surfactant (s) in the laundry detergent composition of the present invention may range from about 0.05%to about 100%, preferably from about 0.1%to about 80%, more preferably from about 0.5%to about 50%, most preferably from about 1%to about 30%, for example 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%or any ranges therebetween, by weight of the composition.
  • the weight ratio of LAS to AA x S is at least 0.6, preferably at least 0.8, more preferably at least 0.9, most preferably at least 1, for example 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.5, 2, 2.5, 3, 4, 5, 8, 10 or any ranges therebetween.
  • the anionic surfactant system in the composition according to the present disclosure may be present in an amount ranging from 0.1%to 45%, preferably from 0.5%to 40%, more preferably from 1%to 35%, most preferably from 2%to 30%, for example 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%or any ranges therebetween, by weight of the composition.
  • the anionic surfactant in the composition according to the present disclosure may comprise less than 30%, preferably less than 20%, more preferably less than 10%, most preferably less than 5%, of soap by weight of the anionic surfactant.
  • the laundry detergent composition of the present invention may comprise a nonionic surfactant system.
  • the nonionic surfactant system may comprise a nonionic surfactant selected from the group consisting of alkyl alkoxylated alcohols, alkyl alkoxylated phenols, alkyl polysaccharides, polyhydroxy fatty acid amides, alkoxylated fatty acid esters, alkyl polyglycosides (APG) , methyl ester ethoxylates (MEE) , sucrose esters, sorbitan esters and alkoxylated derivatives of sorbitan esters, and any combinations thereof.
  • the nonionic surfactant system may comprise a C 6 -C 20 alkoxylated alcohol having a weight average degree of alkoxylation ranging from 1 to 20, preferably from 5 to 15, more preferably from 7 to 10. More preferably, the nonionic surfactant system may comprise a C 8 -C 18 ethoxylated alcohol having a weight average degree of ethoxylation ranging from 1 to 20, preferably from 5 to 15, more preferably from 7 to 10.
  • Non-limiting examples of nonionic surfactants suitable for use herein include: C 12 -C 18 alkyl ethoxylates, such as C 12 -C 14 alkyl ethoxylates with EO 7-9; nonionic surfactants available from Shell; C 6 -C 12 alkyl phenol alkoxylates wherein the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units; C 12 -C 18 alcohol and C 6 -C 12 alkyl phenol condensates with ethylene oxide/propylene oxide block alkyl polyamine ethoxylates such as available from BASF; C 14 -C 22 mid-chain branched alkyl alkoxylates, BAEx, wherein x is from about 1 to about 30; alkylpolysaccharides, specifically alkylpolyglycosides; polyhydroxy fatty acid amides; and ether capped poly (oxyalkylated) alcohol surfactants.
  • alkoxylated ester surfactants such as those having the formula R 1 C (O) O (R 2 O) nR 3 wherein R 1 is selected from linear and branched C 6 -C 22 alkyl or alkylene moieties; R 2 is selected from C 2 H 4 and C 3 H 6 moieties and R 3 is selected from H, CH 3 , C 2 H 5 and C 3 H 7 moieties; and n has a value between about 1 and about 20.
  • alkoxylated ester surfactants include the fatty methyl ester ethoxylates (MEE) and are well-known in the art.
  • the alkoxylated nonionic surfactant contained by the laundry detergent composition of the present invention is a C 6 -C 20 alkoxylated alcohol, preferably C 8 -C 18 alkoxylated alcohol, more preferably C 10 -C 16 alkoxylated alcohol.
  • the C 6 -C 20 alkoxylated alcohol is preferably an alkyl alkoxylated alcohol with an average degree of alkoxylation of from about 1 to about 50, preferably from about 3 to about 30, more preferably from about 5 to about 20, even more preferably from about 5 to about 9.
  • the alkoxylation herein may be ethoxylation, propoxylation, or a mixture thereof, but preferably is ethoxylation.
  • the alkoxylated nonionic surfactant is C 6 -C 20 ethoxylated alcohol, preferably C 8 -C 18 alcohol ethoxylated with an average of about 5 to about 20 moles of ethylene oxides, more preferably C 10 -C 16 alcohol ethoxylated with an average of about 5 to about 9 moles of ethylene oxides.
  • the most preferred alkoxylated nonionic surfactant is C 12 -C 15 alcohol ethoxylated with an average of about 7 moles of ethylene oxide, e.g., 25-7 commercially available from Shell.
  • the nonionic surfactant system in the composition according to the present disclosure may be present in an amount ranging from 1%to 45%, preferably from 2%to 40%, more preferably from 3%to 35%, most preferably from 4%to 30%, for example 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 20%, 25%, 30%or any ranges therebetween, by weight of the composition.
  • the weight ratio of the nonionic surfactant system to the anionic surfactant system is between 1.5 and 20, preferably between 1.7 and 15, more preferably between 1.9 and 10, and most preferably between 2 and 8, for example 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.5, 3, 4, 5, 6, 7, 8, 9, 10 and any ranges therebetween.
  • the laundry detergent composition according to the present disclosure may further comprise from 0.01%to 10%, preferably from 0.1%to 5%, more preferably from 0.2%to 3%, most preferably from 0.3%to 2%, by weight of the composition, of a surfactant boosting polymer, preferably polyvinyl acetate grafted polyethylene oxide copolymer.
  • a surfactant boosting polymer preferably polyvinyl acetate grafted polyethylene oxide copolymer.
  • the laundry detergent composition of the present invention may further comprise a cationic surfactant.
  • cationic surfactants include: quaternary ammonium surfactants, which can have up to 26 carbon atoms include: alkoxylate quaternary ammonium (AQA) surfactants; dimethyl hydroxyethyl quaternary ammonium; dimethyl hydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants; and amino surfactants, specifically amido propyldimethyl amine (APA) .
  • AQA alkoxylate quaternary ammonium
  • APA amino surfactants
  • adjunct ingredients include but are not limited to: builders, chelating agents, rheology modifiers, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic materials, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, preformed peracids, polymeric dispersing agents, clay soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, photobleaches, perfumes, perfume microcapsules, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids, solvents, hueing agents, structurants and/or pigments.
  • the precise nature of these adjunct ingredients and the levels thereof in the laundry detergent composition will depend on the physical form of the composition and the nature of the cleaning operation for which it is to be used.
  • the laundry detergent composition according to the present disclosure may further comprise from 0.01%to 10%, preferably from 0.1%to 5%, more preferably from 0.2%to 3%, most preferably from 0.3%to 2%, by weight of the composition, of a fatty acid.
  • the laundry detergent composition of the present invention is generally prepared by conventional methods such as those known in the art of making laundry detergent compositions. Such methods typically involve mixing the essential and optional ingredients in any desired order to a relatively uniform state, with or without heating, cooling, application of vacuum, and the like, thereby providing laundry detergent compositions containing ingredients in the requisite concentrations.
  • Another aspect of the present invention is directed to a method of using the laundry detergent composition to treat a fabric. Such method can deliver a color protection benefit.
  • the method comprises the step of administering from 5 g to 120 g of the above-mentioned laundry detergent composition into a laundry washing basin comprising water to form a washing solution.
  • the washing solution in a laundry washing basin herein preferably has a volume from 1 L to 50 L, alternatively from 1 L to 20 L for hand washing and from 20 L to 50 L for machine washing.
  • the temperatures of the laundry washing solution preferably range from 5°C to 60°C.
  • the dosing amount in the method herein may be different depending on the washing type.
  • the method comprises administering from about 5 g to about 60 g of the laundry detergent composition into a hand washing basin (e.g., about 2-4 L) .
  • the method comprises administering from about 5 g to about 100 g, preferably from about 10 g to about 65 g of the laundry detergent composition into a washing machine (e.g., about 30-45 L) .
  • Step 2) Store the samples prepared in Step 1) under different temperatures (5 ⁇ or 40 ⁇ ) for a certain period (1, 2 or 4 weeks) or subject the samples prepared in Step 1) to Frozen/Thawed (-18 ⁇ and 15 ⁇ ) cycles (1, 2 or 3 cycles) by freezing the samples in refrigerators (at -18 ⁇ ) for 24 hours and then thawing the samples in containers (at 15 ⁇ ) for 24 hours (repeated if more than 1 cycle) ;
  • Step 2 3) Visually inspect the samples to determine if they are still homogeneous systems after Step 2) . If there is any phase separation such as the formation of separated layers or flocculation, it is determined as “fail” . If there is no phase separation, it is determined as “pass” .
  • Dye bleeding test c is conducted by using Tergotometer (Model: RHLQ1V, from Research Institute of Daily Chemical Industry (RIDCI) ) as below:
  • test fabric (ASIE-130 or ASIE-133) in each piece for each tube of tergotometer;
  • RO reverse osmosis
  • Step 7) Take out ⁇ 30ml solution to measure L*/a*/b under same condition as Step 5) ;
  • Example 1 Stability of Liquid Laundry Detergent Compositions Containing Dye Fixative
  • a liquid laundry detergent composition containing a dye fixative was prepared containing the following ingredients as shown in Table 1.
  • Dye fixative poly (2-hydroxypropyldimethylammonium chloride) commercially available under the trade name of TEXCARE DFC 6 from Clariant.
  • Samples 1 to 6 and Control were prepared by adding different stabilizing agents into the liquid laundry detergent composition containing the dye fixative shown in Table 1, in which hydrogenated castor oil (HCO) , microcrystalline cellulose (MCC) , carboxymethyl cellulose (CMC) , starch, alcohol ethoxylate and polymeric thickener were tested as the stabilizing agent and no stabilizing agent was added for Control.
  • HCO hydrogenated castor oil
  • MCC microcrystalline cellulose
  • CMC carboxymethyl cellulose
  • starch alcohol ethoxylate and polymeric thickener
  • a sample liquid laundry detergent composition containing a dye fixative (Sample 7) and a control (Comparative Sample 2, i.e. China National Standard Liquid Detergent) containing no dye fixative were prepared containing the following ingredients.
  • Dye fixative poly (2-hydroxypropyldimethylammonium chloride) commercially available under the trade name of TEXCARE DFC 6 from Clariant.
  • sample liquid laundry detergent composition containing a dye fixative (Sample 8) and a control (Comparative Sample 3) containing a similar surfactant system but no color fixative were prepared containing the following ingredients.
  • Dye fixative poly (2-hydroxypropyldimethylammonium chloride) commercially available under the trade name of TEXCARE DFC 6 from Clariant.
  • Example 3 Exemplary Formulations of Liquid Laundry Detergent Compositions Containing Dye Fixative
  • liquid laundry detergent compositions shown in Table 5 are made comprising the listed ingredients in the listed proportions (weight %) .
  • Example 4 Exemplary Formulations of Unite Dose Laundry Detergent Compositions Containing a Dye Fixative
  • compositions shown in Table 6 are made for unit dose laundry detergent. These compositions are encapsulated into compartment (s) of the unit dose by using a polyvinyl-alcohol-based film.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Molecular Biology (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

A laundry detergent composition comprises a dye fixative and a crystalline, hydroxyl-containing stabilizing agent. The laundry detergent composition characterized by the stabilizing agent enables an improved stability of the laundry detergent composition containing the dye fixative.

Description

    LAUNDRY DETERGENT COMPOSITION CONTAINING DYE FIXATIVE AND STABILIZING AGENT FIELD OF THE INVENTION
  • The present invention relates to a laundry detergent composition containing a dye fixative and a stabilizing agent.
  • BACKGROUND OF THE INVENTION
  • As detergent products are evolving, consumer needs in the term of cleaning have been well met. However, there are still some other unmet consumer needs in the field of laundry. Particularly, one of the unmet needs is to prevent color fading or color bleeding of colored textiles during the wash cycles.
  • Colored textiles may fade over several wash cycles due to the release of the dyes from the textiles, especially in the case of dark-colored textiles made of cotton and mixed cotton fabrics. On the other hand, color bleeding might occur, i.e., a differently colored or white textile might be stained with the dye released from dyed textiles as a result relatively high dye concentration in the wash liquor if they were washed at the same time. Color fading or color bleeding would result in a rapid deterioration of the appearance of colored textiles. There is therefore a continuing need for laundry detergent compositions that are capable of preventing color fading and/or color bleeding.
  • Currently, to solve the problem of color fading or color bleeding, so-called dye fixatives are employed in detergent compositions. Such dye fixatives are usually cationic polymers which could bind negative-charged dyes on the textiles or in the washing liquor so as to prevent the detachment of dyes from colored textiles or redeposition of dyes onto white textiles or textiles with a different dye. However, the introduction of such dye fixatives into a liquid detergent composition might compromise the stability of the liquid detergent composition, i.e., the dye fixatives have a tendency to separate from the aqueous phase and/or flocculation.
  • Therefore, there are needs for providing a stabilized laundry detergent composition containing a dye fixative. Particularly, it is desirable that the laundry detergent composition containing the dye fixative is sufficiently stable for shelf life.
  • SUMMARY OF THE INVENTION
  • It is a surprising and unexpected discovery of the present invention that incorporation of a crystalline, hydroxyl-containing stabilizing agent into a laundry detergent composition containing a dye fixative can significantly improve the stability of the laundry detergent composition.
  • Correspondingly, the present invention in one aspect relates to a laundry detergent composition, comprising:
  • a) from 0.01%to 10%by weight of the composition, of a dye fixative wherein the dye fixative is selected from the group consisting of:
  • i) reaction products of polyamines with cyanamides and acids such as organic and/or inorganic acids,
  • ii) reaction products of cyanvamides with aldehydes and ammonium salts,
  • iii) reaction products of cyanamides with aldehydes and amines, or
  • iv) reaction products of amines with epichlorohydrin; and
  • v) any combinations thereof.
  • b) from 0.01%to 10%by weight of the composition, of a crystalline, hydroxyl-containing stabilizing agent.
  • In a particularly preferred embodiment of the present disclosure, the composition is a liquid composition comprising:
  • a) from 0.15%to 0.9%by weight of the composition, of a dye fixative wherein the dye fixative is selected from the group consisting of reaction products of dimethylamine with epichlorohydrin;
  • b) from 0.05%to 1%, by weight of the composition, of hydrogenated castor oil (HCO) and/or from 0.05%to 1%, by weight of the composition, of microcrystalline cellulose (MCC) ;
  • c) from 0.15%to 2%by weight of the composition, of an amine oxide which is C6-C20 alkyldimethyl amine oxide;
  • d) from 4%to 15%by weight of the composition, of a nonionic surfactant system comprising C10-C16 ethoxylated alcohol having a weight average degree of ethoxylation ranging from 5to 15, preferably 6 to 12, and more preferably 7 to 10; and
  • e) from 1%to 10%by weight of the composition, of an anionic surfactant system comprising C10-C16 LAS and C10-C16 alkyl ethoxy sulfates in which preferably, the C10-C16 LAS is present in an amount ranging from 10%to 90%, by weight of the anionic surfactant system;
  • wherein the weight ratio of the nonionic surfactant system to the anionic surfactant system is between 1.5 and 8.
  • In a particularly preferred embodiment of the present disclosure, the composition is an unit dose composition comprising:
  • a) from 0.5%to 3%by weight of the composition, of said dye fixative wherein said dye fixative is selected from the group consisting of reaction products of dimethylamine with epichlorohydrin;
  • b) from 0.05%to 1%, by weight of the composition, of hydrogenated castor oil and/or from 0.05%to 2%, by weight of the composition, of microcrystalline cellulose;
  • c) from 0.5%to 8%by weight of the composition, of said amine oxide which is C 6-C 20 alkyldimethyl amine oxide;
  • d) from 10%to 35%by weight of the composition, of said nonionic surfactant system comprising C 10-C 16 ethoxylated alcohol having a weight average degree of ethoxylation ranging from 7 to 9; and
  • e) from 3%to 25%by weight of the composition, of said anionic surfactant system comprising C 10-C 16 LAS and C 10-C 16 alkyl ethoxy sulfates in which said C 10-C 16 LAS is present in an amount ranging from 40%to 90%, by weight of the anionic surfactant system;
  • wherein the weight ratio of the nonionic surfactant system to the anionic surfactant system is between 1.5 and 8.
  • In another aspect, the present invention relates to a method of protecting color in a colored fabric comprising contacting the colored fabric with the laundry detergent composition as mentioned hereinabove. Preferably, the protection of the color is achieved by fixing dyes in the colored fabric and/or preventing color fading or color bleeding from the colored fabric.
  • In another aspect, the present invention relates to a method of preventing color fading or color bleeding of a colored fabric comprising contacting the colored fabric with the laundry detergent composition as mentioned hereinabove.
  • In another aspect, the present invention relates to a method of fixing dyes in a colored fabric comprising contacting the colored fabric with the laundry detergent composition as mentioned hereinabove.
  • It is an advantage of the laundry detergent composition to provide an improved stability of the laundry detergent composition containing a dye fixative.
  • It is another advantage of the laundry detergent composition to deliver an effective color protection for colored fabrics including e.g. the prevention of color fading and/or color bleeding and dye fixing.
  • It is another advantage of the laundry detergent composition to provide a balance of performances between colored fabrics having different colors (e.g., red and blue) .
  • DETAILED DESCRIPTION OF THE INVENTION
  • Definitions
  • As used herein, the articles including “a” and “an” when used in a claim, are understood to mean one or more of what is claimed or described.
  • As used herein, the terms “comprise” , “comprises” , “comprising” , “include” , “includes” , “including” , “contain” , “contains” , and “containing” are meant to be non-limiting, i.e., other steps and other ingredients which do not affect the end of result can be added. The above terms encompass the terms “consisting of” and “consisting essentially of” .
  • As used herein, when a composition is “substantially free” of a specific ingredient, it is meant that the composition comprises less than a trace amount, alternatively less than 0.1%, alternatively less than 0.01%, alternatively less than 0.001%, by weight of the composition, of the specific ingredient.
  • As used herein, the term “laundry detergent composition” means a composition for cleaning soiled materials, including fabrics. Such compositions may be used as a pre-laundering treatment, a post-laundering treatment, or may be added during the rinse or wash cycle of the laundering operation. The laundry detergent composition compositions may have a form selected from liquid, powder, unit dose such as single-compartment or multi-compartment unit dose, pouch, tablet, gel, paste, bar, or flake. Preferably, the laundry detergent composition is a liquid or a unit dose composition. The term of “liquid laundry detergent composition” herein refers to compositions that are in a form selected from the group consisting of pourable liquid, gel, cream, and combinations thereof. The liquid laundry detergent composition may be either aqueous or non-aqueous, and may be anisotropic, isotropic, or combinations thereof. The term of “unit dose laundry detergent composition” herein refers to a water-soluble pouch containing a certain volume of liquid wrapped with a water-soluble film.
  • As used herein, the term “main surfactant” refers to a surfactant that is present in a composition at an amount that is greater than any other surfactant contained by such composition. Similarly, the term “main anionic surfactant” refers to an anionic surfactant that is present in a  composition at an amount that is greater than any other anionic surfactant contained by such composition
  • As used herein, the term “majority surfactant” refers to a surfactant that is present in a composition at an amount that is at least 50%by weight of the total surfactant content in such composition. Similarly, the term “majority anionic surfactant” refers to an anionic surfactant that is present in a composition at an amount that is at least 50%by weight of the total anionic surfactant content in such composition.
  • As used herein, the term "alkyl" means a hydrocarbyl moiety which is branched or unbranched, substituted or unsubstituted. Included in the term "alkyl" is the alkyl portion of acyl groups.
  • As used herein, the term “washing solution” refers to the typical amount of aqueous solution used for one cycle of laundry washing, preferably from 1 L to 50 L, alternatively from 1 L to 20 L for hand washing and from 20 L to 50 L for machine washing.
  • As used herein, the term “soiled fabric” is used non-specifically and may refer to any type of natural or artificial fibers, including natural, artificial, and synthetic fibers, such as, but not limited to, cotton, linen, wool, polyester, nylon, silk, acrylic, and the like, as well as various blends and combinations.
  • Dye fixatives
  • The dye fixatives of the present invention are cationic polymers. Without being bound by any theory, it is believed that such dye fixatives with positive charges can bind dyes with negative charges through charge interactions and then prevent the dyes out of the textiles or prevent the redeposition of the dyes onto a different colored textiles. Particularly, the dye fixatives may be selected from the group consisting of reaction products of: i) polyamines with cyanamides and organic and/or inorganic acids, ii) cyanamides with aldehydes and ammonium salts, iii) cyanamides with aldehydes and amines, or iv) amines with epichlorohydrin. Preferably, the dye fixative may be selected from the group consisting of reaction products of amines with epichlorohydrin in which the amines are primary, secondary or tertiary amines. More preferably, the dye fixative may be selected from the group consisting of reaction products of dimethylamine with epichlorohydrin. Most preferably, the dye fixative may be poly (2-hydroxypropyldimethylammonium chloride) , also called poly (dimethylamine-co-epichlorohydrin) , for example the polymer commercially available under the trade name of TEXCARE DFC 6 from Clariant (CAS#: 25988-97-0) .
  • The term of “amines” comprises monoamines and polyamines. The monoamines used herein may be primary, secondary and tertiary amines. They may be aliphatic amines, for example dialkylamines, especially dimethylamine, alicyclic amines, for example cyclohexylamine, and aromatic amines, for example aniline. However, the amines used herein may also simultaneously have aliphatic, alicyclic and aromatic substituents. In addition, it is also possible to use heterocyclic compounds, for example pyridine. The term "polyamines" herein includes, for example diamines, triamines, tetraamines, etc, and also the analogous N-alkylpolyamines and N, N-dialkylpolyamines. Examples thereof are ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, diethylenetriamine, triethylenetetraamine and higher polyamines. Particularly preferred polyamines may be ethylenediamine, diethylenetriamine and dimethylaminopropylamine. The ammonium salts are salts of ammonia, especially ammonium chloride or the abovementioned amines or polyamines with different inorganic or organic acids, or else quaternary ammonium salts.
  • The cyanamides may be cyanamide or dicyandiamide. Aldehydes used herein may include, for example, aliphatic aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde; dialdehydes, for example glyoxal; unsaturated aldehydes, for example acrolein, crotonaldehyde and aromatic aldehydes, for example benzaldehyde. Particularly preferred aldehydes may be aliphatic aldehydes such as formaldehyde.
  • The dye fixatives used herein may also be homo-and copolymers based on diallyldimethylammonium chloride (DADMAC) . Copolymers based on DADMAC contain, as further components, other vinylic monomers, for example vinylimidazole, vinylpyrrolidone, vinyl alcohol, vinyl acetate, (meth) acrylic acid/ester, acrylamide, styrene, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid (AMPS) , etc. Homopolymers based on DADMAC are obtainable under the trade names 3954, Dodigen 4033 and Genamin PDAC (from Clariant) .
  • Preferably, the dye fixative suitable for use in the present disclosure can be selected from the group consisting of reaction products of amines with epichlorohydrin in which the amines are primary, secondary or tertiary amines. More preferably, the dye fixative suitable for use in the present invention can be selected from the group consisting of reaction products of dimethylamine with epichlorohydrin. Most preferably, the dye fixative may be poly (2-hydroxypropyldimethylammonium chloride) .
  • In one embodiment, the dye fixative is poly (2-hydroxypropyldimethylammonium chloride) of formula (I) :
  • wherein n is an integer from 5 to 1000.
  • The dye fixative in the composition according to the present disclosure may be present in an amount ranging from 0.02%to 5%, preferably from 0.05%to 2%, more preferably from 0.1%to 1.5%, most preferably from 0.15%to 0.9%, for example 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%or any ranges therebetween, by weight of the composition.;
  • Stabilizing agent
  • The stabilizing agent suitable for use in the present invention may be a crystalline, hydroxyl-containing stabilizing agent.
  • Preferably, the stabilizing agent may be selected from the group consisting of microcrystalline cellulose (MCC) or derivatives thereof, castor oil or derivatives thereof, hydrogenated castor oil (HCO) or derivatives thereof, and any combinations thereof. More preferably, the stabilizing agent may be microcrystalline cellulose or derivatives thereof and/or hydrogenated castor oil or derivatives thereof.
  • MCC is a naturally occurring polymer. It is composed of glucose units connected by a 1-4 beta glycosidic bond. These linear cellulose chains are bundled together as microfibril spiralled together in plant cell walls. It has been used in food applications and pharmaceutical tablets.
  • Castor oils may include glycerides, especially triglycerides, comprising C 10 to C 22 alkyl or alkenyl moieties which incorporate a hydroxyl group. Hydrogenation of castor oil to make HCO converts double bonds, which may be present in the starting oil as ricinoleyl moieties, to convert ricinoleyl moieties to saturated hydroxyalkyl moieties, e.g., hydroxystearyl. The HCO herein may, in some embodiments, be selected from: trihydroxystearin; dihydroxystearin; and mixtures thereof. The HCO may be processed in any suitable starting form, including, but not limited those selected from solid, molten and mixtures thereof.
  • In some preferred embodiments, the stabilizing agent is incorporated into the liquid detergent composition through the use of external structuring system (s) (ESS) comprising the stabilizing agent. The ESS suitable for use in the present invention may comprise: (a) the stabilizing agent; (b) alkanolamine e.g. monoethanolamine (MEA) ; (c) anionic surfactant such as: linear alkyl benzene sulphonate (LAS) ; and (d) additional components.
  • HCO is typically present in the ESS of the present invention at a level of from about 2%to about 10%, from about 3%to about 8%, or from about 4%to about 6%by weight of the structuring system. In some embodiments, the corresponding percentage of hydrogenated castor oil delivered into a finished laundry detergent product is below about 1.0%, typically from 0.1%to 0.8%.
  • Useful HCO may have the following characteristics: a melting point of from about 40 ℃ to about 100 ℃, or from about 65 ℃ to about 95 ℃; and/or Iodine value ranges of from 0 to about 5, from 0 to about 4, or from 0 to about 2.6. The melting point of HCO can be measured using either ASTM D3418 or ISO 11357; both tests utilize DSC: Differential Scanning Calorimetry.
  • HCO of use in the present invention includes those that are commercially available. Non-limiting examples of commercially available HCO of use in the present invention include:  from Rheox, Inc. The source of the castor oil for hydrogenation to form HCO can be of any suitable origin, such as from Brazil or India. In one suitable embodiment, castor oil is hydrogenated using a precious metal, e.g., palladium catalyst, and the hydrogenation temperature and pressure are controlled to optimize hydrogenation of the double bonds of the native castor oil while avoiding unacceptable levels of dehydroxylation.
  • The stabilizing agent in the composition according to the present disclosure may be present in an amount ranging from 0.01%to 9%, preferably from 0.02%to 8%, more preferably from 0.03%to 5%, yet more preferably from 0.05%to 3%, most preferably from 0.06%to 2%, for example, 0.1%, 0.2%, 0.3%, 0.5%, 0.7%, 1%, 2%or any ranges therebetween, by weight of the composition.
  • Amine Oxide
  • The amine oxide suitable for use in the present invention may be selected from the group consisting of C 6-C 20 alkyldimethyl amine oxides (AO) and combinations thereof.
  • Preferably, the amine oxide is characterized by the following structure:
  • where R 1 is a C 6-20 alkyl, a C 6-20 hydroxyalkyl, or a C 6-20 alkyl phenyl group; each R 2 is a C 2-5 alkylene, or a C 2-5 hydroxyalkylene group; x is from 0 to about 3; and each R 3 is a C 1-3 alkyl, a C 1-3 hydroxyalkyl, or a polyethylene oxide containing from about 1 to about 3 ethoxylene (EO) units. Preferably, the amine oxide may be a C 8-18 alkyldimethyl amine oxide, preferably a C 10-16 alkyldimethyl amine oxide.
  • Preferably, the amine oxide is selected from the group consisting of dodecyldimethyl amine oxide, tetradecyldimethyl amino oxide, and a combination thereof. More preferably, the amine oxide contains dodecyldimethyl amino oxide having the following formula (III) :
  • Such a compound is also referred to as lauryldimethyl amine oxide or dodecydimethyl amine-N-oxide (DDAO) . It is commercially available from Huntsman under the tradename  LO.
  • The amine oxide in the composition according to the present disclosure may be present in an amount ranging from 0.01%to 10%, preferably from 0.02%to 8%, more preferably from 0.1%to 3%, most preferably from 0.15%to 2%, for example 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%or any ranges therebetween, by weight of the composition.
  • Anionic Surfactant
  • The laundry detergent composition of the present invention may comprise an anionic surfactant system. Particularly, the laundry detergent composition of the present invention may comprise from 0.1%to 50%by weight of the composition, of an anionic surfactant system.
  • Preferably, the anionic surfactant system may comprise an anionic surfactant selected from the group consisting of C 6-C 20 linear alkylbenzene sulfonates (LAS) , C 6-C 20 alkyl sulfates (AS) , C 6-C 20 alkyl alkoxy sulfates (AAS) , C 6-C 20 methyl ester sulfonates (MES) , C 6-C 20 alkyl ether carboxylates (AEC) , and any combinations thereof. More preferably, the anionic surfactant system may comprise a C 6-C 20 LAS and optionally an additional anionic surfactant such as a C 6-C 20 AS and/or a C 6-C 20 AAS. In one embodiment, LAS is C 10-C 16 LAS, preferably C 12-C 14 LAS.
  • The LAS is normally prepared by sulfonation (using SO 2 or SO 3) of alkylbenzenes followed by neutralization. Suitable alkylbenzene feedstocks can be made from olefins, paraffins or mixtures thereof using any suitable alkylation scheme, including sulfuric and HF-based  processes. By varying the precise alkylation catalyst, it is possible to widely vary the position of covalent attachment of benzene to an aliphatic hydrocarbon chain. Accordingly, the LAS herein can vary widely in 2-phenyl isomer and/or internal isomer content.
  • In some embodiments of the laundry detergent composition, C 6-C 20 LAS may be present in an amount ranging from 1%to 100%, preferably from 10%to 99%, more preferably from 20%to 95%, most preferably from 30%to 90%, for example 40%, 50%, 60%, 70%, 80%, 90%or any ranges therebetween, by weight of the anionic surfactant.
  • In some embodiments of the laundry detergent composition, the level of LAS is preferably higher than that of any other anionic surfactant contained by such composition, i.e., the LAS is the main anionic surfactant in such composition.
  • The anionic surfactant suitable for use in the present disclosure may further comprise C 6-C 20 alkyl sulfates (AS) , C 6-C 20 alkyl alkoxy sulfates (AAS) , C 6-C 20 methyl ester sulfonates (MES) , C 6-C 20 alkyl ether carboxylates (AEC) , or any combinations thereof. For example, the laundry detergent composition may contain a C 6-C 20 alkyl alkoxy sulfates (AA xS) , wherein x is about 1-30, preferably about 1-15, more preferably about 1-10, most preferably x is about 1-3. The alkyl chain in such AA xS can be either linear or branched, with mid-chain branched AA xS surfactants being particularly preferred. A preferred group of AA xS include C 12-C 14 alkyl alkoxy sulfates with x of about 1-3. The amount of AA xS surfactant (s) in the laundry detergent composition of the present invention may range from about 0.05%to about 100%, preferably from about 0.1%to about 80%, more preferably from about 0.5%to about 50%, most preferably from about 1%to about 30%, for example 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%or any ranges therebetween, by weight of the composition.
  • In some embodiments, the weight ratio of LAS to AA xS is at least 0.6, preferably at least 0.8, more preferably at least 0.9, most preferably at least 1, for example 0.6, 0.7, 0.8, 0.9, 1, 1.2, 1.5, 2, 2.5, 3, 4, 5, 8, 10 or any ranges therebetween.
  • The anionic surfactant system in the composition according to the present disclosure may be present in an amount ranging from 0.1%to 45%, preferably from 0.5%to 40%, more preferably from 1%to 35%, most preferably from 2%to 30%, for example 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%or any ranges therebetween, by weight of the composition.
  • In some embodiments of the present disclosure, the anionic surfactant in the composition according to the present disclosure may comprise less than 30%, preferably less than 20%, more  preferably less than 10%, most preferably less than 5%, of soap by weight of the anionic surfactant.
  • Nonionic Surfactants (NI)
  • The laundry detergent composition of the present invention may comprise a nonionic surfactant system. The nonionic surfactant system may comprise a nonionic surfactant selected from the group consisting of alkyl alkoxylated alcohols, alkyl alkoxylated phenols, alkyl polysaccharides, polyhydroxy fatty acid amides, alkoxylated fatty acid esters, alkyl polyglycosides (APG) , methyl ester ethoxylates (MEE) , sucrose esters, sorbitan esters and alkoxylated derivatives of sorbitan esters, and any combinations thereof. Preferably, the nonionic surfactant system may comprise a C 6-C 20 alkoxylated alcohol having a weight average degree of alkoxylation ranging from 1 to 20, preferably from 5 to 15, more preferably from 7 to 10. More preferably, the nonionic surfactant system may comprise a C 8-C 18 ethoxylated alcohol having a weight average degree of ethoxylation ranging from 1 to 20, preferably from 5 to 15, more preferably from 7 to 10.
  • Non-limiting examples of nonionic surfactants suitable for use herein include: C 12-C 18 alkyl ethoxylates, such as C 12-C 14 alkyl ethoxylates with EO 7-9;  nonionic surfactants available from Shell; C 6-C 12 alkyl phenol alkoxylates wherein the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units; C 12-C 18 alcohol and C 6-C 12 alkyl phenol condensates with ethylene oxide/propylene oxide block alkyl polyamine ethoxylates such as  available from BASF; C 14-C 22 mid-chain branched alkyl alkoxylates, BAEx, wherein x is from about 1 to about 30; alkylpolysaccharides, specifically alkylpolyglycosides; polyhydroxy fatty acid amides; and ether capped poly (oxyalkylated) alcohol surfactants. Also useful herein as nonionic surfactants are alkoxylated ester surfactants such as those having the formula R 1C (O) O (R 2O) nR 3 wherein R 1 is selected from linear and branched C 6-C 22 alkyl or alkylene moieties; R 2 is selected from C 2H 4 and C 3H 6 moieties and R 3 is selected from H, CH 3, C 2H 5 and C 3H 7 moieties; and n has a value between about 1 and about 20. Such alkoxylated ester surfactants include the fatty methyl ester ethoxylates (MEE) and are well-known in the art.
  • In a particular embodiment, the alkoxylated nonionic surfactant contained by the laundry detergent composition of the present invention is a C 6-C 20 alkoxylated alcohol, preferably C 8-C 18 alkoxylated alcohol, more preferably C 10-C 16 alkoxylated alcohol. The C 6-C 20 alkoxylated alcohol is preferably an alkyl alkoxylated alcohol with an average degree of alkoxylation of from about 1 to about 50, preferably from about 3 to about 30, more preferably from about 5 to about  20, even more preferably from about 5 to about 9. The alkoxylation herein may be ethoxylation, propoxylation, or a mixture thereof, but preferably is ethoxylation. In one embodiment, the alkoxylated nonionic surfactant is C 6-C 20 ethoxylated alcohol, preferably C 8-C 18 alcohol ethoxylated with an average of about 5 to about 20 moles of ethylene oxides, more preferably C 10-C 16 alcohol ethoxylated with an average of about 5 to about 9 moles of ethylene oxides. The most preferred alkoxylated nonionic surfactant is C 12-C 15 alcohol ethoxylated with an average of about 7 moles of ethylene oxide, e.g.,  25-7 commercially available from Shell.
  • The nonionic surfactant system in the composition according to the present disclosure may be present in an amount ranging from 1%to 45%, preferably from 2%to 40%, more preferably from 3%to 35%, most preferably from 4%to 30%, for example 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 20%, 25%, 30%or any ranges therebetween, by weight of the composition.
  • In some embodiments, the weight ratio of the nonionic surfactant system to the anionic surfactant system is between 1.5 and 20, preferably between 1.7 and 15, more preferably between 1.9 and 10, and most preferably between 2 and 8, for example 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.5, 3, 4, 5, 6, 7, 8, 9, 10 and any ranges therebetween.
  • Other ingredients
  • The laundry detergent composition according to the present disclosure may further comprise from 0.01%to 10%, preferably from 0.1%to 5%, more preferably from 0.2%to 3%, most preferably from 0.3%to 2%, by weight of the composition, of a surfactant boosting polymer, preferably polyvinyl acetate grafted polyethylene oxide copolymer.
  • The laundry detergent composition of the present invention may further comprise a cationic surfactant. Non-limiting examples of cationic surfactants include: quaternary ammonium surfactants, which can have up to 26 carbon atoms include: alkoxylate quaternary ammonium (AQA) surfactants; dimethyl hydroxyethyl quaternary ammonium; dimethyl hydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants; and amino surfactants, specifically amido propyldimethyl amine (APA) .
  • The laundry detergent composition herein may comprise adjunct ingredients. Suitable adjunct materials include but are not limited to: builders, chelating agents, rheology modifiers, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic materials, bleach activators, hydrogen peroxide, sources of hydrogen peroxide, preformed peracids, polymeric dispersing agents, clay soil removal/anti-redeposition agents, brighteners, suds  suppressors, dyes, photobleaches, perfumes, perfume microcapsules, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids, solvents, hueing agents, structurants and/or pigments. The precise nature of these adjunct ingredients and the levels thereof in the laundry detergent composition will depend on the physical form of the composition and the nature of the cleaning operation for which it is to be used.
  • In some embodiments, the laundry detergent composition according to the present disclosure may further comprise from 0.01%to 10%, preferably from 0.1%to 5%, more preferably from 0.2%to 3%, most preferably from 0.3%to 2%, by weight of the composition, of a fatty acid.
  • Composition Preparation
  • The laundry detergent composition of the present invention is generally prepared by conventional methods such as those known in the art of making laundry detergent compositions. Such methods typically involve mixing the essential and optional ingredients in any desired order to a relatively uniform state, with or without heating, cooling, application of vacuum, and the like, thereby providing laundry detergent compositions containing ingredients in the requisite concentrations.
  • Method of Use
  • Another aspect of the present invention is directed to a method of using the laundry detergent composition to treat a fabric. Such method can deliver a color protection benefit. The method comprises the step of administering from 5 g to 120 g of the above-mentioned laundry detergent composition into a laundry washing basin comprising water to form a washing solution. The washing solution in a laundry washing basin herein preferably has a volume from 1 L to 50 L, alternatively from 1 L to 20 L for hand washing and from 20 L to 50 L for machine washing. The temperatures of the laundry washing solution preferably range from 5℃ to 60℃.
  • The dosing amount in the method herein may be different depending on the washing type. In one embodiment, the method comprises administering from about 5 g to about 60 g of the laundry detergent composition into a hand washing basin (e.g., about 2-4 L) . In an alternative embodiment, the method comprises administering from about 5 g to about 100 g, preferably from about 10 g to about 65 g of the laundry detergent composition into a washing machine (e.g., about 30-45 L) .
  • Test Method
  • Test 1: Stability test
  • Stability test is conducted through visual inspection as below:
  • 1) Prepare liquid composition samples to be tested by mixing ingredients in 30ml transparent glass bottles;
  • 2) Store the samples prepared in Step 1) under different temperatures (5□ or 40□) for a certain period (1, 2 or 4 weeks) or subject the samples prepared in Step 1) to Frozen/Thawed (-18□ and 15□) cycles (1, 2 or 3 cycles) by freezing the samples in refrigerators (at -18□) for 24 hours and then thawing the samples in containers (at 15□) for 24 hours (repeated if more than 1 cycle) ;
  • 3) Visually inspect the samples to determine if they are still homogeneous systems after Step 2) . If there is any phase separation such as the formation of separated layers or flocculation, it is determined as “fail” . If there is no phase separation, it is determined as “pass” .
  • Test 2: Dye bleeding test
  • Dye bleeding test cis conducted by using Tergotometer (Model: RHLQ1V, from Research Institute of Daily Chemical Industry (RIDCI) ) as below:
  • 1) Cut ~1.0 g of test fabric (ASIE-130 or ASIE-133) in each piece for each tube of tergotometer;
  • 2) Add 1L reverse osmosis (RO) water that has water hardness level of about 9gpg (with a Ca 2+-to-Mg 2+ weight ratio of about 4: 1) heated to 40℃ with a water bath;
  • 3) Dissolve about 2.0grams of the sample liquid detergent composition to form a wash liquor with a detergent dosage of about 2000ppm;
  • 4) Adjust pH of solution to ~8.5;
  • 5) Take out ~30ml solution to measure L*/a*/b*before wash, (measured with UltraScan VIS (from HunterLab, Virginia, USA) by using 5cm x 1cm sample cell) ;
  • 6) Add one piece of 1.0g test fabric into each tube and wash for about 20 minutes;
  • 7) Take out ~30ml solution to measure L*/a*/b under same condition as Step 5) ; and
  • 8) Calculate ΔE based on before and after wash measurement, the higher ΔE indicates the worse dye bleeding.
  • EXAMPLES
  • Example 1: Stability of Liquid Laundry Detergent Compositions Containing Dye Fixative
  • A liquid laundry detergent composition containing a dye fixative was prepared containing the following ingredients as shown in Table 1.
  • Table 1
  • 1 Dye fixative : poly (2-hydroxypropyldimethylammonium chloride) commercially available under the trade name of TEXCARE DFC 6 from Clariant.
  • Then, Samples 1 to 6 and Control (i.e. Comparative Sample 1) were prepared by adding different stabilizing agents into the liquid laundry detergent composition containing the dye fixative shown in Table 1, in which hydrogenated castor oil (HCO) , microcrystalline cellulose (MCC) , carboxymethyl cellulose (CMC) , starch, alcohol ethoxylate and polymeric thickener were tested as the stabilizing agent and no stabilizing agent was added for Control. The stability of these samples under various circumstances, i.e., storing at 5℃ or 40℃ for 2 weeks or Frozen/Thawed (F/T) at -18℃/15℃ for 1 or 2 cycles, was determined in accordance with Test 1: Stability test as described hereinabove. The results of stability for these samples are shown in Table 2. Surprisingly, only HCO and MCC can stabilize the liquid laundry detergent composition containing the dye fixative, i.e. to pass the all stability tests.
  • Table 2
  • 1 HCO available from Nidera BV
  • 2 MCC available from CP Kelco
  • 3 CMC available from UGUR SELULOZ KIMYA
  • 4 Starch available from Tianjin Zhiyuan
  • 5 Lutensol XP available from BASF
  • 6 ACUSOL TM 845 available from Dow
  • Example 2: Color Protection Achieved by Laundry Detergent Compositions Containing Dye  Fixative
  • A sample liquid laundry detergent composition containing a dye fixative (Sample 7) and a control (Comparative Sample 2, i.e. China National Standard Liquid Detergent) containing no dye fixative were prepared containing the following ingredients.
  • Table 3
  • 1 Dye fixative : poly (2-hydroxypropyldimethylammonium chloride) commercially available under the trade name of TEXCARE DFC 6 from Clariant.
  • 2 HCO available from Nidera BV
  • In accordance with Test 2: Dye bleeding test as described hereinabove in which fabrics colored by Blue dye (ASIE-133) is used, the △E for these samples was measured as a measurement of dye bleeding. The higher △E indicates the worse dye bleeding, while the lower △E indicates the more effective color protection. The results are shown in the table above, indicating the laundry detergent compositions containing a color fixative show excellent performance in color protection (0.85 vs. 1.4) compared to the Comparative Sample 2 containing no color fixative.
  • Further, another sample liquid laundry detergent composition containing a dye fixative (Sample 8) and a control (Comparative Sample 3) containing a similar surfactant system but no color fixative were prepared containing the following ingredients.
  • Table 4
  • 1 Dye fixative : poly (2-hydroxypropyldimethylammonium chloride) commercially available under the trade name of TEXCARE DFC 6 from Clariant.
  • In accordance with Test 2: Dye bleeding test as described hereinabove in which fabrics colored by Blue dye (ASIE-133) is used. The results indicate the laundry detergent composition containing a color fixative shows significantly better performance (0.63 vs. 1.09) in color protection compared to the Comparative Sample containing a similar surfactant system but no color fixative.
  • Example 3: Exemplary Formulations of Liquid Laundry Detergent Compositions Containing Dye  Fixative
  • The following liquid laundry detergent compositions shown in Table 5 are made comprising the listed ingredients in the listed proportions (weight %) .
  • Table 5
  • 1 Dye Fixative: poly (2-hydroxypropyldimethylammonium chloride) commercially available under the trade name of TEXCARE DFC 6 from Clariant
  • Example 4: Exemplary Formulations of Unite Dose Laundry Detergent Compositions  Containing a Dye Fixative
  • The exemplary formulations shown in Table 6 are made for unit dose laundry detergent. These compositions are encapsulated into compartment (s) of the unit dose by using a polyvinyl-alcohol-based film.
  • Table 6
  • 1 Dye Fixative: poly (2-hydroxypropyldimethylammonium chloride) commercially available under the trade name of TEXCARE DFC 6 from Clariant
  • The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 mm” is intended to mean “about 40 mm. ”
  • Every document cited herein, including any cross referenced or related patent or application and any patent application or patent to which this application claims priority or benefit thereof, is hereby incorporated herein by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior  art with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or references, teaches, suggests or discloses any such invention. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.
  • While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims (14)

  1. A laundry detergent composition, comprising:
    a) from 0.01%to 10%, by weight of the composition, of a dye fixative wherein said dye fixative is selected from the group consisting of:
    i) reaction products of polyamines with cyanamides and acids,
    ii) reaction products of cyanvamides with aldehydes and ammonium salts,
    iii) reaction products of cyanamides with aldehydes and amines, or
    iv) reaction products of amines with epichlorohydrin; and
    v) any combinations thereof,
    b) from 0.01%to 10%, by weight of the composition, of a crystalline, hydroxyl-containing stabilizing agent.
  2. The laundry detergent composition according to Claim 1, wherein said dye fixative is present in an amount ranging from 0.02%to 5%, preferably from 0.03%to 2%, more preferably from 0.04%to 1.5%, most preferably from 0.05%to 0.9%, by weight of the composition;
    preferably, wherein said dye fixative is selected from the group consisting of reaction products of amines with epichlorohydrin in which the amines are primary, secondary or tertiary amines;
    more preferably, wherein said dye fixative is selected from the group consisting of reaction products of dimethylamine with epichlorohydrin;
    most preferably, wherein said dye fixative is poly (2-hydroxypropyldimethylammonium chloride) .
  3. The laundry detergent composition according to Claims 1 or 2, wherein said stabilizing agent is present in an amount ranging from 0.01%to 9%, preferably from 0.02%to 8%, more preferably from 0.03%to 5%, yet more preferably from 0.05%to 3%, most preferably from 0.06%to 2%, by weight of the composition;
    preferably, wherein said stabilizing agent is selected from the group consisting of microcrystalline cellulose or derivatives thereof, castor oil or derivatives thereof, hydrogenated castor oil or derivatives thereof, and any combinations thereof;
    more preferably, wherein said stabilizing agent is microcrystalline cellulose and/or hydrogenated castor oil.
  4. The laundry detergent composition according to any one of Claims 1 to 3, wherein said composition further comprises:
    c) from 0.01%to 10%, by weight of the composition, of an amine oxide; and/or
    d) from 0.1%to 50%, by weight of the composition, of a nonionic surfactant system; and/or
    e) from 0.1%to 50%, by weight of the composition, of an anionic surfactant system.
  5. The laundry detergent composition according to any one of Claims 1 to 4, wherein said amine oxide is present in an amount ranging from 0.02%to 8%, preferably from 0.05%to 5%, more preferably from 0.1%to 3%, most preferably from 0.15%to 2%, by weight of the composition;
    preferably, wherein said amine oxide is selected from the group consisting of amine oxides, fatty amine derivatives, and any combinations thereof;
    more preferably, wherein said amine oxide is selected from the group consisting of C 6-C 20 alkyldimethyl amine oxide and any combinations thereof.
    most preferably, wherein said amine oxide is selected from the group consisting of C 10-C 16 alkyldimethyl amine oxides and any combinations thereof, such as dodecyldimethyl amine oxide and/or tetradecyldimethyl amino oxide.
  6. The laundry detergent composition according to any one of Claims 1 to 5, wherein said nonionic surfactant system is present in an amount ranging from 1%to 45%, preferably from 2%to 40%, more preferably from 3%to 35%, most preferably from 4%to 30%;
    preferably, wherein said nonionic surfactant system comprises a nonionic surfactant selected from the group consisting of alkyl alkoxylated alcohols, alkyl alkoxylated phenols, alkyl polysaccharides, alkyl polyglycosides, methyl ester ethoxylates, polyhydroxy fatty acid amides, alkoxylated fatty acid esters, sucrose esters, sorbitan esters and alkoxylated derivatives of sorbitan esters, and any combinations thereof;
    more preferably, wherein said nonionic surfactant system comprises a C 6-C 20 alkoxylated alcohol having a weight average degree of alkoxylation ranging from 1 to 20, preferably from 5 to 15, more preferably from 7 to 10;
    most preferably, wherein said nonionic surfactant system comprises a C 8-C 18 ethoxylated alcohol having a weight average degree of ethoxylation ranging from 1 to 20, preferably from 5 to 15, more preferably from 7 to 10.
  7. The laundry detergent composition according to any one of Claims 1 to 6, wherein said anionic surfactant system is present in an amount ranging from 0.1%to 45%, preferably from 0.5%to 40%, more preferably from 1%to 35%, most preferably from 2%to 30%, by weight of the composition;
    preferably, wherein said anionic surfactant system comprises an anionic surfactant selected from the group consisting of C 6-C 20 linear alkylbenzene sulfonates (LAS) , C 6-C 20 alkyl sulfates (AS) , C 6-C 20 alkyl alkoxy sulfates (AAS) , C 6-C 20 methyl ester sulfonates (MES) , C 6-C 20 alkyl ether carboxylates (AEC) , and any combinations thereof.
    more preferably, wherein said anionic surfactant system comprises a C 6-C 20 LAS and optionally an additional anionic surfactant such as a C 6-C 20 AS and/or a C 6-C 20 AAS.
  8. The laundry detergent composition according to Claim 7, wherein said C 6-C 20 LAS is present in an amount ranging from 10%to 100%, preferably from 20%to 99%, more preferably from 30%to 95%, most preferably from 40%to 90%, by weight of the anionic surfactant system.
  9. The laundry detergent composition according to any one of Claims 1 to 8, wherein said composition further comprises from 0.01%to 10%, preferably from 0.1%to 5%, more preferably from 0.2%to 3%, most preferably from 0.3%to 2%, by weight of the composition, of a fatty acid.
  10. The laundry detergent composition according to any one of Claims 1 to 9, wherein said composition is a liquid composition or a unit dose composition.
  11. The laundry detergent composition according to Claim 10, wherein said composition is a liquid composition comprising:
    a) from 0.15%to 0.9%, by weight of the composition, of said dye fixative wherein said dye fixative is selected from the group consisting of reaction products of dimethylamine with epichlorohydrin;
    b) from 0.1%to 1%, by weight of the composition, of hydrogenated castor oil and/or from 0.5%to 5%, by weight of the composition, of microcrystalline cellulose;
    c) from 0.15%to 2%, by weight of the composition, of said amine oxide which is C 6-C 20 alkyldimethyl amine oxide;
    d) from 4%to 15%, by weight of the composition, of said nonionic surfactant system comprising C 10-C 16 ethoxylated alcohol having a weight average degree of ethoxylation ranging from 7 to 9; and
    e) from 1%to 10%, by weight of the composition, of said anionic surfactant system comprising C 10-C 16 LAS and C 10-C 16 alkyl ethoxy sulfates in which said C 10-C 16 LAS is present in an amount ranging from 40%to 90%, by weight of the anionic surfactant system;
    wherein the weight ratio of said nonionic surfactant system to said anionic surfactant system is between 2 and 8.
  12. The laundry detergent composition according to Claim 10, wherein said composition is an unit dose composition comprising:
    a) from 0.5%to 3%, by weight of the composition, of said dye fixative wherein said dye fixative is selected from the group consisting of reaction products of dimethylamine with epichlorohydrin;
    b) from 0.1%to 1%, by weight of the composition, of hydrogenated castor oil and/or from 0.1%to 1%, by weight of the composition, of microcrystalline cellulose;
    c) from 0.5%to 8%, by weight of the composition, of said amine oxide which is C 6-C 20 alkyldimethyl amine oxide;
    d) from 10%to 35%, by weight of the composition, of said nonionic surfactant system comprising C 10-C 16 ethoxylated alcohol having a weight average degree of ethoxylation ranging from 7 to 9; and
    e) from 3%to 25%, by weight of the composition, of said anionic surfactant system comprising C 10-C 16 LAS and C 10-C 16 alkyl ethoxy sulfates in which said C 10-C 16 LAS is present in an amount ranging from 40%to 90%, by weight of the anionic surfactant system;
    wherein the weight ratio of said nonionic surfactant system to said anionic surfactant system is between 2 and 8.
  13. A method of protecting color in a colored fabric comprising contacting the colored fabric with the laundry detergent composition according to any one of the preceding claims.
  14. The method according to claim 13, wherein the protection of the color is achieved by fixing dyes in the colored fabric and/or preventing color fading or color bleeding from the colored fabric.
EP20966231.1A 2020-12-21 2020-12-21 Laundry detergent composition containing dye fixative and stabilizing agent Pending EP4263770A1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2020/138032 WO2022133650A1 (en) 2020-12-21 2020-12-21 Laundry detergent composition containing dye fixative and stabilizing agent

Publications (1)

Publication Number Publication Date
EP4263770A1 true EP4263770A1 (en) 2023-10-25

Family

ID=81992179

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20966231.1A Pending EP4263770A1 (en) 2020-12-21 2020-12-21 Laundry detergent composition containing dye fixative and stabilizing agent

Country Status (3)

Country Link
EP (1) EP4263770A1 (en)
CN (1) CN114644963A (en)
WO (1) WO2022133650A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20230029458A1 (en) * 2021-07-16 2023-02-02 The Procter & Gamble Company Liquid hand dishwashing cleaning composition
US20230018865A1 (en) * 2021-07-16 2023-01-19 The Procter & Gamble Company Liquid hand dishwashing cleaning composition
US20230034095A1 (en) * 2021-07-16 2023-02-02 The Procter & Gamble Company Liquid hand dishwashing cleaning composition
CN115572643A (en) * 2022-10-19 2023-01-06 宝洁公司 Laundry detergent compositions containing dye fixing agent and water soluble calcium salt

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001032815A1 (en) * 1999-10-29 2001-05-10 The Procter & Gamble Company Laundry detergent compositions with fabric care
EP1978081B1 (en) * 2000-10-27 2014-04-30 The Procter and Gamble Company Stabilized liquid compositions
DE102004018051A1 (en) * 2004-04-08 2005-11-10 Clariant Gmbh Detergents and cleaning agents containing dye fixing agents and soil release polymers
DE102004051011A1 (en) * 2004-10-20 2005-06-23 Clariant Gmbh Liquid laundry and other detergents, e.g. for wool, delicate or heavy wash, contain secondary alkanesulfonate and color fixative, e.g. diallyl-dimethyl-ammonium chloride polymer or reaction product of cyanamide, aldehyde and amine
AR078363A1 (en) * 2009-09-14 2011-11-02 Procter & Gamble COMPACT FLUID DETERGENT COMPOSITION FOR LAUNDRY
CN110198991A (en) * 2016-11-01 2019-09-03 美利肯公司 Procrypsis polymer as the blueing agent in laundry care composition

Also Published As

Publication number Publication date
CN114644963A (en) 2022-06-21
WO2022133650A1 (en) 2022-06-30

Similar Documents

Publication Publication Date Title
EP4263770A1 (en) Laundry detergent composition containing dye fixative and stabilizing agent
JP6661545B2 (en) How to wash fabric
US20230203405A1 (en) Laundry detergent composition containing dye fixative and amine oxide
US20230193159A1 (en) Laundry detergent composition containing dye fixative and amine-based surfactant
JP6749378B2 (en) Antibacterial laundry detergent composition
US20190048298A1 (en) Water-soluble unit dose article comprising an amphiphilic graft polymer and a polyester terephthalate
EP3143112A1 (en) Anti-microbial laundry detergent composition
CN115572643A (en) Laundry detergent compositions containing dye fixing agent and water soluble calcium salt
EP4217453A1 (en) Laundry detergent composition containing dye fixative and linear alkylbenzene sulfonate
EP4267710A1 (en) A process of removing microorganism from an article of clothing
KR101903977B1 (en) Etheramines based on dialcohols
CN118202028A (en) Water-soluble unit dose articles comprising a narrow range of ethoxylated alcohol nonionic surfactants
JP2023547669A (en) Low viscosity liquid detergent composition containing antifoaming agent and nonionic surfactant
JP2023548699A (en) How to remove microorganisms from clothes after washing
WO2022134891A1 (en) A process of removing microorganism from an article of clothing
CN118202029A (en) Water-soluble unit dose articles comprising ethoxylated alcohol nonionic surfactant

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

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

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20230503

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

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)