WO2022062752A1 - Water-soluble unit dose article comprising amine oxide surfactant, diol solvent and polyol solvent - Google Patents

Water-soluble unit dose article comprising amine oxide surfactant, diol solvent and polyol solvent Download PDF

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Publication number
WO2022062752A1
WO2022062752A1 PCT/CN2021/112267 CN2021112267W WO2022062752A1 WO 2022062752 A1 WO2022062752 A1 WO 2022062752A1 CN 2021112267 W CN2021112267 W CN 2021112267W WO 2022062752 A1 WO2022062752 A1 WO 2022062752A1
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Prior art keywords
composition
weight
water
solvent
unit dose
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PCT/CN2021/112267
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French (fr)
Inventor
Yanjie WENG
Ming Tang
Zhen Liu
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Procter and Gamble Co
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Procter and Gamble Co
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Filing date
Publication date
Priority claimed from PCT/CN2020/118325 external-priority patent/WO2022061868A1/en
Priority claimed from PCT/CN2020/118408 external-priority patent/WO2022061889A1/en
Priority claimed from PCT/CN2020/138032 external-priority patent/WO2022133650A1/en
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to CN202111138347.9A priority Critical patent/CN114317133A/en
Publication of WO2022062752A1 publication Critical patent/WO2022062752A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/40Monoamines or polyamines; 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
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/86Mixtures of anionic, cationic, and non-ionic 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
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/043Liquid or thixotropic (gel) 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
    • C11D3/0005Other 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
    • C11D3/16Organic 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
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/30Amines; Substituted amines ; Quaternized amines
    • 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
    • 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
    • C11D1/72Ethers 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
    • 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
    • C11D2111/00Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10Objects to be cleaned
    • C11D2111/12Soft surfaces, e.g. textile
    • 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
    • C11D3/3788Graft polymers

Definitions

  • the present invention relates to water-soluble unit dose articles comprising an amine oxide surfactant, a diol solvent and a polyol solvent, as well as methods of making.
  • Water-soluble unit dose articles are liked by consumers due their convenience and ease of use. Consumers also like the fact that they do not need to measure a detergent dose and so this eliminates accidental spillage during the dosing operation. Accidental dosage can be messy and inconvenient.
  • an amphoteric surfactant particularly amine oxide surfactant is commonly used in personal care products (e.g. shower body lotions) , hair care products (e.g. shampoo) , and home care products (e.g. dish washing) .
  • Amine oxide surfactants have a great performance in the aspect of grease cleaning.
  • the use of amine oxide surfactants is very limiting.
  • a water-soluble unit dose article comprising a liquid detergent composition wherein the liquid detergent composition comprises a diol solvent and a polyol solvent at a preferred ratio (e.g. from 1.25: 1 to 6: 1) solved the above technical problem, i.e. to provide a water-soluble unit dose article containing an amine oxide surfactant without any intolerable defects (e.g. significant weeping or instability) .
  • the present invention in one aspect relates to a water-soluble unit dose article comprising a water-soluble film and a liquid laundry detergent composition wrapped with the water-soluble film, wherein the liquid laundry detergent composition comprises: a) from 0.1%to 50%, by weight of the composition, of an amine oxide surfactant, b) from 0.1%to 50%, by weight of the composition, of a non-amine-oxide surfactant, c) from 0.1%to 40%, by weight of the composition, of a diol solvent, and d) from 0.1%to 30%, by weight of the composition, of a polyol solvent, wherein the sum of the amounts of said diol solvent and said polyol solvent is higher than the amount of the non-amine-oxide surfactant, and wherein the weight ratio of said diol solvent to said polyol solvent is from 1.25: 1 to 6: 1.
  • a second aspect of the present invention is a packaged product comprising a recloseable container and at least one water-soluble unit dose article according to the present invention.
  • a third aspect of the present invention is a method making a water-soluble unit dose article according to the present invention, wherein the liquid laundry detergent composition is prepared by preparing a base composition comprising the non-amine-oxide surfactant and adding the amine oxide surfactant to said base composition, wherein the amine oxide surfactant is added in the form of a powder or a premix wherein said premix comprises the amine oxide surfactant and the diol solvent and the polyol solvent.
  • water-soluble unit dose article provides an improved mechanical performance of the water-soluble unit dose article (e.g., improved pouch tightness to have better feel when consumer hold the pouch as well as improved shape retention after story. ) .
  • 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.
  • 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.
  • unit dose laundry detergent composition herein refers to a water-soluble pouch containing a certain volume of liquid wrapped with a water-soluble film.
  • 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 present invention discloses a water-soluble unit dose article comprising a water-soluble film and a liquid laundry detergent composition. Particularly, the liquid laundry detergent composition is wrapped with the water-soluble film.
  • the water-soluble film and the liquid detergent composition are described in more detail below.
  • the water-soluble unit dose article comprises the water-soluble film shaped such that the unit-dose article comprises at least one internal compartment surrounded by the water-soluble film.
  • the unit dose article may comprise a first water-soluble film and a second water-soluble film sealed to one another such to define the internal compartment.
  • the water-soluble unit dose article is constructed such that the detergent composition does not leak out of the compartment during storage. However, upon addition of the water-soluble unit dose article to water, the water-soluble film dissolves and releases the contents of the internal compartment into the wash liquor.
  • the compartment should be understood as meaning a closed internal space within the unit dose article, which holds the detergent composition.
  • a first water-soluble film may be shaped to comprise an open compartment into which the detergent composition is added.
  • a second water-soluble film is then laid over the first film in such an orientation as to close the opening of the compartment. The first and second films are then sealed together along a seal region.
  • the unit dose article may comprise more than one compartment, even at least two compartments, or even at least three compartments.
  • the compartments may be arranged in superposed orientation, i.e. one positioned on top of the other. In such an orientation the unit dose article will comprise three films, top, middle and bottom.
  • the compartments may be positioned in a side-by-side orientation, i.e. one orientated next to the other.
  • the compartments may even be orientated in a ‘tyre and rim’ arrangement, i.e. a first compartment is positioned next to a second compartment, but the first compartment at least partially surrounds the second compartment, but does not completely enclose the second compartment.
  • one compartment may be completely enclosed within another compartment.
  • the unit dose article comprises at least two compartments, one of the compartments may be smaller than the other compartment.
  • the unit dose article comprises at least three compartments, two of the compartments may be smaller than the third compartment, and preferably the smaller compartments are superposed on the larger compartment.
  • the superposed compartments preferably are orientated side-by-side.
  • the detergent composition according to the present invention may be comprised in at least one of the compartments. It may for example be comprised in just one compartment, or may be comprised in two compartments, or even in three compartments.
  • Each compartment may comprise the same or different compositions.
  • the different compositions could all be in the same form, or they may be in different forms.
  • the water-soluble unit dose article may comprise at least two internal compartments, wherein the liquid laundry detergent composition is comprised in at least one of the compartments, preferably wherein the unit dose article comprises at least three compartments, wherein the detergent composition is comprised in at least one of the compartments.
  • the film of the present invention is soluble or dispersible in water.
  • the water-soluble film preferably comprises polyvinyl alcohol or a copolymer thereof.
  • the water-soluble film comprises a blend of at least two different polyvinylalcohol homopolymers, at least two different polyvinylalcohol copolymers, at least one polyvinylalcohol homopolymer and at least one polyvinylalcohol copolymer or a combination thereof.
  • the water-soluble film has a thickness between 50microns and 100microns, preferably between 70 microns and 90 microns before being deformed into a unit dose article.
  • the film has a water-solubility of at least 50%, preferably at least 75%or even at least 95%, as measured by the method set out here after using a glass-filter with a maximum pore size of 20 microns:
  • Preferred film materials are preferably polymeric materials.
  • the film material can, for example, be obtained by casting, blow-moulding, extrusion or blown extrusion of the polymeric material, as known in the art.
  • Preferred polymers, copolymers or derivatives thereof suitable for use as pouch material are selected from polyvinyl alcohols, polyvinyl pyrrolidone, polyalkylene oxides, acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polycarboxylic acids and salts, polyaminoacids or peptides, polyamides, polyacrylamide, copolymers of maleic/acrylic acids, polysaccharides including starch and gelatine, natural gums such as xanthum and carragum.
  • More preferred polymers are selected from polyacrylates and water-soluble acrylate copolymers, methylcellulose, carboxymethylcellulose sodium, dextrin, ethylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, maltodextrin, polymethacrylates, and most preferably selected from polyvinyl alcohols, polyvinyl alcohol copolymers and hydroxypropyl methyl cellulose (HPMC) , and combinations thereof.
  • the level of polymer in the pouch material for example a PVA polymer, is at least 60%.
  • the polymer can have any weight average molecular weight, preferably from about 1000 to 1,000,000, more preferably from about 10,000 to 300,000 yet more preferably from about 20,000 to 150,000.
  • the water-soluble unit dose article comprises polyvinylalcohol.
  • Mixtures of polymers can also be used as the pouch material. This can be beneficial to control the mechanical and/or dissolution properties of the compartments or pouch, depending on the application thereof and the required needs.
  • Suitable mixtures include for example mixtures wherein one polymer has a higher water-solubility than another polymer, and/or one polymer has a higher mechanical strength than another polymer.
  • mixtures of polymers having different weight average molecular weights for example a mixture of PVA or a copolymer thereof of a weight average molecular weight of about 10,000-40,000, preferably around 20,000, and of PVA or copolymer thereof, with a weight average molecular weight of about 100,000 to 300,000, preferably around 150,000.
  • polymer blend compositions for example comprising hydrolytically degradable and water-soluble polymer blends such as polylactide and polyvinyl alcohol, obtained by mixing polylactide and polyvinyl alcohol, typically comprising about 1-35%by weight polylactide and about 65%to 99%by weight polyvinyl alcohol.
  • PVA polymers which are from about 60%to about 98%hydrolysed, preferably about 80%to about 90%hydrolysed, to improve the dissolution characteristics of the material.
  • Preferred films exhibit good dissolution in cold water, meaning unheated distilled water.
  • Preferably such films exhibit good dissolution at temperatures of 24°C, even more preferably at 10°C.
  • good dissolution it is meant that the film exhibits water-solubility of at least 50%, preferably at least 75%or even at least 95%, as measured by the method set out here after using a glass-filter with a maximum pore size of 20 microns, described above.
  • Preferred films are those supplied by Monosol.
  • the PVA resin can comprise about 30 to about 85 wt%of the first PVA polymer, or about 45 to about 55 wt%of the first PVA polymer.
  • the PVA resin can contain about 50 w. %of each PVA polymer, wherein the viscosity of the first PVA polymer is about 13 cP and the viscosity of the second PVA polymer is about 23 cP, measured as a 4%polymer solution in demineralized water at 20°C.
  • the film comprises a blend of at least two different polyvinylalcohol homopolymers and/or copolymers.
  • the water soluble film comprises a blend of at least two different polyvinylalcohol homopolymers, especially a water soluble film comprising a blend of at least two different polyvinylalcohol homopolymers of different average molecular weight, especially a blend of 2 different polyvinylalcohol homopolymers having an absolute average viscosity difference
  • the first homopolymer preferably has an average viscosity of 10 to 20 cP preferably 10 to 15 cP
  • the second homopolymer preferably has an average viscosity of 20 to 30 cP preferably 20 to 25 cP. Most preferably the two homopolymers are blended in a 40/60 to a 60/40 weight %ratio.
  • the water soluble film comprises a polymer blend comprising at least one copolymer comprising polyvinylalcohol and anionically modified monomer units.
  • the polymer blend might comprise a 90/10 to 50/50 weight %ratio of a polyvinylalcohol homopolymer and a copolymer comprising polyvinylalcohol and anionically modified monomer units.
  • the polymer blend might comprise a 90/10 to 10/90 weight %ratio of two different copolymers comprising polyvinylalcohol and anionically modified monomer units.
  • suitable anionic monomer units include the vinyl polymerization units corresponding to vinyl anionic monomers including vinyl acetic acid, maleic acid, monoalkyl maleate, dialkyl maleate, monomethyl maleate, dimethyl maleate, maleic anyhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, fumaric anyhydride, itaconic acid, monomethyl itaconate, dimethyl itaconate, itaconic anhydride, vinyl sulfonic acid, allyl sulfonic acid, ethylene sulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid, 2-sufoethyl acrylate, alkali metal salts of the foregoing (e.g., sodium, potassium, or other alkali metal salts) , esters of the for
  • the anionic monomer can be one or more acrylamido methylpropanesulfonic acids (e.g., 2-acrylamido-1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid) , alkali metal salts thereof (e.g., sodium salts) , and combinations thereof.
  • the anionic monomer can be one or more of monomethyl maleate, alkali metal salts thereof (e.g., sodium salts) , and combinations thereof.
  • the level of incorporation of the one or more anionic monomer units in the PVOH copolymers is not particularly limited.
  • the one or more anionic monomer units are present in a PVOH copolymer in an amount in a range of about 2 mol. %to about 10 mol. % (e.g., at least 2.0, 2.5, 3.0, 3.5, or 4.0 mol. %and/or up to about 3.0, 4.0, 4.5, 5.0, 6.0, 8.0, or 10 mol. %in various embodiments) , individually or collectively.
  • compartments of the present invention may be employed in making the compartments of the present invention.
  • a benefit in selecting different films is that the resulting compartments may exhibit different solubility or release characteristics.
  • the film material herein can also comprise one or more additive ingredients.
  • plasticisers for example glycerol, ethylene glycol, diethyleneglycol, propylene glycol, dipropylene glycol (DPG) , sorbitol and mixtures thereof.
  • Other additives may include water and functional detergent additives, including surfactant, to be delivered to the wash water, for example organic polymeric dispersants, etc.
  • Preferred films are those supplied by Monosol under the trade references M8630, M8900, M8779, M8310, films described in US 6 166 117 and US 6 787 512 and PVA films of corresponding solubility and deformability characteristics.
  • the water-soluble unit dose article comprises a liquid laundry detergent composition.
  • liquid laundry detergent composition refers to any laundry detergent composition comprising a liquid capable of wetting and treating a fabric, and includes, but is not limited to, liquids, gels, pastes, dispersions and the like.
  • the liquid composition can include solids or gases in suitably subdivided form, but the liquid composition excludes forms which are non-fluid overall, such as tablets or granules.
  • the liquid detergent composition can be used in a fabric hand wash operation or may be used in an automatic machine fabric wash operation.
  • the liquid laundry detergent composition comprises an amine oxide surfactant, a non-amine-oxide surfactant, a diol solvent and a polyol solvent. Particularly, the sum of the amounts of the diol solvent and the polyol solvent may be higher than the amount of the non-amine-oxide surfactant.
  • the liquid laundry detergent composition may further comprise a hydroxyl ether solvent.
  • a hydroxyl ether solvent Particularly, the sum of the amounts of the diol solvent, the polyol solvent and the hydroxyl ether solvent may be higher than the sum of the amounts of the amine oxide surfactant and the non-amine-oxide surfactant.
  • the liquid laundry detergent composition may comprise a cleaning or care polymer, preferably wherein the cleaning or care polymer is selected from an ethoxylated polyethyleneimine, alkoxylated polyalkyl phenol, an amphiphilic graft copolymer, a polyester terephthalate, a hydroxyethylcellulose, a carboxymethylcellulose or a mixture thereof.
  • a cleaning or care polymer selected from an ethoxylated polyethyleneimine, alkoxylated polyalkyl phenol, an amphiphilic graft copolymer, a polyester terephthalate, a hydroxyethylcellulose, a carboxymethylcellulose or a mixture thereof.
  • the water-soluble unit dose article may comprise an adjunct ingredient selected from hueing dyes, polymers, builders, dye transfer inhibiting agents, dispersants, enzymes, enzyme stabilizers, catalytic materials, bleach, bleach activators, polymeric dispersing agents, anti-redeposition agents, suds suppressors, aesthetic dyes, opacifiers, perfumes, perfume delivery systems, structurants, hydrotropes, processing aids, pigments and mixtures thereof.
  • an adjunct ingredient selected from hueing dyes, polymers, builders, dye transfer inhibiting agents, dispersants, enzymes, enzyme stabilizers, catalytic materials, bleach, bleach activators, polymeric dispersing agents, anti-redeposition agents, suds suppressors, aesthetic dyes, opacifiers, perfumes, perfume delivery systems, structurants, hydrotropes, processing aids, pigments and mixtures thereof.
  • the liquid laundry detergent composition is non-Newtonian.
  • a non-Newtonian liquid has properties that differ from those of a Newtonian liquid, more specifically, the viscosity of non-Newtonian liquids is dependent on shear rate, while a Newtonian liquid has a constant viscosity independent of the applied shear rate.
  • the liquid laundry detergent composition may have a viscosity of at least 2Pa. s at a shear rate of 0.5s-1 as measured using a TA Rheometer AR2000 at 25°C, preferably wherein the liquid detergent composition has a viscosity of between 2Pa. s and 35Pa. s, preferably between 2.5Pa. s and 30Pa. as, more preferably between 3Pa. s and 25Pa. s, even more preferably between 5Pa. s and 20Pa. s, most preferably between 10Pa. s and 16Pa. s at a shear rate of 0.5s-1 as measured using a TA Rheometer AR2000 at 25°C.
  • the liquid laundry detergent composition may comprise: a) from 2%to 8%, by weight of the composition, of an amine oxide surfactant which is dodecyldimethyl amine oxide and/or tetradecyldimethyl amine oxide, b) from 20%to 35%, by weight of the composition, of a non-amine-oxide surfactant which comprises a C 6 -C 20 LAS, a C 6 -C 20 AAS, and a C 6 -C 20 alkoxylated alcohol having a weight average degree of alkoxylation ranging from 7 to 10, c) from 20%to 36%, by weight of the composition, of a diol solvent comprising 1, 2-propanediol, 1, 3-propanediol, Methylpropanediol and dipropylene glycol, and d) from 5%to 16%, by weight of the composition, of a polyol solvent comprising glycerine, wherein the sum of the amounts of said dio
  • Typical amine oxide surfactants may include water-soluble amine oxides containing one R 1 C 8-18 alkyl moiety and two R 2 and R 3 moieties selected from the group consisting of C 1-3 alkyl groups and C 1-3 hydroxyalkyl groups.
  • amine oxide may be characterized by the formula R 1 –N (R 2 ) (R 3 ) O wherein R 1 is a C 8-18 alkyl and R 2 and R 3 re selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxethyl, 2-hydroxypropyl and 3-hydroxypropyl, preferably methyl.
  • the linear amine oxide surfactants in particular may include linear C 10 -C 18 alkyl dimethyl amine oxides and linear C 8 -C 12 alkoxy ethyl dihydroxy ethyl amine oxides.
  • Preferred amine oxides include linear C 10 , linear C 10 -C 12 , and linear C 12 -C 14 alkyl dimethyl amine oxides, most preferably linear C 12-14 alkyl dimethyl amine oxide.
  • the amine oxide surfactant may be present in an amount ranging from 0.3%to 30%, preferably from 0.5%to 20%, more preferably from 0.8%to 15%, most preferably from 1%to 10%, for example 2%, 4%, 6%, 8%, 10%or any ranges thereof, by weight of the composition.
  • the amine oxide surfactant may be selected from the group consisting of C 6 -C 20 alkyldimethyl amine oxides, C 6-20 amido alkyl dimethyl amine oxides and any combinations thereof. More preferably, the amine oxide surfactant may be selected from the group consisting of C 10 -C 16 alkyldimethyl amine oxides and any combinations thereof. Most preferably, the amine oxide surfactant may be selected from the group consisting of dodecyldimethyl amine oxide, tetradecyldimethyl amino oxide and any combinations thereof.
  • the liquid detergent composition of the present invention may comprise a non-amine-oxide surfactant which is preferably selected from the group consisting of an anionic surfactant, a non-ionic surfactant and any combinations thereof.
  • a non-amine-oxide surfactant which is preferably selected from the group consisting of an anionic surfactant, a non-ionic surfactant and any combinations thereof.
  • the non-amine-oxide surfactant is present in an amount ranging from 1%to 45%, preferably from 3%to 40%, more preferably from 5%to 37%, most preferably from 7%to 35%, by weight of the composition.
  • the anionic surfactant may be 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) , fatty acids and any combinations thereof.
  • LAS linear alkylbenzene sulfonates
  • AS alkyl sulfates
  • AAS alkyl alkoxy sulfates
  • MES C 6 -C 20 methyl ester sulfonates
  • AEC alkyl ether carboxylates
  • 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 non-ionic surfactant may be 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, the nonionic surfactant 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.
  • the non-amine-oxide surfactant may comprise an anionic surfactant and a non-ionic surfactant in which the anionic surfactant comprises a C 6 -C 20 LAS and optionally a C 6 -C 20 AS and/or a C 6 -C 20 AAS and the non-ionic surfactant 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.
  • 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 C 6 -C 20 LAS is present in an amount ranging from 1%to 20%, preferably from 2%to 15%, more preferably from 3%to 10%, by weight of the composition.
  • the C 6 -C 20 AAS is present in an amount ranging from 1%to 20%, preferably from 2%to 15%, more preferably from 3%to 10%, by weight of the composition.
  • the C 6 -C 20 alkoxylated alcohol is present in an amount ranging from 1%to 30%, preferably from 2%to 25%, more preferably from 3%to 20%, by weight of the composition.
  • the liquid detergent composition may comprise a non-aqueous solvent.
  • the liquid detergent composition may comprise a diol solvent and a polyol solvent, in which the weight ratio of said diol solvent to said polyol solvent is from 1.3: 1 to 5.5: 1, preferably from 1: 4 to 4.5: 1, more preferably from 1.5: 1 to 3.5: 1, for example 1.6: 1, 1.7: 1, 1.8: 1, 2: 1, 2.5: 1, 3: 1, 3.5: 1, 4: 1, 4.5: 1, 5: 1, 5.5: 1 or any ranges thereof.
  • diol solvent means a solvent which is an alcohol compound having two hydroxyl groups.
  • polyol solvent as used herein means a solvent which is an alcohol compound having three or more hydroxyl groups.
  • hydroxyl ether solvent means a solvent which is an ether compound having at least one hydroxyl group.
  • the sum of the amount of said diol solvent and said polyol solvent is from 20%to 65%, preferably from 25%to 60%, more preferably from 30%to 55%, most preferably from 35%to 50%, for example 35%, 40%, 45%, 50%or any ranges thereof, by weight of the composition.
  • the diol solvent may be present in an amount ranging from 10%to 40%, preferably from 15%to 35%, more preferably from 20%to 36%, for example 22%, 25%, 27%, 30%, 36%or any ranges thereof, by weight of the composition; and/or the polyol solvent is present in an amount ranging from 5%to 20%, preferably from 8%to 18%, more preferably from 10%to 16%, for example 11%, 12%, 13%, 14%, 15%or any ranges thereof, by weight of the composition.
  • the diol solvent is selected from the group consisting of ethylene glycol, 1, 2-propanediol (p-diol) , 1, 3-propanediol, Methylpropanediol, butanediol and any combinations thereof. More preferably, the diol solvent comprises 1, 2-propanediol.
  • the polyol solvent is selected from the group consisting of glycerine, butanetriol, pentaerythritol and any combinations thereof. More preferably, the polyol solvent comprises glycerine.
  • 1, 2-propanediol is present in an amount ranging from 5%to 40%, preferably from 10%to 35%, more preferably from 15%to 30%, by weight of the composition; and/or glycerin is present in an amount ranging from 1%to 30%, preferably from 3%to 25%, more preferably from 5%to 20%, by weight of the composition.
  • the liquid laundry detergent composition may further comprise a hydroxyl ether solvent.
  • the hydroxyl ether solvent may be present in an amount ranging from 0.1%to 20%, preferably from 1%to 15%, more preferably from 2%to 10%, for example 3%, 4%, 5%, 6%, 7%, 8%, 9%or any ranges therebetween, by weight of the composition.
  • the hydroxyl ether solvent may be selected from the group consisting of dipropylene glycol (DPG) , n-butoxy propoxy propanol (nBPP) , diethylene glycol, and any combinations thereof. More preferably, the hydroxyl ether solvent may comprise DPG.
  • the liquid detergent composition of the present invention may comprise a dye fixative.
  • 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 4%, more preferably from 0.1% to 3%, most preferably from 0.15%to 2%, for example 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%or any ranges therebetween, by weight of the composition.
  • a further aspect of the present invention is a method making a water-soluble unit dose article according to the present invention, wherein the liquid laundry detergent composition is prepared by preparing a base composition comprising the non-amine-oxide surfactant and adding the amine oxide surfactant to said base composition, wherein the amine oxide surfactant is added;
  • premix wherein said premix comprises the amine oxide surfactant and a non-aqueous solvent
  • the amine oxide surfactant –non-aqueous solvent premix preferably is substantially non-aqueous i.e. preferably comprising less than 20%more preferable less than 10%most preferably less than 5%of water.
  • This premix preferably comprises at least 10%preferably at least 20%more preferably at least 30%by weight of the premix of the amine oxide surfactant.
  • the premix may comprise at most 35%, preferably, 40%, more preferably 50%, even more preferably 60%by weight of the premix of the amine oxide surfactant.
  • a further aspect of the present invention is a method of washing comprising the steps of adding the water-soluble unit dose article according to the present invention to sufficient water to dilute the liquid detergent composition by a factor of at least 300 fold to create a wash liquor and contacting items to be washed with said wash liquor.
  • a further aspect of the present invention is a packaged product comprising a recloseable container and at least one water-soluble unit dose article according to the present invention comprised therein.
  • the storage receptacle is a flexible, preferably resealable, bag, a rigid, preferably recloseable, tub or a mixture thereof, preferably, wherein the storage receptacle comprises a child resistant closure.
  • suitable child resistant closures Those skilled in the art will be aware of suitable child resistant closures.
  • the package may be made from any suitable material.
  • the container may be made from metallic materials, Aluminium, plastic materials, cardboard materials , laminates, cellulose pulp materals or a mixture thereof.
  • the package may be made from a plastic material, preferably a polyolefin material.
  • the package may be made from polypropylene, polystyrene, polyethylene, polyethylene terephthalate, PVC or a mixture thereof or more durable engineering plastics like Acrylonitrile Butadiene Styrene (ABS) , Polycarbonates, Polyamides and the like
  • ABS Acrylonitrile Butadiene Styrene
  • the material used to make the container may comprise other ingredients, such as colorants, preservatives, plasticisers, UV stabilizers, Oxygen, perfume and moisture barriers recycled materials and the like.
  • a further aspect of the present invention is the use of an amphoteric surfactant in a liquid detergent composition comprised within a water-soluble unit dose article according to the present invention to provide excellent grease cleaning benefits and improved stability.
  • liquid detergent compositions ⁇ 10ml
  • the liquid detergent compositions ( ⁇ 10ml) containing all required ingredients were encapsulated into compartment (s) of the unit dose by using a polyvinyl-alcohol-based film in which the PVA film and the shape of the unit dose were the same with CN Ariel Laundry two chamber side-by-side pouches.
  • Step 2) Store the samples prepared in Step 1) sealed in closed container, under 40 ⁇ in an oven for a certain period (1, 2, 3 or 4 weeks) ;
  • weeping If there is any weeping on the surface of the unit dose article or inside the container wall, it is determined as “fail” . If there is no apparent weeping, it is determined as “pass” .
  • Phase separation (not maintaining homogeneous systems after Step 2) . If there is any phase separation such as the formation of separated layers, flocculation or becoming turbid, it is determined as “fail” . If there is no phase separation, it is determined as “pass” .
  • liquid detergent compositions ⁇ 10ml
  • the liquid detergent compositions ( ⁇ 10ml) containing all required ingredients were encapsulated into compartment (s) of the unit dose by using a polyvinyl-alcohol-based film in which the PVA film and the shape of the unit dose were the same with CN Ariel Laundry two chamber side-by-side pouches.
  • Step 2) Store the samples prepared in Step 1) sealed in closed container, under 40 ⁇ in an oven for a certain period (1, 2, 3 or 4 weeks) ;
  • Example 1 Stability of Unit Dose Article Containing Amine Oxide, Diol Solvent and Polyol Solvent
  • sample unit dose articles comprising liquid detergent compositions were prepared containing the following ingredients, in which all samples contain an amine oxide surfactant, an anionic surfactant, a non-ionic surfactant, a diol solvent and a polyol solvent with different ratio of the diol solvent to the polyol solvent.
  • the liquid detergent compositions ( ⁇ 10ml) were encapsulated into compartment (s) of the unit dose by using a polyvinyl-alcohol-based film in which the PVA film and the shape of the unit dose were the same with CN Ariel Laundry two chamber side-by-side pouches.
  • Dye fixative poly (2-hydroxypropyldimethylammonium chloride) commercially available under the trade name of TEXCARE DFC 6 from Clariant.
  • sample unit dose articles comprising liquid detergent compositions were prepared containing the following ingredients, in which all samples contain an amine oxide surfactant, an anionic surfactant, a non-ionic surfactant, a diol solvent (i.e. P-diol) and a polyol solvent (i.e. glycerine) and only Sample 6 further comprises a hydroxyl ether solvent (i.e. DPG) .
  • the liquid detergent compositions ( ⁇ 10ml) were encapsulated into compartment (s) of the unit dose by using a polyvinyl-alcohol-based film in which the PVA film and the shape of the unit dose were the same with CN Ariel Laundry two chamber side-by-side pouches.
  • Dye fixative poly (2-hydroxypropyldimethylammonium chloride) commercially available under the trade name of TEXCARE DFC 6 from Clariant.
  • Sample 6 Sample 7
  • Sample 8 Hydroxyl Ether Solvent wt% 6% -- -- Ratio of Diol/Polyol 2.1: 1 2.0: 1 3.0: 1 Tightness 10.7mm 9.5mm 9.4mm

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Abstract

The present invention relates to water-soluble unit dose articles comprising an amine oxide surfactant together with a diol solvent and a polyol solvent, as well as methods of making.

Description

WATER-SOLUBLE UNIT DOSE ARTICLE COMPRISING AMINE OXIDE SURFACTANT, DIOL SOLVENT AND POLYOL SOLVENT FIELD OF THE INVENTION
The present invention relates to water-soluble unit dose articles comprising an amine oxide surfactant, a diol solvent and a polyol solvent, as well as methods of making.
BACKGROUND OF THE INVENTION
Water-soluble unit dose articles are liked by consumers due their convenience and ease of use. Consumers also like the fact that they do not need to measure a detergent dose and so this eliminates accidental spillage during the dosing operation. Accidental dosage can be messy and inconvenient.
On the other hand, an amphoteric surfactant, particularly amine oxide surfactant is commonly used in personal care products (e.g. shower body lotions) , hair care products (e.g. shampoo) , and home care products (e.g. dish washing) . Amine oxide surfactants have a great performance in the aspect of grease cleaning. However, in the area of fabric care, the use of amine oxide surfactants is very limiting. Especially, for laundry products in the form of water-soluble unit dose, it is quite difficult to formulate a highly concentrated liquid detergent composition in the presence of amine oxide surfactants. Because the commercially available raw materials of amine oxides are aqueous solution containing around 60%to 70%water, the addition of amine oxides may introduce too much water resulting in instability of water-soluble unit dose articles (e.g. liquid leakage from prematurely ruptured unit dose articles) .
In order to formulate a stable water-soluble unit dose article containing an amine oxide surfactant, a possible approach is to increase the content of non-aqueous solvent so as to maintain a tolerably low level of water content in the liquid detergent composition contained in the water-soluble unit dose article. However, such increased level of non-aqueous solvents can be also problematic. Also, it was unexpected how such non-aqueous solvents work at a relatively high level in the context of concentrated liquid detergent compositions. Particularly, it was found that some non-aqueous solvents at a relatively high level cannot provide a stable liquid detergent composition (e.g., occurrence of phase separation and/or flocculation) and some non-aqueous solvents might cause “weeping” phenomenon, i.e., solvent might migrate through the water-soluble film to the outside of the water-soluble unit dose article. Thus, there is a need for stable  laundry detergent products in the form of water-soluble unit dose articles that contain amine oxide surfactants.
It was surprisingly found that a water-soluble unit dose article comprising a liquid detergent composition wherein the liquid detergent composition comprises a diol solvent and a polyol solvent at a preferred ratio (e.g. from 1.25: 1 to 6: 1) solved the above technical problem, i.e. to provide a water-soluble unit dose article containing an amine oxide surfactant without any intolerable defects (e.g. significant weeping or instability) .
SUMMARY OF THE INVENTION
The present invention in one aspect relates to a water-soluble unit dose article comprising a water-soluble film and a liquid laundry detergent composition wrapped with the water-soluble film, wherein the liquid laundry detergent composition comprises: a) from 0.1%to 50%, by weight of the composition, of an amine oxide surfactant, b) from 0.1%to 50%, by weight of the composition, of a non-amine-oxide surfactant, c) from 0.1%to 40%, by weight of the composition, of a diol solvent, and d) from 0.1%to 30%, by weight of the composition, of a polyol solvent, wherein the sum of the amounts of said diol solvent and said polyol solvent is higher than the amount of the non-amine-oxide surfactant, and wherein the weight ratio of said diol solvent to said polyol solvent is from 1.25: 1 to 6: 1.
A second aspect of the present invention is a packaged product comprising a recloseable container and at least one water-soluble unit dose article according to the present invention.
A third aspect of the present invention is a method making a water-soluble unit dose article according to the present invention, wherein the liquid laundry detergent composition is prepared by preparing a base composition comprising the non-amine-oxide surfactant and adding the amine oxide surfactant to said base composition, wherein the amine oxide surfactant is added in the form of a powder or a premix wherein said premix comprises the amine oxide surfactant and the diol solvent and the polyol solvent.
It is an advantage of the water-soluble unit dose article to provide an improved stability of the water-soluble unit dose article containing an amine oxide surfactant.
It is another advantage of the water-soluble unit dose article to deliver an excellent grease cleaning performance.
It is another advantage of the water-soluble unit dose article to provide an improved mechanical performance of the water-soluble unit dose article (e.g., improved pouch tightness to have better feel when consumer hold the pouch as well as improved shape retention after story. ) .
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 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 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 "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.
Water-soluble unit dose article
The present invention discloses a water-soluble unit dose article comprising a water-soluble film and a liquid laundry detergent composition. Particularly, the liquid laundry detergent composition is wrapped with the water-soluble film. The water-soluble film and the liquid detergent composition are described in more detail below.
The water-soluble unit dose article comprises the water-soluble film shaped such that the unit-dose article comprises at least one internal compartment surrounded by the water-soluble film. The unit dose article may comprise a first water-soluble film and a second water-soluble film sealed to one another such to define the internal compartment. The water-soluble unit dose article is constructed such that the detergent composition does not leak out of the compartment during storage. However, upon addition of the water-soluble unit dose article to water, the water-soluble film dissolves and releases the contents of the internal compartment into the wash liquor.
The compartment should be understood as meaning a closed internal space within the unit dose article, which holds the detergent composition. During manufacture, a first water-soluble film may be shaped to comprise an open compartment into which the detergent composition is added. A second water-soluble film is then laid over the first film in such an orientation as to close the opening of the compartment. The first and second films are then sealed together along a seal region.
The unit dose article may comprise more than one compartment, even at least two compartments, or even at least three compartments. The compartments may be arranged in superposed orientation, i.e. one positioned on top of the other. In such an orientation the unit dose article will comprise three films, top, middle and bottom. Alternatively, the compartments may be positioned in a side-by-side orientation, i.e. one orientated next to the other. The compartments may even be orientated in a ‘tyre and rim’ arrangement, i.e. a first compartment is positioned next to a second compartment, but the first compartment at least partially surrounds the second compartment, but does not completely enclose the second compartment. Alternatively one compartment may be completely enclosed within another compartment.
Wherein the unit dose article comprises at least two compartments, one of the compartments may be smaller than the other compartment. Wherein the unit dose article comprises at least three compartments, two of the compartments may be smaller than the third compartment, and preferably the smaller compartments are superposed on the larger compartment. The superposed compartments preferably are orientated side-by-side.
In a multi-compartment orientation, the detergent composition according to the present invention may be comprised in at least one of the compartments. It may for example be  comprised in just one compartment, or may be comprised in two compartments, or even in three compartments.
Each compartment may comprise the same or different compositions. The different compositions could all be in the same form, or they may be in different forms.
The water-soluble unit dose article may comprise at least two internal compartments, wherein the liquid laundry detergent composition is comprised in at least one of the compartments, preferably wherein the unit dose article comprises at least three compartments, wherein the detergent composition is comprised in at least one of the compartments.
Water-soluble film
The film of the present invention is soluble or dispersible in water. The water-soluble film preferably comprises polyvinyl alcohol or a copolymer thereof. Preferably, the water-soluble film comprises a blend of at least two different polyvinylalcohol homopolymers, at least two different polyvinylalcohol copolymers, at least one polyvinylalcohol homopolymer and at least one polyvinylalcohol copolymer or a combination thereof.
Preferably, the water-soluble film has a thickness between 50microns and 100microns, preferably between 70 microns and 90 microns before being deformed into a unit dose article.
Preferably, the film has a water-solubility of at least 50%, preferably at least 75%or even at least 95%, as measured by the method set out here after using a glass-filter with a maximum pore size of 20 microns:
5 grams ± 0.1 gram of film material is added in a pre-weighed 3L beaker and 2L ± 5ml of distilled water is added. This is stirred vigorously on a magnetic stirrer, Labline model No. 1250 or equivalent and 5 cm magnetic stirrer, set at 600 rpm, for 30 minutes at 30℃. Then, the mixture is filtered through a folded qualitative sintered-glass filter with a pore size as defined above (max. 20 micron) . The water is dried off from the collected filtrate by any conventional method, and the weight of the remaining material is determined (which is the dissolved or dispersed fraction) . Then, the percentage solubility or dispersability can be calculated.
Preferred film materials are preferably polymeric materials. The film material can, for example, be obtained by casting, blow-moulding, extrusion or blown extrusion of the polymeric material, as known in the art.
Preferred polymers, copolymers or derivatives thereof suitable for use as pouch material are selected from polyvinyl alcohols, polyvinyl pyrrolidone, polyalkylene oxides, acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates,  polycarboxylic acids and salts, polyaminoacids or peptides, polyamides, polyacrylamide, copolymers of maleic/acrylic acids, polysaccharides including starch and gelatine, natural gums such as xanthum and carragum. More preferred polymers are selected from polyacrylates and water-soluble acrylate copolymers, methylcellulose, carboxymethylcellulose sodium, dextrin, ethylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose, maltodextrin, polymethacrylates, and most preferably selected from polyvinyl alcohols, polyvinyl alcohol copolymers and hydroxypropyl methyl cellulose (HPMC) , and combinations thereof. Preferably, the level of polymer in the pouch material, for example a PVA polymer, is at least 60%. The polymer can have any weight average molecular weight, preferably from about 1000 to 1,000,000, more preferably from about 10,000 to 300,000 yet more preferably from about 20,000 to 150,000.
Preferably, the water-soluble unit dose article comprises polyvinylalcohol.
Mixtures of polymers can also be used as the pouch material. This can be beneficial to control the mechanical and/or dissolution properties of the compartments or pouch, depending on the application thereof and the required needs. Suitable mixtures include for example mixtures wherein one polymer has a higher water-solubility than another polymer, and/or one polymer has a higher mechanical strength than another polymer. Also suitable are mixtures of polymers having different weight average molecular weights, for example a mixture of PVA or a copolymer thereof of a weight average molecular weight of about 10,000-40,000, preferably around 20,000, and of PVA or copolymer thereof, with a weight average molecular weight of about 100,000 to 300,000, preferably around 150,000. Also suitable herein are polymer blend compositions, for example comprising hydrolytically degradable and water-soluble polymer blends such as polylactide and polyvinyl alcohol, obtained by mixing polylactide and polyvinyl alcohol, typically comprising about 1-35%by weight polylactide and about 65%to 99%by weight polyvinyl alcohol.
Preferred for use herein are PVA polymers which are from about 60%to about 98%hydrolysed, preferably about 80%to about 90%hydrolysed, to improve the dissolution characteristics of the material.
Preferred films exhibit good dissolution in cold water, meaning unheated distilled water. Preferably such films exhibit good dissolution at temperatures of 24℃, even more preferably at 10℃. By good dissolution it is meant that the film exhibits water-solubility of at least 50%, preferably at least 75%or even at least 95%, as measured by the method set out here after using a glass-filter with a maximum pore size of 20 microns, described above.
Preferred films are those supplied by Monosol.
Of the total PVA resin content in the film described herein, the PVA resin can comprise about 30 to about 85 wt%of the first PVA polymer, or about 45 to about 55 wt%of the first PVA polymer. For example, the PVA resin can contain about 50 w. %of each PVA polymer, wherein the viscosity of the first PVA polymer is about 13 cP and the viscosity of the second PVA polymer is about 23 cP, measured as a 4%polymer solution in demineralized water at 20℃.
Preferably the film comprises a blend of at least two different polyvinylalcohol homopolymers and/or copolymers.
Most preferably the water soluble film comprises a blend of at least two different polyvinylalcohol homopolymers, especially a water soluble film comprising a blend of at least two different polyvinylalcohol homopolymers of different average molecular weight, especially a blend of 2 different polyvinylalcohol homopolymers having an absolute average viscosity difference |μ 2 -μ 1| for the first PVOH homopolymer and the second PVOH homopolymer, measured as a 4%polymer solution in demineralized water, in a range of 5 cP to about 15 cP, and both homopolymers having an average degree of hydrolysis between 85%and 95%preferably between 85%and 90%. The first homopolymer preferably has an average viscosity of 10 to 20 cP preferably 10 to 15 cP The second homopolymer preferably has an average viscosity of 20 to 30 cP preferably 20 to 25 cP. Most preferably the two homopolymers are blended in a 40/60 to a 60/40 weight %ratio.
Alternatively the water soluble film comprises a polymer blend comprising at least one copolymer comprising polyvinylalcohol and anionically modified monomer units. In particular the polymer blend might comprise a 90/10 to 50/50 weight %ratio of a polyvinylalcohol homopolymer and a copolymer comprising polyvinylalcohol and anionically modified monomer units. Alternatively the polymer blend might comprise a 90/10 to 10/90 weight %ratio of two different copolymers comprising polyvinylalcohol and anionically modified monomer units.
General classes of anionic monomer units which can be used for the PVOH corpolymer include the vinyl polymerization units corresponding to monocarboxylic acid vinyl monomers, their esters and anhydrides, dicarboxylic monomers having a polymerizable double bond, their esters and anhydrides, vinyl sulfonic acid monomers, and alkali metal salts of any of the foregoing. Examples of suitable anionic monomer units include the vinyl polymerization units corresponding to vinyl anionic monomers including vinyl acetic acid, maleic acid, monoalkyl maleate, dialkyl maleate, monomethyl maleate, dimethyl maleate, maleic anyhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, fumaric  anyhydride, itaconic acid, monomethyl itaconate, dimethyl itaconate, itaconic anhydride, vinyl sulfonic acid, allyl sulfonic acid, ethylene sulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid, 2-sufoethyl acrylate, alkali metal salts of the foregoing (e.g., sodium, potassium, or other alkali metal salts) , esters of the foregoing (e.g., methyl, ethyl, or other C 1-C 4 or C 6 alkyl esters) , and combinations thereof (e.g., multiple types of anionic monomers or equivalent forms of the same anionic monomer) . In an aspect, the anionic monomer can be one or more acrylamido methylpropanesulfonic acids (e.g., 2-acrylamido-1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid) , alkali metal salts thereof (e.g., sodium salts) , and combinations thereof. In an aspect, the anionic monomer can be one or more of monomethyl maleate, alkali metal salts thereof (e.g., sodium salts) , and combinations thereof.
The level of incorporation of the one or more anionic monomer units in the PVOH copolymers is not particularly limited. In some aspects, the one or more anionic monomer units are present in a PVOH copolymer in an amount in a range of about 2 mol. %to about 10 mol. % (e.g., at least 2.0, 2.5, 3.0, 3.5, or 4.0 mol. %and/or up to about 3.0, 4.0, 4.5, 5.0, 6.0, 8.0, or 10 mol. %in various embodiments) , individually or collectively.
Naturally, different film material and/or films of different thickness may be employed in making the compartments of the present invention. A benefit in selecting different films is that the resulting compartments may exhibit different solubility or release characteristics.
The film material herein can also comprise one or more additive ingredients. For example, it can be beneficial to add plasticisers, for example glycerol, ethylene glycol, diethyleneglycol, propylene glycol, dipropylene glycol (DPG) , sorbitol and mixtures thereof. Other additives may include water and functional detergent additives, including surfactant, to be delivered to the wash water, for example organic polymeric dispersants, etc.
Preferred films are those supplied by Monosol under the trade references M8630, M8900, M8779, M8310, films described in US 6 166 117 and US 6 787 512 and PVA films of corresponding solubility and deformability characteristics.
Liquid laundry detergent composition
The water-soluble unit dose article comprises a liquid laundry detergent composition. The term ‘liquid laundry detergent composition’ refers to any laundry detergent composition comprising a liquid capable of wetting and treating a fabric, and includes, but is not limited to,  liquids, gels, pastes, dispersions and the like. The liquid composition can include solids or gases in suitably subdivided form, but the liquid composition excludes forms which are non-fluid overall, such as tablets or granules.
The liquid detergent composition can be used in a fabric hand wash operation or may be used in an automatic machine fabric wash operation.
The liquid laundry detergent composition comprises an amine oxide surfactant, a non-amine-oxide surfactant, a diol solvent and a polyol solvent. Particularly, the sum of the amounts of the diol solvent and the polyol solvent may be higher than the amount of the non-amine-oxide surfactant.
The liquid laundry detergent composition may further comprise a hydroxyl ether solvent. Particularly, the sum of the amounts of the diol solvent, the polyol solvent and the hydroxyl ether solvent may be higher than the sum of the amounts of the amine oxide surfactant and the non-amine-oxide surfactant.
The liquid laundry detergent composition may comprise a cleaning or care polymer, preferably wherein the cleaning or care polymer is selected from an ethoxylated polyethyleneimine, alkoxylated polyalkyl phenol, an amphiphilic graft copolymer, a polyester terephthalate, a hydroxyethylcellulose, a carboxymethylcellulose or a mixture thereof.
The water-soluble unit dose article may comprise an adjunct ingredient selected from hueing dyes, polymers, builders, dye transfer inhibiting agents, dispersants, enzymes, enzyme stabilizers, catalytic materials, bleach, bleach activators, polymeric dispersing agents, anti-redeposition agents, suds suppressors, aesthetic dyes, opacifiers, perfumes, perfume delivery systems, structurants, hydrotropes, processing aids, pigments and mixtures thereof.
Preferably, the liquid laundry detergent composition is non-Newtonian. Without wishing to be bound by theory, a non-Newtonian liquid has properties that differ from those of a Newtonian liquid, more specifically, the viscosity of non-Newtonian liquids is dependent on shear rate, while a Newtonian liquid has a constant viscosity independent of the applied shear rate.
The liquid laundry detergent composition may have a viscosity of at least 2Pa. s at a shear rate of 0.5s-1 as measured using a TA Rheometer AR2000 at 25℃, preferably wherein the liquid detergent composition has a viscosity of between 2Pa. s and 35Pa. s, preferably between 2.5Pa. s and 30Pa. as, more preferably between 3Pa. s and 25Pa. s, even more preferably between 5Pa. s and 20Pa. s, most preferably between 10Pa. s and 16Pa. s at a shear rate of 0.5s-1 as measured using a TA Rheometer AR2000 at 25℃.
In an embodiment, the liquid laundry detergent composition may comprise: a) from 2%to 8%, by weight of the composition, of an amine oxide surfactant which is dodecyldimethyl amine oxide and/or tetradecyldimethyl amine oxide, b) from 20%to 35%, by weight of the composition, of a non-amine-oxide surfactant which comprises a C 6-C 20 LAS, a C 6-C 20 AAS, and a C 6-C 20 alkoxylated alcohol having a weight average degree of alkoxylation ranging from 7 to 10, c) from 20%to 36%, by weight of the composition, of a diol solvent comprising 1, 2-propanediol, 1, 3-propanediol, Methylpropanediol and dipropylene glycol, and d) from 5%to 16%, by weight of the composition, of a polyol solvent comprising glycerine, wherein the sum of the amounts of said diol solvent and said polyol solvent is higher than the amount of the non-amine-oxide surfactant, and wherein the weight ratio of said diol solvent to said polyol solvent is from 1.5: 1 to 3: 1.
Amine oxide surfactant
Typical amine oxide surfactants may include water-soluble amine oxides containing one R 1 C 8-18 alkyl moiety and two R 2 and R 3 moieties selected from the group consisting of C 1-3 alkyl groups and C 1-3 hydroxyalkyl groups. Preferably amine oxide may be characterized by the formula R 1 –N (R 2) (R 3) O wherein R 1 is a C 8-18 alkyl and R 2 and R 3 re selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxethyl, 2-hydroxypropyl and 3-hydroxypropyl, preferably methyl. The linear amine oxide surfactants in particular may include linear C 10-C 18 alkyl dimethyl amine oxides and linear C 8-C 12 alkoxy ethyl dihydroxy ethyl amine oxides. Preferred amine oxides include linear C 10, linear C 10-C 12, and linear C 12-C 14 alkyl dimethyl amine oxides, most preferably linear C 12-14 alkyl dimethyl amine oxide.
In some embodiments, the amine oxide surfactant may be present in an amount ranging from 0.3%to 30%, preferably from 0.5%to 20%, more preferably from 0.8%to 15%, most preferably from 1%to 10%, for example 2%, 4%, 6%, 8%, 10%or any ranges thereof, by weight of the composition.
Preferably, the amine oxide surfactant may be selected from the group consisting of C 6-C 20 alkyldimethyl amine oxides, C 6-20 amido alkyl dimethyl amine oxides and any combinations thereof. More preferably, the amine oxide surfactant may be selected from the group consisting of C 10-C 16 alkyldimethyl amine oxides and any combinations thereof. Most preferably, the amine oxide surfactant may be selected from the group consisting of dodecyldimethyl amine oxide, tetradecyldimethyl amino oxide and any combinations thereof.
Non-amine-oxide surfactant
The liquid detergent composition of the present invention may comprise a non-amine-oxide surfactant which is preferably selected from the group consisting of an anionic surfactant, a non-ionic surfactant and any combinations thereof. Particularly, the non-amine-oxide surfactant is present in an amount ranging from 1%to 45%, preferably from 3%to 40%, more preferably from 5%to 37%, most preferably from 7%to 35%, by weight of the composition.
Preferably, the anionic surfactant may be 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) , fatty acids 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.
Preferably, the non-ionic surfactant may be 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, the nonionic surfactant 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.
In some embodiments, the non-amine-oxide surfactant may comprise an anionic surfactant and a non-ionic surfactant in which the anionic surfactant comprises a C 6-C 20 LAS and optionally a C 6-C 20 AS and/or a C 6-C 20 AAS and the non-ionic surfactant 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.
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.
In some embodiments, the C 6-C 20 LAS is present in an amount ranging from 1%to 20%, preferably from 2%to 15%, more preferably from 3%to 10%, by weight of the composition.
In some embodiments, the C 6-C 20 AAS is present in an amount ranging from 1%to 20%, preferably from 2%to 15%, more preferably from 3%to 10%, by weight of the composition.
In some embodiments, the C 6-C 20 alkoxylated alcohol is present in an amount ranging from 1%to 30%, preferably from 2%to 25%, more preferably from 3%to 20%, by weight of the composition.
Solvents
The liquid detergent composition may comprise a non-aqueous solvent. Particularly, the liquid detergent composition may comprise a diol solvent and a polyol solvent, in which the weight ratio of said diol solvent to said polyol solvent is from 1.3: 1 to 5.5: 1, preferably from 1: 4 to 4.5: 1, more preferably from 1.5: 1 to 3.5: 1, for example 1.6: 1, 1.7: 1, 1.8: 1, 2: 1, 2.5: 1, 3: 1, 3.5: 1, 4: 1, 4.5: 1, 5: 1, 5.5: 1 or any ranges thereof.
The term of “diol solvent” as used herein means a solvent which is an alcohol compound having two hydroxyl groups. The term of “polyol solvent” as used herein means a solvent which is an alcohol compound having three or more hydroxyl groups. The term of “hydroxyl ether solvent” as used herein means a solvent which is an ether compound having at least one hydroxyl group.
In some embodiments, the sum of the amount of said diol solvent and said polyol solvent is from 20%to 65%, preferably from 25%to 60%, more preferably from 30%to 55%, most preferably from 35%to 50%, for example 35%, 40%, 45%, 50%or any ranges thereof, by weight of the composition.
Particularly, the diol solvent may be present in an amount ranging from 10%to 40%, preferably from 15%to 35%, more preferably from 20%to 36%, for example 22%, 25%, 27%, 30%, 36%or any ranges thereof, by weight of the composition; and/or the polyol solvent is present in an amount ranging from 5%to 20%, preferably from 8%to 18%, more preferably from 10%to 16%, for example 11%, 12%, 13%, 14%, 15%or any ranges thereof, by weight of the composition.
Preferably, the diol solvent is selected from the group consisting of ethylene glycol, 1, 2-propanediol (p-diol) , 1, 3-propanediol, Methylpropanediol, butanediol and any combinations thereof. More preferably, the diol solvent comprises 1, 2-propanediol.
Preferably, the polyol solvent is selected from the group consisting of glycerine, butanetriol, pentaerythritol and any combinations thereof. More preferably, the polyol solvent comprises glycerine.
In some embodiments, 1, 2-propanediol is present in an amount ranging from 5%to 40%, preferably from 10%to 35%, more preferably from 15%to 30%, by weight of the composition;  and/or glycerin is present in an amount ranging from 1%to 30%, preferably from 3%to 25%, more preferably from 5%to 20%, by weight of the composition.
Furthermore, the liquid laundry detergent composition may further comprise a hydroxyl ether solvent. Particularly, the hydroxyl ether solvent may be present in an amount ranging from 0.1%to 20%, preferably from 1%to 15%, more preferably from 2%to 10%, for example 3%, 4%, 5%, 6%, 7%, 8%, 9%or any ranges therebetween, by weight of the composition.
Preferably, the hydroxyl ether solvent may be selected from the group consisting of dipropylene glycol (DPG) , n-butoxy propoxy propanol (nBPP) , diethylene glycol, and any combinations thereof. More preferably, the hydroxyl ether solvent may comprise DPG.
Dye fixatives
The liquid detergent composition of the present invention may comprise a dye fixative. 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
Figure PCTCN2021112267-appb-000001
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) :
Figure PCTCN2021112267-appb-000002
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 4%, more preferably from 0.1% to 3%, most preferably from 0.15%to 2%, for example 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%or any ranges therebetween, by weight of the composition.
Method of making
Those skilled in the art will know how to make the unit dose article and liquid laundry detergent composition of the present invention using known techniques in the art.
A further aspect of the present invention is a method making a water-soluble unit dose article according to the present invention, wherein the liquid laundry detergent composition is prepared by preparing a base composition comprising the non-amine-oxide surfactant and adding the amine oxide surfactant to said base composition, wherein the amine oxide surfactant is added;
a. in the form of a powder; or
b. a premix wherein said premix comprises the amine oxide surfactant and a non-aqueous solvent; or
c. a mixture thereof.
The amine oxide surfactant –non-aqueous solvent premix preferably is substantially non-aqueous i.e. preferably comprising less than 20%more preferable less than 10%most preferably less than 5%of water. This premix preferably comprises at least 10%preferably at least 20%more preferably at least 30%by weight of the premix of the amine oxide surfactant. The premix may comprise at most 35%, preferably, 40%, more preferably 50%, even more preferably 60%by weight of the premix of the amine oxide surfactant.
Method of washing
A further aspect of the present invention is a method of washing comprising the steps of adding the water-soluble unit dose article according to the present invention to sufficient water to dilute the liquid detergent composition by a factor of at least 300 fold to create a wash liquor and contacting items to be washed with said wash liquor.
Packaged product
A further aspect of the present invention is a packaged product comprising a recloseable container and at least one water-soluble unit dose article according to the present invention comprised therein.
Those skilled in the art will be aware of relevant storage receptacles. Preferably, the storage receptacle is a flexible, preferably resealable, bag, a rigid, preferably recloseable, tub or a mixture thereof, preferably, wherein the storage receptacle comprises a child resistant closure. Those skilled in the art will be aware of suitable child resistant closures.
The package may be made from any suitable material. The container may be made from metallic materials, Aluminium, plastic materials, cardboard materials , laminates, cellulose pulp materals or a mixture thereof. The package may be made from a plastic material, preferably a polyolefin material. The package may be made from polypropylene, polystyrene, polyethylene, polyethylene terephthalate, PVC or a mixture thereof or more durable engineering plastics like Acrylonitrile Butadiene Styrene (ABS) , Polycarbonates, Polyamides and the like The material used to make the container may comprise other ingredients, such as colorants, preservatives, plasticisers, UV stabilizers, Oxygen, perfume and moisture barriers recycled materials and the like.
Use
A further aspect of the present invention is the use of an amphoteric surfactant in a liquid detergent composition comprised within a water-soluble unit dose article according to the present invention to provide excellent grease cleaning benefits and improved stability.
Test Method
Test 1: Stability test
Stability test is conducted through visual inspection as below:
1) Prepare sample unit dose articles comprising liquid detergent compositions (~10ml) . The liquid detergent compositions (~10ml) containing all required ingredients were encapsulated into compartment (s) of the unit dose by using a polyvinyl-alcohol-based film in which the PVA film and the shape of the unit dose were the same with CN Ariel Laundry two chamber side-by-side pouches.
2) Store the samples prepared in Step 1) sealed in closed container, under 40□ in an oven for a certain period (1, 2, 3 or 4 weeks) ;
3) Visually inspect the samples to determine:
a) Weeping: If there is any weeping on the surface of the unit dose article or inside the container wall, it is determined as “fail” . If there is no apparent weeping, it is determined as “pass” .
b) Phase separation (not maintaining homogeneous systems after Step 2) . If there is  any phase separation such as the formation of separated layers, flocculation or becoming turbid, it is determined as “fail” . If there is no phase separation, it is determined as “pass” .
Test 2: Mechanical performance test
Mechanical performance test is conducted through tightness measurement as below:
1) Prepare sample unit dose articles comprising liquid detergent compositions (~10ml) . The liquid detergent compositions (~10ml) containing all required ingredients were encapsulated into compartment (s) of the unit dose by using a polyvinyl-alcohol-based film in which the PVA film and the shape of the unit dose were the same with CN Ariel Laundry two chamber side-by-side pouches.
2) Store the samples prepared in Step 1) sealed in closed container, under 40□ in an oven for a certain period (1, 2, 3 or 4 weeks) ;
3) Determine mechanical performance (tightness) of the pouch by using Instron Universal Materials Testing machine from Instron Industrial Products. Place the pouch horizontally on the center of the bottom compression plant. Set the compression force at 10N and record the compressed Height value on the output screen.
EXAMPLES
Example 1: Stability of Unit Dose Article Containing Amine Oxide, Diol Solvent and Polyol  Solvent
Five (5) sample unit dose articles comprising liquid detergent compositions were prepared containing the following ingredients, in which all samples contain an amine oxide surfactant, an anionic surfactant, a non-ionic surfactant, a diol solvent and a polyol solvent with different ratio of the diol solvent to the polyol solvent. The liquid detergent compositions (~10ml) were encapsulated into compartment (s) of the unit dose by using a polyvinyl-alcohol-based film in which the PVA film and the shape of the unit dose were the same with CN Ariel Laundry two chamber side-by-side pouches.
Table 1
Figure PCTCN2021112267-appb-000003
Figure PCTCN2021112267-appb-000004
1: Dye fixative: poly (2-hydroxypropyldimethylammonium chloride) commercially available under the trade name of TEXCARE DFC 6 from Clariant.
2: 1, 2-propanediol
3: Glycerine
Then, Samples 1 to 5 were tested for determining the stability in accordance with Test 1: Stability test as described hereinabove. The results of stability for these samples after storage for 3 weeks are shown in Table 2. Surprisingly, only within a preferred range of ratios of the diol solvent to the polyol solvent, the non-aqueous solvent can stabilize the liquid laundry detergent composition containing the amine oxide surfactant, i.e. to pass the all stability tests.
Table 2
Figure PCTCN2021112267-appb-000005
1: The juice is transparent and clear.
2: The juice becomes turbid due to phase separation.
Example 2: Mechanical Performance of Unit Dose Article Containing Amine Oxide, Diol  Solvent and Polyol Solvent
Three (3) sample unit dose articles comprising liquid detergent compositions were prepared containing the following ingredients, in which all samples contain an amine oxide surfactant, an anionic surfactant, a non-ionic surfactant, a diol solvent (i.e. P-diol) and a polyol solvent (i.e. glycerine) and only Sample 6 further comprises a hydroxyl ether solvent (i.e. DPG) . The liquid detergent compositions (~10ml) were encapsulated into compartment (s) of the unit dose by using a polyvinyl-alcohol-based film in which the PVA film and the shape of the unit dose were the same with CN Ariel Laundry two chamber side-by-side pouches.
Table 3
Figure PCTCN2021112267-appb-000006
1: Dye fixative: poly (2-hydroxypropyldimethylammonium chloride) commercially available under the trade name of TEXCARE DFC 6 from Clariant.
2: 1, 2-propanediol
3: Glycerine
4: DPG
Then, Samples 6 to 8 were tested for determining the mechanical performance in accordance with Test 2: Mechanical performance test as described hereinabove. The results of tightness for these samples after storage of 3 weeks are shown in Table 4. Surprisingly, the addition of DPG can provide surprisingly better mechanical performance, i.e., significantly improved pouch tightness which indicates improved elasticity.
Table 4
  Sample 6 Sample 7 Sample 8
Hydroxyl Ether Solvent wt% 6% -- --
Ratio of Diol/Polyol 2.1: 1 2.0: 1 3.0: 1
Tightness 10.7mm 9.5mm 9.4mm
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 (15)

  1. A water-soluble unit dose article comprising a water-soluble film and a liquid laundry detergent composition wrapped with the water-soluble film, wherein the liquid laundry detergent composition comprises:
    a) from 0.1%to 50%, by weight of the composition, of an amine oxide surfactant,
    b) from 0.1%to 50%, by weight of the composition, of a non-amine-oxide surfactant,
    c) from 0.1%to 40%, by weight of the composition, of a diol solvent, and
    d) from 0.1%to 30%, by weight of the composition, of a polyol solvent,
    wherein the sum of the amounts of said diol solvent and said polyol solvent is higher than the amount of the non-amine-oxide surfactant, and
    wherein the weight ratio of said diol solvent to said polyol solvent is from 1.25: 1 to 6: 1.
  2. The water-soluble unit dose article according to claim 1, wherein the weight ratio of said diol solvent to said polyol solvent is from 1.3: 1 to 5.5: 1, preferably from 1: 4 to 4.5: 1, more preferably from 1.5: 1 to 3.5: 1.
  3. The water-soluble unit dose article according to claim 1 or 2, wherein said diol solvent is present in an amount ranging from 10%to 40%, preferably from 15%to 36%, more preferably from 20%to 32%, by weight of the composition;
    preferably, wherein said diol solvent is selected from the group consisting of ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, butanediol and any combinations thereof;
    more preferably, wherein said diol solvent comprises 1, 2-propanediol.
  4. The water-soluble unit dose article according to claim 1 or 2, wherein said polyol solvent is present in an amount ranging from 5%to 20%, preferably from 8%to 18%, more preferably from 10%to 16%, by weight of the composition;
    preferably, wherein said polyol solvent is selected from the group consisting of glycerine, butanetriol, pentaerythritol and any combinations thereof; and
    more preferably, wherein said polyol solvent comprises glycerine.
  5. The water-soluble unit dose article according to any preceding claims, wherein said amine oxide surfactant is present in an amount ranging from 0.3%to 30%, preferably from 0.5%to 20%, more preferably from 0.8%to 15%, most preferably from 1%to 10%, by weight of the composition;
    preferably, wherein said amine oxide surfactant is selected from the group consisting of C 6-C 20 alkyldimethyl amine oxides, C 6-20 amido alkyl dimethyl amine oxides and any combinations thereof;
    more preferably, wherein said amine oxide surfactant is selected from the group consisting of C 10-C 16 alkyldimethyl amine oxides and any combinations thereof.
    most preferably, wherein said amine oxide surfactant is selected from the group consisting of dodecyldimethyl amine oxide, tetradecyldimethyl amino oxide and any combinations thereof.
  6. The water-soluble unit dose article according to any preceding claims, wherein. said non-amine-oxide surfactant is present in an amount ranging from 1%to 45%, preferably from 3%to 40%, more preferably from 5%to 37%, most preferably from 7%to 35%, by weight of the composition;
    preferably, wherein said non-amine-oxide surfactant comprises an anionic surfactant and/or a non-ionic surfactant;
    more preferably, wherein said non-amine-oxide surfactant comprises an anionic surfactant and/or a non-ionic surfactant in which said anionic surfactant is 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) , fatty acids and any combinations thereof and said non-ionic surfactant is 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;
    most preferably, wherein said non-amine-oxide surfactant comprises an anionic surfactant and a non-ionic surfactant in which said anionic surfactant comprises a C 6-C 20 LAS and optionally a C 6-C 20 AS and/or a C 6-C 20 AAS and said non-ionic surfactant  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.
  7. The water-soluble unit dose article according to any preceding claims, wherein the sum of the amount of said diol solvent and said polyol solvent is from 20%to 65%, preferably from 25%to 60%, more preferably from 30%to 55%, most preferably from 35%to 50%, by weight of the composition.
  8. The water-soluble unit dose article according to any preceding claims, wherein said liquid laundry detergent composition further comprises a hydroxyl ether solvent which is present in an amount ranging from 0.1%to 20%, preferably from 1%to 15%, more preferably from 2%to 10%, by weight of the composition;
    preferably, wherein said hydroxyl ether solvent is selected from the group consisting of dipropylene glycol (DPG) , n-butoxy propoxy propanol (nBPP) , diethylene glycol, and any combinations thereof; and
    more preferably, wherein said hydroxyl ether solvent comprises DPG.
  9. The water-soluble unit dose article according to any preceding claims, wherein said liquid laundry detergent composition further comprises a dye fixative which is present in an amount ranging from 0.02%to 5%, preferably from 0.05%to 4%, more preferably from 0.1%to 3%, most preferably from 0.15%to 2%, 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) .
  10. The water-soluble unit dose article according to any preceding claims, wherein the water-soluble film is a polymeric water-soluble film, preferably wherein the polymeric film comprises polyvinyl alcohol.
  11. The water-soluble unit dose article according to any preceding claims comprising an adjunct ingredient selected from hueing dyes, polymers, builders, dye transfer inhibiting agents, dispersants, enzymes, enzyme stabilizers, catalytic materials, bleach, bleach activators, polymeric dispersing agents, anti-redeposition agents, suds suppressors, aesthetic dyes, opacifiers, perfumes, perfume delivery systems, structurants, hydrotropes, processing aids, pigments and mixtures thereof.
  12. The water-soluble unit dose article according to any preceding claims, wherein the liquid laundry detergent composition comprises:
    a) from 2%to 8%, by weight of the composition, of an amine oxide surfactant which is dodecyldimethyl amine oxide and/or tetradecyldimethyl amine oxide,
    b) from 20%to 35%, by weight of the composition, of a non-amine-oxide surfactant which comprises a C 6-C 20 LAS, a C 6-C 20 AAS, and a C 6-C 20 alkoxylated alcohol having a weight average degree of alkoxylation ranging from 7 to 10,
    c) from 20%to 36%, by weight of the composition, of a diol solvent comprising 1,2-propanediol,
    d) from 5%to 16%, by weight of the composition, of a polyol solvent comprising glycerine, and
    e) from 3%to 10%, by weight of the composition, of a polyol solvent comprising DPG, and
    f) from 0.3%to 2%, by weight of the composition, of a dye fixative which is poly (2-hydroxypropyldimethylammonium chloride) ,
    wherein the sum of the amounts of said diol solvent and said polyol solvent is higher than the amount of the non-amine-oxide surfactant, and
    wherein the weight ratio of said diol solvent to said polyol solvent is from 2.0: 1 to 2.4: 1.
  13. The water-soluble unit dose article according to any one of Claims 6 to 10, wherein the C 6-C 20 LAS is present in an amount ranging from 1%to 20%, preferably from 2%to 15%, more preferably from 3%to 10%, by weight of the composition; and/or
    wherein the C 6-C 20 AAS is present in an amount ranging from 1%to 20%, preferably from 2%to 15%, more preferably from 3%to 10%, by weight of the composition; and/or
    wherein the C 6-C 20 alkoxylated alcohol is present in an amount ranging from 1%to 30%, preferably from 2%to 25%, more preferably from 3%to 20%, by weight of the composition; and/or
    wherein propylene glycol is present in an amount ranging from 5%to 40%, preferably from 10%to 35%, more preferably from 15%to 30%, by weight of the composition; and/or
    wherein dipropylene glycol is present in an amount ranging from 1%to 20%, preferably from 2%to 15%, more preferably from 3%to 10%, by weight of the composition; and/or
    wherein glycerin is present in an amount ranging from 1%to 30%, preferably from 3%to 25%, more preferably from 5%to 20%, by weight of the composition.
  14. A packaged product comprising a recloseable container and at least one water-soluble unit dose article according to any preceding claims comprised therein
  15. A method making a water-soluble unit dose article according to any one of Claims 1 to 12, wherein the liquid laundry detergent composition is prepared by preparing a base composition comprising the non-amine-oxide surfactant and adding the amine oxide surfactant to said base composition, wherein the amine oxide surfactant is added in the form of a powder or a premix wherein said premix comprises the amine oxide surfactant and the diol solvent and the polyol solvent.
PCT/CN2021/112267 2020-09-28 2021-08-12 Water-soluble unit dose article comprising amine oxide surfactant, diol solvent and polyol solvent Ceased WO2022062752A1 (en)

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CN202111138347.9A CN114317133A (en) 2020-09-28 2021-09-27 Water soluble unit dose articles comprising amine oxide surfactant, glycol solvent and polyol solvent

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PCT/CN2020/118325 WO2022061868A1 (en) 2020-09-28 2020-09-28 Laundry detergent composition containing dye fixative and amine oxide
PCT/CN2020/118408 WO2022061889A1 (en) 2020-09-28 2020-09-28 Laundry detergent composition containing dye fixative and linear alkylbenzene sulfonate
CNPCT/CN2020/118325 2020-09-28
CNPCT/CN2020/118408 2020-09-28
CNPCT/CN2020/138032 2020-12-21
PCT/CN2020/138032 WO2022133650A1 (en) 2020-12-21 2020-12-21 Laundry detergent composition containing dye fixative and stabilizing agent

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PCT/CN2021/112296 Ceased WO2022062755A1 (en) 2020-09-28 2021-08-12 Water-soluble unit dose article comprising laundry detergent composition containing dye fixative
PCT/CN2021/112267 Ceased WO2022062752A1 (en) 2020-09-28 2021-08-12 Water-soluble unit dose article comprising amine oxide surfactant, diol solvent and polyol solvent
PCT/CN2021/112297 Ceased WO2022062756A1 (en) 2020-09-28 2021-08-12 Water-soluble unit dose article comprising amine oxide surfactant with dominant non-aqueous solvent

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CN114317133A (en) 2022-04-12

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