WO2019049725A1 - 水系ゲル化剤を含む化粧料組成物、並びに該水系ゲル化剤及び該化粧料組成物の製造方法 - Google Patents
水系ゲル化剤を含む化粧料組成物、並びに該水系ゲル化剤及び該化粧料組成物の製造方法 Download PDFInfo
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/88—Polyamides
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/042—Gels
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
- A61K8/062—Oil-in-water emulsions
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/36—Carboxylic acids; Salts or anhydrides thereof
- A61K8/361—Carboxylic acids having more than seven carbon atoms in an unbroken chain; Salts or anhydrides thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
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- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
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- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8135—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers, e.g. vinyl esters (polyvinylacetate)
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- A—HUMAN NECESSITIES
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- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
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- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
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- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
- C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/48—Thickener, Thickening system
Definitions
- the present invention is a cosmetic composition having high salt resistance and temperature stability of viscosity, high temporal stability at the time of emulsification, and a good feel at the time of use, and an aqueous gelling agent contained in the cosmetic composition. And a method of producing the cosmetic composition.
- viscosity modifiers those well-known as gelling agents, and thickeners with a natural gelling agent such as carboxymethyl cellulose and hydroxyethyl cellulose, and an alkali such as polyacrylic acid and polyacrylic acid-containing copolymer
- a natural gelling agent such as carboxymethyl cellulose and hydroxyethyl cellulose
- an alkali such as polyacrylic acid and polyacrylic acid-containing copolymer
- alkali-thickening type gelling agents urethane-type gelling agents such as urethane-modified polyether, and the like.
- urethane type gelling agents are capable of freely gelling various kinds of products as compared with other gelling agents, being able to impart various viscosity to the added products, and less susceptible to pH and salt Many types are manufactured and used for many reasons.
- hydrophobically-modified polyether urethane forms unique gels (soft) and elastic gels, and gels having excellent temperature stability can be obtained, so it is used in various cosmetics etc. and widely used.
- Patent Documents 1 to 4 For example, Patent Documents 1 to 4).
- the hydrophobically modified polyether urethane can be used in combination with a polymeric thickener such as carboxyvinyl polymer and xanthan gum, and it is known that a cosmetic composition having excellent usability can be obtained.
- Patent Document 5 discloses a cosmetic composition comprising hydrophobic modified polyether urethane, carboxy vinyl polymer and xanthan gum, wherein the hydrophobic modified polyether urethane is associated by hydrophobic interaction in an aqueous solvent. Is disclosed.
- JP 2002-080329 A JP, 2011-006371, A JP, 2016-023180, A JP, 2014-040385, A JP 2000-239120 A
- the cosmetic composition described in Patent Document 5 may satisfy sufficient performance with respect to salt resistance and temperature stability of viscosity, it is all including the aging stability at the time of emulsification and the feeling at the time of use. The characteristics of the above did not meet the level of practicality, and the above performance was insufficient.
- the present invention relates to a cosmetic composition
- a cosmetic composition comprising the following components (A) and (B), wherein the viscosity of a 1% by mass aqueous solution of component (A) at 25 ° C. is 1,000 to 5,000 mPa.
- a cosmetic composition wherein the cloud point of a 1% by mass aqueous solution of component (A) is 60 ° C. or more and 80 ° C. or less, and the weight average molecular weight of component (A) is 10,000 to 30,000. is there.
- Component (A) an aqueous gelling agent represented by the following general formula (1)
- R 1 , R 2 , R 8 and R 9 each independently represent a hydrocarbon group having 4 to 20 carbon atoms, and R 3 , R 5 and R 7 each independently have 2 to 4 carbon atoms And R 4 and R 6 each independently represent a divalent hydrocarbon group having 3 to 16 carbon atoms, and a and e each independently represent a number of 10 to 100.
- D represents a number of 100 to 500, and g represents a number of 0 to 10.
- the present invention also provides a process for producing an aqueous gelling agent represented by the general formula (1), using the compounds of the general formulas (2) to (4) described later and a higher fatty acid metal salt as a catalyst. Furthermore, the present invention also provides a method for producing a cosmetic composition, which comprises the step of combining the aqueous gelling agent obtained by the above-mentioned production method with a polymeric thickener.
- the cosmetic composition of the present invention is high in the salt resistance and temperature stability of viscosity, and further, the temporal stability at the time of emulsification and the feel at the time of use are good.
- the component (A) constituting the cosmetic composition of the present invention is an aqueous gelling agent represented by the following general formula (1).
- R 1 , R 2 , R 8 and R 9 each independently represent a hydrocarbon group having 4 to 20 carbon atoms, and R 3 , R 5 and R 7 each independently have 2 to 4 carbon atoms
- R 4 and R 6 each independently represent a divalent hydrocarbon group having 3 to 16 carbon atoms, and a and e each independently represent a number of 10 to 100.
- D represents a number of 100 to 500
- g represents a number of 0 to 10.
- R 1 , R 2 , R 8 and R 9 each independently represent a hydrocarbon group having 4 to 20 carbon atoms, and examples of the hydrocarbon group include n-butyl and isobutyl.
- R 1 , R 2 , R 8 and R 9 are such hydrocarbon groups, it is not possible to obtain a cosmetic composition satisfying all the effects of the present invention, and in particular, at the time of emulsification. It is not possible to obtain a cosmetic composition having high stability over time.
- R 1 , R 2 , R 8 and R 9 may be identical to or different from each other.
- a saturated aliphatic hydrocarbon group and an unsaturated aliphatic hydrocarbon group are preferable, and a saturated aliphatic hydrocarbon group is more preferable because the effects of the present invention are easily obtained, and procurement and production of raw materials are easy.
- a saturated aliphatic hydrocarbon group having 5 to 18 carbon atoms is more preferable, a saturated aliphatic hydrocarbon group having 8 to 14 carbon atoms is still more preferable, and a saturated aliphatic hydrocarbon group having 10 to 12 carbon atoms is most preferable.
- R 3 , R 5 and R 7 each independently represent a divalent hydrocarbon group having 2 to 4 carbon atoms.
- the hydrocarbon group for example, ethylene group; propane-1,3-diyl (linear propylene) group; branched propylene group such as propane-1,2-diyl group, propane-2,2-diyl group; Butane-1,4-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-2,3-diyl group, butane-1,1-diyl group, butane-2,2
- a linear butylene group such as -diyl group; a branched butylene group such as 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, and the like.
- a divalent linear hydrocarbon group having 2 to 4 carbon atoms is preferable, and an ethylene group and propane-1,3-diyl (linear propylene) group are more preferable because the effects of the present invention can be easily obtained.
- ethylene groups are more preferred.
- R 3 may be all the same groups, may be different groups, and R 5 may also be all the same groups, may be different groups, R 7 In addition, all of them may be the same group or different groups.
- R 4 and R 6 each independently represent a divalent hydrocarbon group having 3 to 16 carbon atoms.
- the hydrocarbon group include a divalent aliphatic hydrocarbon group having 3 to 16 carbon atoms, an aromatic hydrocarbon group or an alicyclic hydrocarbon group. These hydrocarbon groups may have any carbon number in the range of 3 to 16.
- the two isocyanate groups are removed from the diisocyanate compound represented by the general formula (4) described later. This will be described in detail later.
- a and e each independently represent a number of 10 to 100. Among them, 12 to 50 is preferable and 15 to 30 is more preferable because the raw materials can be easily produced or obtained and the effects of the present invention can be easily obtained.
- D represents a number of 100 to 500. Among them, it is preferably 120 to 450, more preferably 150 to 400, still more preferably 180 to 350, since an aqueous gelling agent which can easily obtain the effects of the present invention can be obtained. Most preferably, it is ⁇ 300.
- G represents a number of 0 to 10; Among them, from the viewpoint of easily obtaining the effects of the present invention, it is preferably 0 to 8, and more preferably 0 to 6.
- the aqueous gelling agent in which g is 0 exhibits a function like a gelation accelerator when used in combination with the aqueous gelling agent in which g is 1 to 10.
- a mixture of an aqueous gelling agent wherein g is 0 and an aqueous gelling agent wherein g is 1 to 10 is more preferable since the effects of the invention are more easily obtained, and an aqueous member wherein g is 0 Still more preferably, it is a mixture of a gelling agent and an aqueous gelling agent having a g of 1 to 8, and a mixture of an aqueous gelling agent having a g of 0 and an aqueous gelling agent having a g of 1 to 6 Is most preferred.
- the aqueous gelation is mixed in a mass ratio of 95: 5 to 85:15 (the aqueous gelling agent having g of 1 to 10) and the aqueous gelling agent having g of 0 (zero). If it is an agent, it becomes possible to exhibit the effect of the present invention to the full.
- the water-based gelling agent is a mixture of (a water-based gelling agent whose g is 1 to 10) and (a water-based gelling agent whose g is 0) in a weight ratio of 95: 5 to 85:15. If it is possible to obtain an elastic soft gel which has particularly good self-smoothness and can be used in a spray bottle, it can be suitably used in a cosmetic which requires those effects.
- self-smoothness refers to the property of the gel to naturally return to its original smooth surface after being given a physical stimulus (eg, skimming the gel, scraping the gel, etc.).
- available as a spray bottle means that when it is contained in a spray bottle, it has the properties of an elastic soft gel, and when it is sprayed from the spray bottle (when the gel is subjected to shear stress) It has the property of being easily sprayed like water.
- the component (A) constituting the cosmetic composition of the present invention has a viscosity of 1,000 to 5,000 mPa ⁇ s of a 1% by mass aqueous solution at 25 ° C., and a cloud point of 60% or more of a 1% by mass aqueous solution
- It is an aqueous gelling agent represented by the general formula (1) which has a weight average molecular weight of 10,000 to 30,000 at a temperature of 80 ° C. or less.
- a manufacturing method of a component (A) it must be a method of obtaining the component (A) of the said property. This can be synthesized from the compounds represented by the following general formulas (2) to (4) as a raw material and in the presence of a specific catalyst.
- R 10 and R 11 each independently represent a hydrocarbon group having 4 to 20 carbon atoms
- R 12 represents a divalent hydrocarbon group having 2 to 4 carbon atoms
- r is 10 to 100
- R 13 represents a divalent hydrocarbon group having 2 to 4 carbon atoms, and t represents a number of 100 to 500).
- Q represents a divalent hydrocarbon group having 3 to 16 carbon atoms.
- R 10 and R 11 each independently represent a hydrocarbon group having 4 to 20 carbon atoms.
- the hydrocarbon group include n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, branched pentyl group, secondary pentyl group, tertiary pentyl group, n -Hexyl group, branched hexyl group, secondary hexyl group, tertiary hexyl group, n-heptyl group, branched heptyl group, secondary heptyl group, tertiary heptyl group, n-octyl group, 2- Ethylhexyl group, branched octyl group, secondary octyl group, tertiary octyl group, n-nonyl group, branched nonyl group, secondary nonyl group, secondary non
- R 10 and R 11 may be identical to or different from each other.
- a saturated aliphatic hydrocarbon group and an unsaturated aliphatic hydrocarbon group are preferable, and a saturated aliphatic hydrocarbon group is more preferable because the effects of the present invention are easily obtained, and procurement and production of raw materials are easy.
- a saturated aliphatic hydrocarbon group having 5 to 18 carbon atoms is more preferable, a saturated aliphatic hydrocarbon group having 8 to 14 carbon atoms is still more preferable, and a saturated aliphatic hydrocarbon group having 10 to 12 carbon atoms is most preferable.
- R 12 represents a divalent hydrocarbon group having 2 to 4 carbon atoms.
- the hydrocarbon group for example, ethylene group; propane-1,3-diyl (linear propylene) group; branched propylene group such as propane-1,2-diyl group, propane-2,2-diyl group; Butane-1,4-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-2,3-diyl group, butane-1,1-diyl group, butane-2,2 A linear butylene group such as -diyl group; a branched butylene group such as 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, and the like.
- a divalent linear hydrocarbon group having 2 to 4 carbon atoms is preferable, and an ethylene group and propane-1,3-diyl (linear propylene) group are more preferable because the effects of the present invention can be easily obtained.
- ethylene groups are more preferred.
- all R ⁇ 12> may be the same group, and may be different groups.
- R represents a number of 10 to 100. Among them, the number is preferably 12 to 50, and more preferably 15 to 30, because the compound of the general formula (2) is easily produced or obtained.
- R 13 represents a divalent hydrocarbon group having 2 to 4 carbon atoms, and examples of such a group include ethylene group; propane-1,3-diyl (linear propylene) group; propane Branched propylene groups such as -1,2-diyl group, propane-2,2-diyl group; butane-1,4-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, Straight-chain butylene groups such as butane-2,3-diyl group, butane-1,1-diyl group, butane-2,2-diyl group; 2-methylpropane-1,3-diyl group, 2-methylpropane- Examples thereof include branched butylene groups such as 1,2-diyl group.
- a divalent linear hydrocarbon group having 2 to 4 carbon atoms is preferable, and an ethylene group and propane-1,3-diyl (linear propylene) group are more preferable because the effects of the present invention can be easily obtained. And ethylene groups are more preferred.
- R 13 may all be the same group or may be different groups.
- t represents a number of 100 to 500, and is preferably 120 to 450, more preferably 150 to 400, and more preferably 180 to 350 because the effects of the present invention are easily obtained. More preferably, it is 200 to 300.
- diisocyanate compound represented by the general formula (4) examples include trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), 2,2-dimethylpentane diisocyanate, octamethylene diisocyanate, 2,2 2,4-trimethylpentane diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), hydrogenated xylylene diisocyanate (hydrogenated XDI) and 2,4,4,4 Aliphatic diisocyanates such as (or 2,2,4) -trimethylhexamethylene diisocyanate (TMDI) Tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI
- Q in the general formula (4) may be any divalent hydrocarbon group having 3 to 16 carbon atoms, but is preferably a group in which two isocyanate groups have been removed from the diisocyanate compounds exemplified above. .
- diisocyanates aliphatic diisocyanates are preferred, and trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), octamethylene diisocyanate, isophorone diisocyanate (IPDI) and dicyclohexylmethane diisocyanate (hydrogenated MDI), hydrogenated xylylene diisocyanate ( Hydrogenated XDI) and 2,4,4 (or 2,2,4) -trimethylhexamethylene diisocyanate (TMDI) are more preferred, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI)
- R 4 and R 6 in the general formula (1) described above each independently represent a divalent hydrocarbon group having 3 to 16 carbon atoms. More specifically, a group in which two isocyanate groups are removed from the diisocyanate compounds exemplified above is preferable, a group in which two isocyanate groups are removed from aliphatic diisocyanate is more preferable, and trimethylene diisocyanate is more preferable.
- HDI hexamethylene diisocyanate
- IPDI isophorone diisocyanate
- MDI dicyclohexylmethane diisocyanate
- hydrogenated xylylene diisocyanate hydrogenated xylylene diisocyanate
- 2,4,4 2,4,4 (or
- isocyanate groups are removed from any of methylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and dicyclohexylmethane diisocyanate (hydrogenated MDI), and two isocyanates from hexamethylene diisocyanate (HDI)
- the group is a group other than a group.
- Specific catalysts used in producing the component (A) include metal salts of lauric acid, metal salts of myristic acid, metal salts of palmitic acid, metal salts of stearic acid and metal salts of higher fatty acids, and metal salts of higher fatty acids selected from metal salts of oleic acid Salts may be mentioned, and one or more may be used.
- the metal salt refers to any of calcium salt, potassium salt, sodium salt and magnesium salt. Among them, metal laurates are preferable, and potassium laurate or sodium laurate is more preferable, because it is possible to produce an aqueous gelling agent exhibiting the remarkable effects of the present invention.
- the aqueous gelling agent represented by the general formula (1) can be produced with or without a catalyst.
- a catalyst metal halides such as titanium tetrachloride, hafnium chloride, zirconium chloride, aluminum chloride, gallium chloride, indium chloride, iron chloride, tin chloride, boron fluoride, etc .; sodium hydroxide, potassium hydroxide , Hydroxides of alkali metals or alkaline earth metals such as sodium methylate and sodium carbonate, alcoholates, carbonates; metal oxides such as aluminum oxide, calcium oxide, barium oxide and sodium oxide; tetraisopropyl titanate, Organic metal compounds such as dibutyltin dichloride, dibutyltin oxide, dibutyltin dilaurate, dibutyltin bis (2-ethylhexyl thioglycolate) and the like; and soaps such as sodium octylate and potassium octy
- the viscosity of a 1% by mass aqueous solution at 25 ° C. of component (A) is 1,000 to 5,000 mPa ⁇ s
- the cloud point of a 1% by mass aqueous solution of component (A) is 60 ° C. to 80 ° C.
- the aqueous gelling agent represented by the general formula (1) having a weight average molecular weight of 10,000 to 30,000 of the component (A) can be obtained by using the above-mentioned higher fatty acid metal salt.
- any one of 1% by mass aqueous solution viscosity, 1% by mass aqueous solution cloud point and weight average molecular weight of the present invention (A) It may deviate from the specification of ingredients.
- the amount of the higher fatty acid metal salt used as a catalyst can be 0.01 to 5% by mass based on the total amount of the reaction system at the production of the component (A).
- 0.1 to 2% by mass is preferably used with respect to the whole system, and 0.5 to 1% by mass is more preferable, because sufficiently significant effects as a catalyst can be obtained. If the amount is less than 0.01% by mass, the function as a catalyst may not be sufficiently exhibited, and the component (A) used in the present invention may not be obtained. If the amount is more than 5% by mass, an effect corresponding to the addition amount May not be obtained.
- this catalyst does not perform the removal process after component (A) manufacture, it will remain in cosmetics containing component (A) and (B) of this invention, and the said residual amount is It is determined by the use amount of the catalyst at the time of production of the component (A) described above and the compounding amount of the component (A) in the cosmetic composition described later.
- Examples of the method for producing the component (A) include a method in which the compounds represented by the general formulas (2) to (4) listed above are used as a raw material and synthesized in the presence of a specific catalyst.
- a specific catalyst For example, 1.5 to 2.4 moles, preferably 1.8 to 2.2 moles of the alcohol compound represented by the general formula (2) relative to 2 moles of the diisocyanate compound represented by the general formula (4) More preferably, it is 1.9 to 2.1 mol, and 0.5 to 1.4 mol, preferably 0.8 to 1.2 mol, more preferably 0 to 0.5 mol of the polyalkylene glycol represented by the general formula (3).
- 9 to 1.1 moles of catalyst may be further added and reacted.
- Specific reaction conditions include adding a diisocyanate compound represented by the general formula (4), an alcohol compound represented by the general formula (2) and a polyalkylene glycol represented by the general formula (3) into a system together with a catalyst And a reaction at 60 to 100 ° C. for 1 to 10 hours.
- a system containing an alcohol compound represented by the general formula (2) and a polyalkylene glycol represented by the general formula (3) is uniformly mixed and then represented by the general formula (4) And the reaction is carried out at 60 to 100.degree. C. for 1 to 10 hours.
- the viscosity of a 1% by mass aqueous solution at 25 ° C. of the component (A) constituting the cosmetic composition of the present invention is 1,000 to 5,000 mPa ⁇ s.
- the viscosity is preferably 1,500 to 4,000 mPa ⁇ s, and more preferably 2,000 to 3,500 mPa ⁇ s because the effects of the present invention appear more remarkably.
- As a measuring method of the viscosity of 1 mass% aqueous solution in 25 ° C the viscosity measuring method by B type viscosity meter in 25 ° C of a statement to JIS Z 8803: 2011 can be used.
- the cloud point of a 1% by mass aqueous solution of the component (A) constituting the cosmetic composition of the present invention is 60 ° C. or more and 80 ° C. or less.
- the cloud point is preferably 60 ° C. or more and 70 ° C. or less because the effects of the present invention appear more remarkably.
- a method of measuring the cloud point a method of preparing a 1% by mass aqueous solution of the component (A) and gradually heating to make the temperature at which turbidity occurs be the cloud point can be used.
- the weight average molecular weight of the component (A) constituting the cosmetic composition of the present invention is 10,000 to 30,000. Among these, the weight average molecular weight is preferably 12,000 to 25,000, and more preferably 15,000 to 20,000, because the effects of the present invention are more prominent.
- the weight average molecular weight can be measured by standard polystyrene conversion using GPC (Gel Permeation Chromatography gel permeation chromatography).
- GPC Gel Permeation Chromatography gel permeation chromatography
- the component (A) constituting the cosmetic composition of the present invention is solid or viscous at room temperature. It is preferable to dissolve it in a solvent such as water beforehand to make it liquid when it is mixed in a cosmetic, because it is easy to handle. Although the amount of the solvent is not particularly specified, it is preferable to adjust the component (A) to be 10 to 50% by mass, and to be 15 to 40% by mass because of easy handling. More preferable.
- Examples of the solvent that can be used include water or volatile primary alcohol compounds such as methanol, ethanol and propanol. On the other hand, since the volatile solvent may be regulated depending on the use site, water is most preferable among these.
- the amount of the component (A) constituting the cosmetic composition of the present invention is not particularly limited, but in order to form an aqueous gel in which the effects of the present invention can be easily obtained, the total amount of the cosmetic composition is: It is preferable to blend 0.05 to 20% by mass, more preferably 0.1 to 10% by mass, and still more preferably 0.5 to 5% by mass, and 1 to 3% by mass Most preferred.
- the component (B) which comprises the cosmetics composition of this invention is a polymeric thickener. It is not particularly limited as long as it is a polymer thickener generally known in the cosmetic industry (note that the compound represented by the above general formula (1) does not correspond to a polymer thickener).
- polymer thickeners suitable for the cosmetic composition of the present invention include carboxy vinyl polymers, acrylic acid / alkyl methacrylate copolymers, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, sodium polyacrylate, poly Synthetic polymer thickeners such as acrylamide, polyethylene oxide, ethylene oxide and propylene oxide block copolymer; guar gum, locust bing gum, quince seed, carrageenan, galactan, gum arabic, tragacanth gum, pectin, mannan, starch, xanthan gum, dextran, Succinoglucan, curdlan, hyaluronic acid, gelatin, albumin, collagen, cellulose, chondroitin sulfate, dermatan sulfate, glycogen, heparan sulfate, keratan sulfate , Natural-based polymer thickeners such as chondroitin, mucotin sulf
- the polymeric thickener used in the present invention is not particularly limited, the weight average molecular weight is preferably 10,000 to 10,000,000, since the effects of the present invention are easily obtained, and 40,000. It is more preferably ⁇ 5,000,000 and even more preferably 100,000 to 2,000,000.
- the polymeric thickener which is component (B) which comprises the cosmetics composition of this invention may be mix
- the compounding amount thereof is not particularly specified, it is preferable to mix 0.005 to 10% by mass with respect to the total amount of the cosmetic composition, since a remarkable effect of the present invention is obtained, 0.01 to 5 It is more preferable to blend by mass, more preferably 0.05 to 5% by mass, and still more preferably 0.1 to 2% by mass.
- the cosmetic composition of the present invention may be any other additive generally used in cosmetic compositions for the purpose of imparting various properties as needed within the qualitative and quantitative range that does not impair the effects of the present invention.
- powder components liquid oil, ester oil, silicone oil, solid oil, wax, hydrocarbon oil, higher fatty acid, higher alcohol, polyol compound, nonionic surfactant, cationic surfactant, anionic surfactant, amphoteric surfactant Agents, moisturizers, sequestering agents, sugars (except polysaccharides), amino acids and their derivatives, organic amines, pH adjusters, antioxidants, preservatives, blood circulation enhancers, anti-inflammatory agents, activators, whitening agents, anti- Seborrhoea agents, anti-inflammatory agents, various extracts and the like can be mentioned, and one or more of them can be optionally blended.
- inorganic powder for example, talc, kaolin, mica, sericite (sericite), muscovite, phlogopite, synthetic mica, pyromica, biotite, permiculite, magnesium carbonate, calcium carbonate, silicate Aluminum, barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal salt of tungstate, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate (baked gypsum), calcium phosphate, fluoroapatite, hydroxyapatite, ceramic powder , Metal soaps (eg, zinc myristate, calcium palmitate, aluminum stearate), boron nitride etc .; organic powders (eg, polyamide resin powder (nylon powder), polyethylene powder, polymethyl methacrylate powder Polystyrene powder, copolymer resin powder of styrene and acrylic acid,
- organic powders eg
- Organic pigments Red No. 3, Red No. 104, Red No. 106, Red No. 227, Red No. 230, Red No. 401, Red No. 505, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Yellow 203 No., Green No. 3 and Blue No. 1); Natural dyes (eg, chlorophyll, ⁇ -carotene etc.) And the like.
- liquid oils and fats examples include avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, sasanqua oil, castor oil, linseed oil And safflower oil, cotton seed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, Japanese oak oil, Japanese tung oil, jojoba oil, germ oil, triglycerin and the like.
- ester oils isopropyl myristate, octyldodecyl myristate, isopropyl isostearate, isononyl isononanoate, isotridecyl isononanoate, butyl stearate, oleyl oleate, octyldodecyl licinoleate, octyl hydroxystearate, ethylhexyl paramethoxycinnamate , Neopentyl glycol dicaprate, propylene glycol dicaprate, diisostearyl malate, polyglyceryl diisostearate, polyglyceryl triisostearate, glyceryl diisostearate, glyceryl triisostearate, glyceryl tri (capryl capric acid), glyceryl trihexanoate , Glyceryl tri-2-ethylhexanoate, trimethylo tri
- silicone oil polysiloxane, dimethylpolysiloxane, dimethicone, methylphenylpolysiloxane, cyclic dimethicone, amino modified silicone, carbinol modified silicone, methacryl modified silicone, mercapto modified silicone, phenol modified silicone, polyether modified silicone, methylstyryl Modified silicone, alkyl modified silicone, higher fatty acid ester modified silicone and the like can be mentioned.
- solid fats and oils examples include cocoa butter, coconut oil, hydrogenated coconut oil, palm oil, palm kernel oil, Japanese wax kernel oil, hydrogenated oil, coconut wax, hydrogenated castor oil and the like.
- wax examples include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ivory wax, persimmon wax, montan wax, nuka wax, lanolin, kapok wax, lanolin acetate, liquid lanolin acetate, sugar cane wax, lanolin fatty acid isopropyl, hexyl laurate, reduced lanolin, Jojoba wax, hard lanolin, shellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether, etc. may be mentioned.
- hydrocarbon oils examples include liquid paraffin, ozokerite, squalane, pristane, paraffin, ceresin, squalene, vaseline, microcrystalline wax and the like.
- higher fatty acids examples include decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, tall oil fatty acid, 12-hydroxystearic acid, isostearic acid, linoleic acid, linolenic acid, Eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA) and the like.
- linear alcohol such as decyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, monostearyl glycerin ether (butyl alcohol), 2-decyl tetradecyl Alcohol, lanolin alcohol, cholesterol, phytosterol, hexyl dodecanol, isostearyl alcohol, branched-chain alcohol such as octyl dodecanol, etc. may be mentioned.
- polyol compound examples include ethylene glycol, propylene glycol, butylene glycol, glycerin, diethylene glycol, dipropylene glycol, sugar alcohol and the like.
- nonionic surfactants include sorbitan fatty acid esters (eg, sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate Glycerin and polyglycerin fatty acids (eg mono cotton seed oil fatty acid glycerin, glycerin monoerucate, glycerin sesquioleate, glycerin monostearate, etc.) POE-glyceryl monostearate, polyglycerin monoisostearate, ⁇ , ⁇ '-pyroglutamate glycerine oleate, glycerol stearate Glyceryl gorate, etc .; Propylene glycol fatty acid esters (eg, propylene glycol monostearate etc.); Cured castor oil derivatives; Glycerin, polyglycer
- POE-castor oil hydrogenated castor oil derivatives eg POE-castor oil, POE-cured castor oil, POE-hardened castor oil monoisostearate, POE-hardened castor oil triisostearate, POE-hardened castor oil monopyroglutamic acid monoisostearic acid diester, POE-hardened castor oil maleic acid etc); POE- beeswax lanolin derivatives (Eg, POE-sorbit beeswax etc.); alkanolamides (eg, coconut oil fatty acid diethanolamide, coconut oil fatty acid monoethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide etc.); POE-propylene glycol Cole fatty acid esters; POE-alkylamines; N-methylalkyl glucamides (eg, N-methyl lauryl glucamide etc.) N-polyhydroxyalkyl fatty acid amides; POE-fatty acid amides; suc
- alkyl trimethyl ammonium salts such as cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, lauryl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, behenyl trimethyl ammonium methosulfate; cetyl triethyl ammonium chloride, stearyl triethyl ammonium chloride Alkyltriethyl ammonium salts such as lauryl triethyl ammonium chloride, behenyl triethyl ammonium chloride, cetyl triethyl ammonium methosulfate, behenyl triethyl ammonium methosulfate; distearyldimethyl ammonium chloride, disetyl dimethyl ammonium chloride, dilauryl Dialkyldimethyl ammonium salts such as methyl ammonium chloride, stearyl dimethyl
- anionic surfactant for example, a higher fatty acid salt surfactant, a sulfonate surfactant, a sulfate ester surfactant, a phosphate ester surfactant, a sulfosuccinate surfactant and the like Can be mentioned.
- the higher fatty acid salt type surfactant for example, saturated or unsaturated fatty acid having 12 to 18 carbon atoms, coconut oil fatty acid, hardened coconut oil fatty acid, palm oil fatty acid, hardened palm oil fatty acid, beef tallow fatty acid, hardened beef tallow fatty acid, etc.
- Salts (potassium salts, sodium salts, triethanolamine salts, ammonium salts and the like) and the like; alkyl ether carboxylates, alkyl allyl ether carboxylates, N-acyl sarcosine salts, N-acyl glutamates and the like.
- sulfonate surfactants include higher fatty acid amido sulfonates, alkyl benzene sulfonates, N-acyl amino sulfonates, ⁇ -olefin sulfonates, and higher fatty acid ester sulfonates.
- sodium N-myristoyl-N-methyl taurine, sodium N-stearoyl-N-methyl taurine, coconut oil fatty acid methyl taurine sodium, coconut oil fatty acid acyl methyl taurine sodium, lauryl methyl taurine sodium, dodecyl benzene Sodium sulfonate, triethanolamine dodecylbenzene sulfonate, N-cocoyl-N-methyl taurine sodium and the like can be mentioned.
- sulfate ester surfactant examples include higher alkyl sulfates, polyoxyethylene alkyl ether sulfates, higher fatty acid ester sulfates, secondary alcohol sulfates, higher fatty acid alkylolamide sulfates and the like. More specifically, sodium lauryl sulfate, potassium lauryl sulfate, polyoxyethylene lauryl sulfate triethanolamine, polyoxyethylene lauryl sulfate sodium, hardened coconut oil fatty acid glycerin sodium sulfate and the like can be mentioned.
- phosphate ester type surfactant examples include triethanolamine monolauryl phosphate, dipotassium monolauryl phosphate, sodium polyoxyethylene oleyl ether phosphate, sodium polyoxyethylene stearyl ether phosphate and the like.
- sulfosuccinate-type surfactants include sodium polyoxyethylene alkyl sulfosuccinate, sodium di-2-ethylhexyl sulfosuccinate, monolauroyl monoethanolamide polyoxyethylene sodium sulfosuccinate, lauryl polypropylene glycol sodium sulfosuccinate and the like.
- amphoteric surfactants include imidazoline type amphoteric surfactants, betaine type amphoteric surfactants, acyl tertiary amine oxides, and acyl tertiary phosphinic oxides.
- imidazoline type amphoteric surfactant examples include 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy Disodium salt etc. are mentioned.
- betaine type amphoteric surfactants include alkylbetaines, alkylamide betaines, alkylsulfobetaines, alkylhydroxysulfobetaines, phosphobetaines and the like. More specifically, for example, lauryl dimethylaminoacetic acid betaine, myristyl dimethylaminoacetic acid betaine, coconut oil fatty acid amidopropyl betaine, coconut oil fatty acid dimethylsulfopropylbetaine, lauryldimethylaminohydroxysulfobetaine, lauryl hydroxyphosphobetaine, 2-heptadecyl And -N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil alkyl-N-hydroxyethylimidazolinium betaine and the like.
- acyl tertiary amine oxide a lauryl dimethylamine oxide etc. are mentioned, for example.
- examples of the acyl tertiary phosphine oxide include lauryl dimethyl phosphine oxide and the like.
- a moisturizing agent for example, polyethylene glycol, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucotin sulfate, caronic acid, atelocollagen, cholesteryl-12-hydroxystearate, sodium lactate, bile salt, dl-pyrrolidonecarboxylic acid
- the acid salt, short chain soluble collagen, diglycerin (EO) PO adduct, extract of Izayoira, extract of Yarrow extract, extract of Meriloto, etc. may be mentioned.
- the sequestering agent for example, 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, edetate disodium, edetate trisodium, edetate tetrasodium Sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, trisodium ethylenediamine hydroxyethyl triacetate and the like.
- monosaccharides include tricarbon sugars (eg, D-glyceryl aldehyde, dihydroxyacetone etc.); tetracarbon sugars (eg, D-erythrose, D-erythrulose, D-Treose, erythritol etc.); , L-arabinose, D-xylose, L-lyxose, D-arabinose, D-ribose, D-ribulose, D-xylulose, L-xylulose, etc .; 6-carbon sugar (eg, D-glucose, D-talose, D -Psicose, D-galactose, D-fructose, L-galactose, L-mannose, D-tagatose etc .; heptacarbon sugars (eg aldoheptose, heprose etc.); octacarbon sugars (eg octulose etc); de
- oligosaccharides include sucrose, umbelliferoses, lactose, planothose, isolicinoses, ⁇ , ⁇ -trehalose, raffinose, lycnoses, umbilicins, stachyose vervascose and the like.
- amino acids examples include neutral amino acids (eg, threonine, cysteine and the like); basic amino acids (eg, hydroxylysine and the like) and the like.
- amino acid derivative examples include sodium acylsarcosine (sodium lauroyl sarcosine), acyl glutamate, sodium acyl ⁇ -alanine, glutathione, pyrrolidone carboxylic acid and the like.
- organic amines examples include monoethanolamine, diethanolamine, triethanolamine, morpholine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol and the like. Can be mentioned.
- pH adjusters examples include buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate.
- vitamins examples include vitamin A, B1, B2, B6, C, E and derivatives thereof, pantothenic acid and derivatives thereof, biotin and the like.
- antioxidant examples include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid esters and the like.
- preservatives methylparaben, ethylparaben, butylparaben, phenoxyethanol, etc.
- anti-inflammatory agents eg, glycyrrhizinic acid derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, zinc oxide, allantoin etc.
- Whitening agents for example, Yukinoshita extract, arbutin etc.
- Extracts for example, Ouchibacus, auula, sikonyaku, peony, serpents, birch, sage, loquat, carrots, aloe, zenia oysters, iris, grapes, yokinin, lichens, lily , Saffron, senkyu, shochu, hyperglossia, onynis, garlic, pepper, chimney, seaweed, etc.
- activator eg, royal jelly, photosen
- the cosmetic composition of the present invention is not particularly limited as long as it is a cosmetic which requires the effects of the present invention, and can be used, for example, in a cosmetic composition for skin.
- the viscosity of the 1 mass% aqueous solution at 25 ° C is 1,000 to 5,000 mPa ⁇ s
- the cloud point of the 1 mass% aqueous solution is 60 ° C to 80 ° C
- the weight average molecular weight is 10,000.
- Salt resistance and viscosity of a cosmetic composition containing a polymeric thickener and the aqueous gelling agent represented by the above general formula (1) of the component (A) of the present invention which is ⁇ 30,000 It can be used to improve at least one, and preferably all of the effects selected from the group consisting of: temperature stability, feel in use.
- Catalyst 1 potassium laurate catalyst 2: sodium laurate catalyst 3: tetraisopropyl titanate catalyst 4: dibutyltin dilaurate
- components (A) -2 to (A) -12 were produced in the same manner using the raw materials listed in Table 1.
- the components (A) -9 and (A) -10 are produced without using a catalyst, and the components (A) -1 to (A) -12 are all starting compounds (2), compounds The total mass (mass of the whole reaction system) of (3) and a compound (4) is unified and manufactured.
- Each component (A) obtained may be a mixture of an aqueous gelling agent having g of 1 to 10 and an aqueous gelling agent having g of 0 in the general formula (1), and the mass ratio thereof Table 2 also shows the results.
- GPC Gel Permeation Chromatography gel permeation chromatography
- HLC-8220GPC made by Tosoh Corporation
- the mass ratio of the compound having 0 in the general formula (1) of the component (A) and the compound having 1 to 10 of g was calculated from the area ratio using the chart obtained from the above-mentioned GPC.
- Component (B) used for the present Example and the comparative example is shown below.
- Component (B) -1 Carboxyvinyl Polymer
- Component (B) -2 Xanthan Gum
- ⁇ Performance evaluation of gel> The performance of the gel obtained in Table 3 was evaluated.
- the evaluation items are (1) salt resistance of viscosity, (2) temperature stability of viscosity, and (3) feel at the time of use (pull pull, etc.).
- the respective evaluation criteria are as follows. The viscosity was measured using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd., model number TVB-10).
- Viscosity change rate is 50% or more
- A Compared with the viscosity of the 25 ° C. storage sample, the change in viscosity of the 50 ° C. storage sample was 10% or less.
- B Compared with the viscosity of the 25 ° C. storage sample, the change in viscosity of the 50 ° C. storage sample was more than 10% and not more than 20%.
- C Compared with the viscosity of the 25 ° C. storage sample, the change rate of the viscosity of the 50 ° C. storage sample was more than 20% and not more than 30%.
- D The change in viscosity of the 50 ° C. stored sample was greater than 30% as compared to the viscosity of the 25 ° C. stored sample.
- the total score is 45 to 50 points B: The total score is 40 to 44 points C: The total score is 35 to 39 points D: The total score is 30 to 34 points E: The total score is 29 or less
- Viscosity change rate is 50% or more
- A Compared with the viscosity of the 25 ° C. storage sample, the change in viscosity of the 50 ° C. storage sample was 10% or less.
- B Compared with the viscosity of the 25 ° C. storage sample, the change in viscosity of the 50 ° C. storage sample was more than 10% and not more than 20%.
- C Compared with the viscosity of the 25 ° C. storage sample, the change rate of the viscosity of the 50 ° C. storage sample was more than 20% and not more than 30%.
- D The change in viscosity of the 50 ° C. stored sample was greater than 30% as compared to the viscosity of the 25 ° C. stored sample.
- the total score is 45 to 50 points B: The total score is 40 to 44 points C: The total score is 35 to 39 points D: The total score is 30 to 34 points E: The total score is 29 or less
- the product of the present invention is (4) salt resistance of viscosity, (5) temperature stability of viscosity, (6) feel when used, (7) stability over time of emulsification, cosmetic composition good in all items It turned out that it was.
- the product of the present invention has improved performance, has high salt resistance and temperature stability of viscosity, has high stability over time at the time of emulsification, and further has improved performance as compared with the cosmetic composition hitherto known.
- the cosmetic composition has a good feeling of Since the cosmetic composition is an invention with a better feeling of use from the user's point of view, needs are high and its usefulness is very large.
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Abstract
Description
成分(A):下記の一般式(1)で表される水系ゲル化剤
成分(B):高分子増粘剤
さらに、本発明は上記の製造方法で得られた水系ゲル化剤と高分子増粘剤を組み合わせる工程を含む、化粧料組成物の製造方法も提供する。
なお、本発明に用いる高分子増粘剤は特に限定されないが、本発明の効果が得られやすいことから、重量平均分子量が10,000~10,000,000であることが好ましく、40,000~5,000,000であることがより好ましく、100,000~2,000,000であることがさらに好ましい。
高級脂肪酸塩型界面活性剤としては、例えば、炭素数12~18の飽和又は不飽和脂肪酸、ヤシ油脂肪酸、硬化ヤシ油脂肪酸、パーム油脂肪酸、硬化パーム油脂肪酸、牛脂脂肪酸、硬化牛脂脂肪酸などの塩(カリウム塩、ナトリウム塩、トリエタノールアミン塩、アンモニウム塩など)など;アルキルエーテルカルボン酸塩、アルキルアリルエーテルカルボン酸塩、N-アシルサルコシン塩、N-アシルグルタミン酸塩などが挙げられる。より具体的には、例えば、ラウリン酸カリウム、ラウリン酸ナトリウム、パルミチン酸ナトリウム、ミリスチン酸カリウム、ラウリルエーテルカルボン酸ナトリウム、N-ラウロイルサルコシンナトリウム、N-ラウロイルグルタミン酸ナトリウム、ヤシ油脂肪酸グルタミン酸ナトリウム、N-ステアロイルグルタミン酸ジナトリウム、N-ミリストイル-L-グルタミン酸モノナトリウム、ヤシ油脂肪酸イセチオン酸ナトリウム、ヤシ油脂肪酸トリエタノールアミンなどが挙げられる。
イミダゾリン型両性界面活性剤としては、例えば、2-ウンデシル-N,N,N-(ヒドロキシエチルカルボキシメチル)-2-イミダゾリンナトリウム、2-ココイル-2-イミダゾリニウムヒドロキサイド-1-カルボキシエチロキシ2ナトリウム塩などが挙げられる。
ビタミンとしては、例えば、ビタミンA、B1、B2、B6、C、E及びその誘導体、パントテン酸及びその誘導体、ビオチンなどが挙げられる。
酸化防止剤としては、例えば、トコフェロール類、ジブチルヒドロキシトルエン、ブチルヒドロキシアニソール、没食子酸エステル類などが挙げられる。
まず、実施例及び比較例に使用する成分(A)を製造する。
成分(A)を製造するにあたり使用した原料を以下に示す。
化合物(2)-1:一般式(2)において、R10=デシル基、R11=ドデシル基、R12=エチレン基、r=20である化合物
化合物(2)-2:一般式(2)において、R10=オクチル基、R11=デシル基、R12=エチレン基、r=20である化合物
化合物(2)-3:一般式(2)において、R10=ドデシル基、R11=テトラデシル基、R12=エチレン基、r=20である化合物
化合物(2)-4:一般式(2)において、R10=デシル基、R11=ドデシル基、R12=エチレン基、r=100である化合物
化合物(3)-1:一般式(3)において、R13=エチレン基、t=250である化合物
化合物(3)-2:一般式(3)において、R13=エチレン基、t=450である化合物
化合物(3)-3:一般式(3)において、R13=エチレン基、t=135である化合物
化合物(4)-1:ヘキサメチレンジイソシアネート
化合物(4)-2:ジシクロヘキシルメタンジイソシアネート(水添MDI)
触媒2:ラウリン酸ナトリウム
触媒3:テトライソプロピルチタネート
触媒4:ジブチル錫ジラウレート
温度計、窒素導入管及び攪拌機を付した4つ口フラスコに、化合物(3)-1を620g(0.06mol)、化合物(2)-1を139g(0.11mol)仕込み、40~50℃に昇温し、各成分が均一になるまで撹拌し、各成分が均一に混合されたことを確認した後、化合物(4)-1を18.9g(0.11mol)、触媒1を5.8g(0.02mol)仕込み、系内を窒素置換した。その後、更に80~90℃まで昇温し、同温度で6時間反応させ、成分(A)-1を得た。
得られた各成分(A)をそれぞれ1質量%水溶液になるよう水を加え測定用試料を調製し、25℃にてB型粘度計(東機産業株式会社製、型番TVB-10)を用い測定した。
上記調製した各成分(A)の1質量%水溶液を恒温槽に設置し、徐々に加温(約1℃/分)して濁りが生じる温度を曇点(℃)とした。
GPC(Gel Permeation Chromatographyゲル浸透クロマトグラフィー)を用いて測定した。詳細な測定条件は以下の通りである。
GPC装置:HLC-8220GPC(東ソー株式会社製)
カラム:TSKgel guardcolumn SuperMP(HZ)-N(1本)、TSKgel SuperMultiporeHZ-N(4本)の5本のカラムを直列に接続して使用。
検出器:RI
サンプル濃度:5mg/ml(in THF溶液)
カラム温度:40℃
標準サンプル:ポリスチレン
本実施例及び比較例に使用した成分(B)を以下に示す。
成分(B)-1:カルボキシビニルポリマー
成分(B)-2:キサンタンガム
次に、前述した各成分(A)と各成分(B)を表3に記載の量で配合し、各種ゲルの調製を行った(表3)。
表3にて得られたゲルに関して、性能の評価を行なった。評価項目としては、(1)粘度の耐塩性、(2)粘度の温度安定性、(3)使用時の感触(プルプル感など)である。各評価基準に関しては以下の通りである。なお、粘度の測定は、B型粘度計(東機産業株式会社製、型番TVB-10)を使用し測定を行った。
表3にて調製した各ゲル100gに、0.5gのNaClを加え、撹拌混合した。塩添加前後の粘度を25℃にて測定し、粘度の耐塩性を評価した。評価は以下の基準にて行った。評価がB以上を合格とした。
B:粘度の変化率が5%以上10%未満
C:粘度の変化率が10%以上30%未満
D:粘度の変化率が30%以上50%未満
E:粘度の変化率が50%以上
表3に記載の各ゲルをそれぞれ透明ガラス容器に100g入れ、25℃及び50℃の恒温槽にて2ヵ月間保存した。その後、サンプルの状態(粘度)を25℃にて測定し、その結果から25℃保存サンプルの粘度(基準値)と50℃保存サンプルの粘度との差を粘度変化率として算出し、以下A~Dにて評価した。評価がB以上を合格とした。
B:25℃保存サンプルの粘度と比較し、50℃保存サンプルの粘度の変化率が10%より大きく、20%以下であった。
C:25℃保存サンプルの粘度と比較し、50℃保存サンプルの粘度の変化率が20%より大きく、30%以下であった。
D:25℃保存サンプルの粘度と比較し、50℃保存サンプルの粘度の変化率が30%より大きかった。
使用時の感触(プルプル感など)が良いとは、具体的には(I)得られたゲルを5g程度手のひらに取り、左右に揺すった際、プルプルとした柔らかいこと、(II)更にはそのゲルを肌全体に塗り広げる際、塗り広げやすい柔らかさをもつことを指す。10人に上記(I)及び(II)について5点満点(最低点は1点)で表3に記載の各ゲルをそれぞれ総合的に評価するよう指示し、更にその合計点数を基準に以下A~Eで評価した。評価がB以上を合格とした。
B:合計点数が40~44点
C:合計点数が35~39点
D:合計点数が30~34点
E:合計点数が29点以下
続いて、各成分(A)と各成分(B)を配合した化粧料組成物(水中油型乳化組成物)の調製を行った(表5、6)。調製方法としては、最初に成分(A)及び(B)以外の成分を配合し、ベースの水中油型乳化組成物を調製した後に、各成分(A)及び各成分(B)を後添加し、化粧料組成物1~20とした。
上記表5、6にて調製した化粧料組成物に関し、(4)粘度の耐塩性、(5)粘度の温度安定性、(6)使用時の感触(プルプル感など)、(7)乳化の経時安定性について評価を行なった。各評価基準に関しては以下の通りである。なお、粘度の測定は、B型粘度計(東機産業株式会社製、型番TVB-10)を使用し測定を行った。
表5、6にて調製した各化粧料組成物100gに、0.5gのNaClを加え、撹拌混合した。塩添加前後の粘度を25℃にて測定し、粘度の耐塩性を評価した。評価は以下の基準にて行った。評価がB以上を合格とした。
B:粘度の変化率が5%以上10%未満
C:粘度の変化率が10%以上30%未満
D:粘度の変化率が30%以上50%未満
E:粘度の変化率が50%以上
表5、6に記載のサンプルをそれぞれ透明ガラス容器に100g入れ、25℃及び50℃の恒温槽にて2ヵ月間保存した。その後、サンプルの状態(粘度)を25℃にて測定し、その結果から25℃保存サンプルの粘度(基準値)と50℃保存サンプルの粘度との差を粘度変化率として算出し、以下A~Dにて評価した。評価がB以上を合格とした。
B:25℃保存サンプルの粘度と比較し、50℃保存サンプルの粘度の変化率が10%より大きく、20%以下であった。
C:25℃保存サンプルの粘度と比較し、50℃保存サンプルの粘度の変化率が20%より大きく、30%以下であった。
D:25℃保存サンプルの粘度と比較し、50℃保存サンプルの粘度の変化率が30%より大きかった。
使用時の感触(プルプル感など)が良いとは、具体的には(I)得られたサンプルを5g程度手のひらに取り、左右に揺すった際、プルプルとして柔らかいこと、(II)更にはそのサンプルを肌全体に塗り広げる際、塗り広げやすい柔らかさをもつことを指す。10人に上記(I)及び(II)について5点満点(最低点は1点)で表5,6に記載のサンプルをそれぞれ総合的に評価するよう指示し、更にその合計点数を基準に以下A~Eで評価した。評価がB以上を合格とした。
B:合計点数が40~44点
C:合計点数が35~39点
D:合計点数が30~34点
E:合計点数が29点以下
調製した化粧料組成物100gを、50℃にて3ヵ月保存した後、乳化状態を観察した。評価は以下の基準にて行った。評価がB以上を合格とした。
A:乳化状態良好(分離なし)
B:乳化状態やや良好(一部分離あり)
C:乳化状態不良(二層に分離)
Claims (9)
- 下記の成分(A)及び(B)を含有する化粧料組成物であって、成分(A)の25℃での1質量%水溶液の粘度が1,000~5,000mPa・sであり、成分(A)の1質量%水溶液の曇点が60℃以上80℃以下であり、成分(A)の重量平均分子量が10,000~30,000である化粧料組成物。
成分(A):下記の一般式(1)で表される水系ゲル化剤
(式中、R1、R2、R8及びR9はそれぞれ独立して炭素数4~20の炭化水素基を表し、R3、R5及びR7はそれぞれ独立して炭素数2~4の2価の炭化水素基を表し、R4及びR6はそれぞれ独立して炭素数3~16の2価の炭化水素基を表し、a及びeはそれぞれ独立して10~100の数を表し、dは100~500の数を表し、gは0~10の数を表す。)
成分(B):高分子増粘剤 - 成分(A)である一般式(1)で表される水系ゲル化剤の、R1、R2、R8及びR9がそれぞれ独立して炭素数10~12の脂肪族炭化水素基である、請求項1に記載の化粧料組成物。
- 成分(A)である一般式(1)で表される水系ゲル化剤の、R4及びR6がそれぞれ独立して炭素数4~8の2価の脂肪族炭化水素基である、請求項1又は2に記載の化粧料組成物。
- 成分(B)である高分子増粘剤が、カルボキシビニルポリマー及びキサンタンガムのいずれか若しくは両方である、請求項1~3のいずれか一項に記載の化粧料組成物。
- 下記一般式(4)で表されるジイソシアネート化合物をモル比で2に対して、一般式(2)で表されるアルコール化合物をモル比で1.5~2.4及び一般式(3)で表されるポリアルキレングリコールをモル比で0.5~1.4の量で加え、高級脂肪酸金属塩の存在下でこれらを反応させることを含む、下記一般式(1)で表される水系ゲル化剤の製造方法。
(式中、R1、R2、R8及びR9はそれぞれ独立して炭素数4~20の炭化水素基を表し、R3、R5及びR7はそれぞれ独立して炭素数2~4の2価の炭化水素基を表し、R4及びR6はそれぞれ独立して炭素数3~16の2価の炭化水素基を表し、a及びeはそれぞれ独立して10~100の数を表し、dは100~500の数を表し、gは0~10の数を表す。)
(式中、R10及びR11は、それぞれ独立して炭素数4~20の炭化水素基を表し、R12は炭素数2~4の2価の炭化水素基を表し、rは10~100の数を表す。)
(式中、R13は炭素数2~4の2価の炭化水素基を表し、tは100~500の数を表す。)
(式中、Qは、炭素数3~16の2価の炭化水素基を表わす。) - 前記高級脂肪酸金属塩が、ラウリン酸金属塩、ミリスチン酸金属塩、パルミチン酸金属塩、ステアリン酸金属塩、オレイン酸金属塩の群から選択される1種又は2種以上の高級脂肪酸金属塩である、請求項5に記載の製造方法。
- 前記高級脂肪酸金属塩が、ラウリン酸金属塩である請求項5に記載の製造方法。
- 前記水系ゲル化剤は化粧料組成物を製造するために用いられる、請求項5~7のいずれかに記載の製造方法。
- 下記一般式(4)で表されるジイソシアネート化合物をモル比で2に対して、一般式(2)で表されるアルコール化合物をモル比で1.5~2.4及び一般式(3)で表されるポリアルキレングリコールをモル比で0.5~1.4の量で加え、高級脂肪酸金属塩の存在下でこれらを反応させて、下記一般式(1)で表される水系ゲル化剤を得る工程、及び
前記水系ゲル化剤及び高分子増粘剤を組み合わせる工程を含む、化粧料組成物の製造方法。
(式中、R1、R2、R8及びR9はそれぞれ独立して炭素数4~20の炭化水素基を表し、R3、R5及びR7はそれぞれ独立して炭素数2~4の2価の炭化水素基を表し、R4及びR6はそれぞれ独立して炭素数3~16の2価の炭化水素基を表し、a及びeはそれぞれ独立して10~100の数を表し、dは100~500の数を表し、gは0~10の数を表す。)
(式中、R10及びR11は、それぞれ独立して炭素数4~20の炭化水素基を表し、R12は炭素数2~4の2価の炭化水素基を表し、rは10~100の数を表す。)
(式中、R13は炭素数2~4の2価の炭化水素基を表し、tは100~500の数を表す。)
(式中、Qは、炭素数3~16の2価の炭化水素基を表わす。)
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| US16/644,031 US11464730B2 (en) | 2017-09-07 | 2018-08-28 | Cosmetic composition containing aqueous gelling agent, and method for producing aqueous gelling agent and cosmetic composition |
| EP18853670.0A EP3679920A4 (en) | 2017-09-07 | 2018-08-28 | Aqueous gelling agent cosmetic composition and process for the preparation of aqueous gelling agent and cosmetic composition |
| JP2019540903A JP7179006B2 (ja) | 2017-09-07 | 2018-08-28 | 水系ゲル化剤を含む化粧料組成物、並びに該水系ゲル化剤及び該化粧料組成物の製造方法 |
| CN201880057975.4A CN111093616B (zh) | 2017-09-07 | 2018-08-28 | 含有水系凝胶化剂的化妆料组合物以及该水系凝胶化剂和该化妆料组合物的制造方法 |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP7179006B2 (ja) | 2022-11-28 |
| US11464730B2 (en) | 2022-10-11 |
| EP3679920A1 (en) | 2020-07-15 |
| EP3679920A4 (en) | 2021-06-16 |
| US20200345617A1 (en) | 2020-11-05 |
| KR20200051678A (ko) | 2020-05-13 |
| JPWO2019049725A1 (ja) | 2020-08-20 |
| CN111093616B (zh) | 2023-02-28 |
| CN111093616A (zh) | 2020-05-01 |
| KR102684829B1 (ko) | 2024-07-12 |
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