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WO2016182006A1 - コポリマー - Google Patents

コポリマー Download PDF

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Publication number
WO2016182006A1
WO2016182006A1 PCT/JP2016/064071 JP2016064071W WO2016182006A1 WO 2016182006 A1 WO2016182006 A1 WO 2016182006A1 JP 2016064071 W JP2016064071 W JP 2016064071W WO 2016182006 A1 WO2016182006 A1 WO 2016182006A1
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WO
WIPO (PCT)
Prior art keywords
group
general formula
acid
present
copolymer
Prior art date
Application number
PCT/JP2016/064071
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English (en)
French (fr)
Japanese (ja)
Inventor
亘 堀江
雄一郎 竹山
恵 加治
厚志 仁王
萌 露木
紗弥香 佐藤
Original Assignee
ポーラ化成工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2015096957A external-priority patent/JP6608612B2/ja
Priority claimed from JP2015096958A external-priority patent/JP6815719B2/ja
Priority claimed from JP2015106260A external-priority patent/JP6618713B2/ja
Priority claimed from JP2015106259A external-priority patent/JP6584141B2/ja
Priority claimed from JP2015113897A external-priority patent/JP6608622B2/ja
Priority to CN202010302755.2A priority Critical patent/CN111358713B/zh
Application filed by ポーラ化成工業株式会社 filed Critical ポーラ化成工業株式会社
Priority to SG11201709288VA priority patent/SG11201709288VA/en
Priority to CN202010301977.2A priority patent/CN111481469B/zh
Priority to CN202010302836.2A priority patent/CN111329787B/zh
Priority to CN201680028097.4A priority patent/CN107614551A/zh
Priority to CN202010302838.1A priority patent/CN111329788B/zh
Priority to AU2016261772A priority patent/AU2016261772B2/en
Publication of WO2016182006A1 publication Critical patent/WO2016182006A1/ja
Priority to HK18103131.4A priority patent/HK1243720A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
    • 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
    • A61K8/8141—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
    • 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
    • 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
    • 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
    • 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
    • A61K8/73—Polysaccharides
    • 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
    • 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)
    • 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
    • A61K8/8141—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
    • 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
    • A61K8/817—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
    • 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
    • A61K8/85—Polyesters
    • 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
    • A61K8/86—Polyethers
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10—General cosmetic use
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/54—Polymers characterized by specific structures/properties

Definitions

  • the present invention relates to a novel copolymer which is a copolymer of a hydrophobic monomer and a hydrophilic monomer.
  • the present invention also relates to an emulsified composition emulsified with a water-soluble copolymer.
  • the present invention also relates to a skin cleanser containing a water-soluble copolymer.
  • the present invention also relates to a sunscreen cosmetic containing a water-soluble copolymer.
  • the present invention also relates to a coating film having a sea-island structure in which island particles of an amphiphilic copolymer are dispersed in an aqueous gel sea and a composition for forming the coating film.
  • oil agents are excellent in use feeling such as elasticity and moist feeling, and have been used for a long time as cosmetic materials.
  • the oil agent exhibits the above-mentioned excellent usability, if it is highly blended, it may become sticky and deteriorate the usability.
  • Patent Document 1 proposes a technique for suppressing stickiness by reducing the particle size of an emulsified particle in the cosmetic composition.
  • the technique for reducing stickiness by devising the composition and structure of cosmetics as described in Patent Document 1 has a problem that the dosage form that can be applied is limited.
  • Patent Document 2 discloses a cosmetic base comprising an alkylene oxide derivative having both excellent feel and moisture retention.
  • An emulsion composition in which an oil phase component and an aqueous phase component are mixed with an emulsifier is widely used as a cosmetic dosage form.
  • general low molecular weight emulsifiers may cause problems such as irritation to the skin and stickiness.
  • various emulsification techniques using a polymer emulsifier have been recently proposed.
  • Patent Document 3 discloses an emulsified composition using hydroxyethyl cellulose as an emulsifier.
  • Patent Document 4 discloses an emulsified composition using an alkyl-modified carboxyvinyl polymer as an emulsifier.
  • oil-in-water emulsified sunscreen cosmetics have a refreshing feel and are easy to use continuously.
  • the oil-in-water emulsion cosmetics use an ultraviolet absorber or an ultraviolet scattering agent that is a metal oxide powder such as zinc oxide or titanium oxide.
  • a metal oxide powder such as zinc oxide or titanium oxide.
  • discoloration occurs and the feeling of use such as poor spread and stickiness is deteriorated.
  • metal oxide powder when a large amount of metal oxide powder is blended, there is a problem that not only the powder aggregates and settles with time, but also the stability with time such as viscosity reduction, emulsification separation, and precipitation decreases. When these are used in combination, the above problem tends to occur more easily.
  • an ultraviolet absorber such as a dibenzoylmethane derivative and titanium oxide treated with silane and / or silicone
  • an ultraviolet absorber such as a dibenzoylmethane derivative and titanium oxide treated with silane and / or silicone
  • oil-in-water emulsified cosmetics using water-soluble polymers such as polyacrylic acid amide, xanthan gum, (sodium acrylate / acryloyldimethyltaurine) copolymer have been proposed (see Patent Documents 15 and 16).
  • the sea-island structure means that two types of incompatible polymers cause phase separation, and a continuous phase (sea phase) containing one polymer is dispersed in a dispersed phase (island phase) containing the other polymer. It refers to the existing structure.
  • the sea-island structure has a heterogeneous structure in which phases are separated, and thus has a different property from a composition having a uniform structure. To take advantage of these properties, sea-island structures are actively researched and developed in the technical fields of plastics, rubber, toner, adhesives, and the like.
  • Patent Document 17 discloses a tire coated with a coating mixture having a sea-island structure including a sea phase containing a thermoplastic resin and an island phase containing a polyurethane-based thermoplastic elastomer.
  • a coating mixture having a sea-island structure including a sea phase containing a thermoplastic resin and an island phase containing a polyurethane-based thermoplastic elastomer.
  • Patent Document 18 discloses a skin external application containing an amphiphilic copolymer having a structural unit derived from a specific hydrophobic acrylic ester monomer and a structural unit derived from a specific hydrophilic acrylic monomer. Agents are disclosed.
  • the oil agent has a preferable feeling of use such as a feeling of elasticity, but also has problems such as stickiness. Under such circumstances, there has been a demand for a new material having elasticity such as an oil agent.
  • An object of the present invention is to provide a novel copolymer having elasticity. Moreover, in the preferable form of this invention, it is set as the 1st subject to provide the copolymer which is hard to produce stickiness and has a moist feeling further.
  • the above-mentioned polymer emulsifier has less irritation to the skin, and has advantages such as less stickiness when contained at a low concentration, but is inferior in emulsifying power compared to conventional low-molecular emulsifiers. there were. Therefore, in order to ensure the stability of the emulsified state, it is necessary to highly blend the polymer emulsifier in the emulsified composition so as to have a high viscosity.
  • a second object of the present invention is to provide an emulsified composition having excellent emulsification stability while having less irritation to the skin and less stickiness.
  • a third problem to be solved by the present invention is to provide a new technique for reducing the feeling of tightness of the skin after using the skin cleansing material.
  • a fourth problem is to provide a technique for reducing the feeling of skin tightness.
  • the fifth problem to be solved by the present invention is that it has an excellent UV protection function, but is excellent in use feeling such as no stickiness and moisturizing feeling, and has emulsion stability. It is to provide an oil-in-water sunscreen cosmetic.
  • the problem to be solved by the present invention is to provide a film having a sea-island structure mainly composed of a water-soluble component and a technique for forming the film. It is another object of the present invention to provide a technique for imparting a milk-like feel containing an oil agent to a film mainly composed of a water-soluble component. It is a sixth object of the present invention to provide a film that preferably has both moisture retention and flexibility and a technique for forming the film.
  • the present inventors have intensively studied for an elastic copolymer, and as a result, have a hydrophobic, polymerizable carboxyl group and two specific branched structures.
  • a copolymer obtained by polymerizing an acrylic ester monomer having an acyl group and a hydrophilic acrylic monomer having a specific structure has excellent solubility, particularly water solubility, and has an elastic feel like an oil agent.
  • the headline, the present invention has been reached. That is, the present invention is as follows.
  • R1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R2 and R3 may be the same or different, have no ring structure, have a branched structure and have 6 to 22 carbon atoms
  • X represents a group in which an OH group is eliminated from a trivalent alcohol.
  • R4 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R5 represents an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group
  • R6 represents a hydrogen atom or carbon atom.
  • R4 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R5 represents an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group
  • R6 represents a hydrogen atom or carbon atom.
  • And represents an aromatic hydrocarbon group having 6 to 10 carbon atoms, an aliphatic hydrocarbon group having 1 to 14 carbon atoms, or an acyl group having 1 to 12 carbon atoms
  • n represents an integer of 6 to 40.
  • Such a copolymer has a feeling of elasticity when applied to the skin, and has a non-sticky and moist feeling.
  • the mass ratio of the structural unit (a) to the structural unit (b) is 25:75 to 35:65.
  • a copolymer having a mass ratio of the structural unit (a) to the structural unit (b) in the above range is excellent in elasticity and non-stickiness.
  • the molar ratio of the structural unit (a) to the structural unit (b) is 35:65 to 46:54.
  • a copolymer having a mass ratio of the structural unit (a) to the structural unit (b) in the above range is excellent in elasticity and non-stickiness.
  • the hydrophobic monomer is a hydrophobic monomer represented by the following general formula (3).
  • R7 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R8 and R9 may be the same or different, have no ring structure, have a branched structure and have 10 to 22 carbon atoms.
  • Y represents a group in which an OH group is eliminated from a trivalent alcohol.
  • the hydrophilic monomer is a hydrophilic monomer represented by the following general formula (4).
  • R10 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R11 represents a hydrogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or an aliphatic hydrocarbon having 1 to 14 carbon atoms.
  • m represents an integer of 6 to 40
  • the trihydric alcohol is glycerin, trimethylolpropane, or trimethylolethane.
  • the hydrophobic monomer is a compound represented by the following general formula (5).
  • the elasticity can be improved by using such a hydrophobic monomer.
  • the hydrophilic monomer is a hydrophilic monomer represented by the following general formula (6).
  • the elasticity can be improved by using such a hydrophilic monomer.
  • the present invention also relates to a skin external preparation containing the above-mentioned copolymer of the present invention.
  • Such an external preparation for skin has a feeling of elasticity after being applied to the skin. In addition, it is excellent in no stickiness and moist feeling.
  • This invention which solves the 2nd subject is 1 type, or 2 or more types of structural units (c) induced
  • the emulsified composition is characterized.
  • R14 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R15 does not include a branched hydrocarbon group that does not include a ring structure having 13 to 30 carbon atoms, or does not include a ring structure. Represents a hydrocarbon group having 6 to 12 carbon atoms having two or more branches.
  • R16 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R17, R18, and R19 may be the same or different, have no ring structure, have a branch, and have 6 carbon atoms.
  • Y represents a group in which an OH group is eliminated from a tetravalent alcohol.
  • the emulsified composition of the present invention has little stickiness during use by including the water-soluble copolymer.
  • the hydrophilic monomer is a polymerizable carboxylic acid, a hydrophilic monomer represented by the general formula (2), a hydrophilic monomer represented by the following general formula (9), the following general formula ( 10) or one or more hydrophilic monomers selected from the group consisting of the hydrophilic monomer represented by the following general formula (11).
  • R21 represents a hydrogen atom or a methyl group
  • G—O— represents a group obtained by removing hydrogen from the hydroxyl group at the 1-position of the reducing sugar
  • m is 2 or 3
  • l is 1-5. Represents an integer.
  • R22 represents a hydrogen atom or a methyl group
  • R23 represents an amino acid residue, a polyamine residue or an amino alcohol residue
  • Q represents an oxygen atom or a group represented by NH.
  • the hydrophobic monomer is a hydrophobic monomer represented by the general formula (1)
  • the water-soluble monomer is a hydrophilic monomer represented by the general formula (2).
  • Such a water-soluble copolymer having a structural unit derived from a hydrophobic monomer and a hydrophilic monomer is excellent in emulsifying power and excellent in the effect of reducing stickiness during use of the emulsified composition of the present invention.
  • the content of the water-soluble copolymer is 0.5 to 30% by mass.
  • the content of the oil phase component is 0.1 to 70% by mass.
  • the emulsion composition of the present invention in which the content of the oil phase component is in the above range is excellent in stability.
  • the emulsified composition of the present invention has little stickiness, it is preferably a cosmetic.
  • the present invention is derived from one or more structural units (c) derived from the hydrophobic monomer represented by the general formula (1), (7) or (8) and a hydrophilic monomer.
  • the present invention also relates to an emulsifier composed of a water-soluble copolymer having one or two or more structural units (d) as essential structural units. Such an emulsifier has excellent emulsifying power while being mild.
  • the present invention also relates to a method for producing an emulsified composition comprising a step of emulsifying using the emulsifier, wherein the emulsifier other than the emulsifier is substantially not used. . According to such a method, it is possible to easily produce an emulsified composition without using a conventional emulsifier that can cause stickiness and without adding a high amount of emulsifier.
  • the skin cleansing material of the present invention includes the above-mentioned water-soluble copolymer, thereby realizing a reduction in the feeling of sticking after use while providing good foaming and creamy foam quality.
  • the hydrophilic monomer is a polymerizable carboxylic acid, a hydrophilic monomer represented by the general formula (2), a hydrophilic monomer represented by the general formula (9), or the general formula ( The hydrophilic monomer represented by 10) and one or more hydrophilic monomers selected from the group consisting of the hydrophilic monomer represented by the general formula (11).
  • the hydrophobic monomer is a hydrophobic monomer represented by the general formula (1)
  • the water-soluble monomer is a hydrophilic monomer represented by the general formula (2).
  • the content of the water-soluble copolymer is 0.1 to 20% by mass.
  • the present invention is preferably applied to a foaming cleaning material. According to the present invention, it is possible to reduce the feeling of tightness of the skin after use without hindering the foaming and foam quality of the foaming detergent.
  • the present invention is preferably applied to a gel-like skin cleansing material.
  • ADVANTAGE OF THE INVENTION According to this invention, the feeling of tightness of the skin after use can be reduced, improving the ease of extending to the skin of a gel-like skin cleansing material.
  • ⁇ Skin cleansing agents containing surfactants have a relatively strong detergency, so they feel strong after use. Therefore, it is preferable to apply this invention to the skin cleansing agent of the form containing surfactant. According to the present invention, it is possible to reduce the feeling of tightness of the skin after using the skin cleansing agent without impairing or improving the excellent cleaning power of the surfactant.
  • the skin cleanser containing fatty acid soap has good foaming, creamy foam quality and excellent cleaning power, but it gives a strong feeling of tension after use. Therefore, it is preferable to apply this invention to the skin cleansing agent of the form containing a fatty acid soap. ADVANTAGE OF THE INVENTION According to this invention, the feeling of firmness of the skin after use can be reduced, without impairing the advantageous effect which the skin cleansing agent containing fatty acid soap has.
  • the content ratio of the water-soluble copolymer to the fatty acid soap is 1: 500 to 1: 2, preferably 1: 200 to 1: 3, more preferably 1: 100 to 1: 5. It is.
  • the present invention is also preferably applied to a skin cleanser containing a nonionic surfactant.
  • ADVANTAGE OF THE INVENTION According to this invention, the feeling of firmness of the skin after use can be reduced, improving the detergency of the skin cleansing agent containing a nonionic surfactant.
  • the content ratio of the water-soluble copolymer and the nonionic surfactant is 1:20 to 1: 0.5, preferably 1:15 to 1: 0.7, more preferably Is from 1:10 to 1: 1.
  • the present invention for solving the fifth problem is an oil-in-water sunscreen cosmetic comprising components (A) to (D).
  • B) One molecule of polyglycerol having a polymerization degree of 10 and 2 to 5 molecules of fatty acids having 16 or more carbon atoms are ester-condensed Polyglycerin fatty acid ester (C) ionic surfactant (D) UV scattering agent and / or UV absorber
  • the sunscreen cosmetics of the present invention have a UV protection function and are less sticky and excellent in moisture retention. Moreover, the sunscreen cosmetic of the present invention has emulsion stability.
  • the hydrophilic monomer is a polymerizable carboxylic acid, a hydrophilic monomer represented by the general formula (2), a hydrophilic monomer represented by the general formula (9), or the general formula ( The hydrophilic monomer represented by 10) and one or more hydrophilic monomers selected from the group consisting of the hydrophilic monomer represented by the general formula (11).
  • the hydrophobic monomer is a hydrophobic monomer represented by the general formula (1)
  • the water-soluble monomer is a hydrophilic monomer represented by the general formula (2).
  • a sunscreen cosmetic containing a water-soluble copolymer having a structural unit derived from a hydrophobic monomer and a hydrophilic monomer has a better feeling of use.
  • the component (C) is an anionic surfactant.
  • an anionic surfactant as the ionic surfactant, the emulsion stability can be further improved.
  • the sunscreen cosmetics of the present invention using an anionic surfactant are also excellent in use feeling.
  • the anionic surfactant is sodium acyl lactate.
  • sodium acyl lactate as the anionic surfactant, the emulsion stability can be further improved.
  • the sunscreen cosmetic of the present invention using sodium acyl lactate is excellent in the feeling of use.
  • the component (B) is polyglyceryl-10 pentastearate.
  • the sunscreen cosmetic of the present invention containing polyglyceryl-10 pentastearate is excellent in emulsion stability and feeling of use.
  • the component (D) is a water-dispersible ultraviolet scattering agent. Since the water-dispersible ultraviolet scattering agent is uniformly dispersed in the aqueous phase, the sunscreen cosmetic in such a form is excellent in the ultraviolet protection function.
  • the water-dispersible ultraviolet scattering agent is an ultraviolet scattering agent that has been surface-treated with sodium polyacrylate.
  • the UV scattering agent is more uniformly dispersed, and the UV protection function is excellent.
  • the present invention that solves the sixth problem includes one or more structural units (i) derived from a hydrophobic monomer and one or more structural units (j) derived from a hydrophilic monomer.
  • a water-soluble polymer and / or a salt thereof, and water As an essential constituent unit, a water-soluble polymer and / or a salt thereof, and water, A composition having a sea-island structure in which island particles containing the amphiphilic copolymer are dispersed in an aqueous gel formed by the water-soluble polymer and / or a salt thereof by evaporation of the water. It is a thing.
  • the film has a sea-island structure mainly composed of water-soluble components, and has a touch like milk containing an oil. According to the composition of the present invention, a film having such a sea-island structure can be formed on the skin.
  • the average major axis / minor axis ratio of the island particles is 0.8 or more, and the number particle size distribution of the island particles having an average particle diameter of 1 to 5 ⁇ m is 80% or more.
  • the coating film having such structural characteristics is excellent in moisture retention and flexibility. And the film which has such an outstanding property can be easily formed by apply
  • the water-soluble polymer is one or more water-soluble polymers selected from the group consisting of an acrylic acid-based water-soluble polymer, a water-soluble polypeptide and a water-soluble polysaccharide and / or its It is salt.
  • the water-solubility of the component of a composition can be improved, and stability of a composition can be improved by suppressing generation
  • the water-soluble polymer is selected from the group consisting of sodium polyacrylate, (acrylates / alkyl acrylate (C10-30)) crosspolymer, sodium polyglutamate, xanthan gum and white jellyfish polysaccharide 1 It is a seed or two or more water-soluble polymers. By setting it as the form containing such a water-soluble polymer, stability of a composition can be improved more.
  • the composition comprises a polyol that promotes phase separation between the aqueous gel and the amphiphilic copolymer and / or a polyol that inhibits phase separation between the aqueous gel and the amphiphilic copolymer.
  • a polyol that promotes phase separation between the aqueous gel and the amphiphilic copolymer and / or a polyol that inhibits phase separation between the aqueous gel and the amphiphilic copolymer.
  • the polyol that promotes phase separation is a polyol that increases the cloud point of the aqueous solution by mixing with an aqueous solution of a nonionic surfactant having a polyether chain in the hydrophilic portion.
  • the polyol that suppresses phase separation is a polyol that lowers the cloud point of an aqueous solution by mixing with an aqueous solution of a nonionic surfactant having a polyether chain in a hydrophilic portion.
  • the polyol for promoting phase separation is one or more polyols selected from the group consisting of 1,3-butylene glycol and polyethylene glycol.
  • the polyol that suppresses phase separation is one or more polyols selected from the group consisting of glycerin, diglycerin, sorbitol, and maltitol.
  • the mass ratio of the total amount of the polyol that promotes phase separation and the polyol that suppresses phase separation to the total amount of the amphiphilic copolymer and the water-soluble polymer is 5: 1 to 20: 1.
  • the mass ratio of the polyol that promotes phase separation and the polyol that inhibits phase separation is 3.5: 1 to 1: 2.5.
  • the content of the amphiphilic copolymer is 0.1 to 5% by mass.
  • content of an oil agent is 1 mass% or less.
  • the amphiphilic copolymer includes one or more copolymers selected from the following group E.
  • Group E Polyquaternium-51, Polyquaternium-61, (glyceryl amidoethyl methacrylate / stearyl methacrylate) copolymer, and a structure derived from a hydrophobic monomer selected from the above general formulas (1), (7), (8) Acrylic acid amphiphilic copolymer containing unit (i)
  • composition of the present invention containing such an amphiphilic copolymer has a stronger feel like milk and can form the above-described coating film with better flexibility.
  • the acrylic acid-based amphiphilic copolymer contains a structural unit (j) derived from one or more hydrophilic monomers selected from the following group F.
  • Group F polymerizable carboxylic acid, copolymer represented by general formula (2), copolymer represented by general formula (9), copolymer represented by general formula (10), and general formula (11) Copolymer represented by
  • composition of the present invention containing the amphiphilic copolymer having the structural unit (j) derived from such a hydrophilic monomer can form the above-described film excellent in the touch like milk and flexibility. it can.
  • the acrylic acid-based amphiphilic copolymer is represented by the structural unit (i) derived from the hydrophobic monomer represented by the general formula (1) and the general formula (2).
  • a structural unit (j) derived from a hydrophilic monomer According to the composition of the present invention containing such an acrylic acid-based amphiphilic copolymer, it is possible to form the coating film with better moisture retention and flexibility.
  • the present invention is a film having a sea-island structure in which island particles containing an amphiphilic copolymer are dispersed in an aqueous gel formed by a water-soluble polymer
  • the amphiphilic copolymer essentially comprises one or more structural units (i) derived from a hydrophobic monomer and one or more structural units (j) derived from a hydrophilic monomer. It also relates to a coating characterized by having as a unit.
  • the film of the present invention has a sea-island structure mainly composed of water-soluble components. And although it has a water-soluble component as a main component, it feels like milk containing an oil.
  • the average major axis / minor axis ratio of the island particles is 0.8 or more, and the number particle size distribution of the island particles having an average particle diameter of 1 to 5 ⁇ m is 80% or more.
  • the coating having such a structural characteristic is excellent in the touch like milk containing an oil agent.
  • the present invention also provides a method for forming the above-described film of the present invention, An amphiphilic copolymer having one or more structural units (i) derived from a hydrophobic monomer and one or more structural units (j) derived from a hydrophilic monomer as essential structural units And a method comprising applying to the skin a composition comprising a water-soluble polymer and / or a salt thereof and water. According to the method of the present invention, the coating film can be easily formed.
  • the composition comprises a polyol that promotes phase separation between the amphiphilic copolymer and the aqueous gel and / or a polyol that suppresses phase separation between the aqueous gel and the amphiphilic copolymer. Including. By using an aqueous solution containing such a polyol, the film having excellent uniformity can be formed.
  • a copolymer having a feeling of elasticity and an external preparation for skin can be provided.
  • an emulsified composition having excellent emulsification stability while having little irritation to the skin and less stickiness.
  • the present invention it is possible to provide a skin cleanser with reduced feeling of tension after use.
  • the present invention when the present invention is applied to a skin cleanser containing a fatty acid soap, it is possible to reduce the feeling of tension after use without inhibiting good-quality foaming and creamy foam quality.
  • this invention is applied to a gel-like skin cleansing agent, the effect of reducing the feeling of tension after use can be obtained.
  • an oil-in-water sunscreen cosmetic that has an excellent UV protection function, is excellent in use feeling such as no stickiness and moisturizing feeling, and has emulsion stability. Can do.
  • the present invention it is possible to provide a film having a sea-island structure mainly composed of a water-soluble component and a technique for forming the film.
  • the coating film has a milk-like feel including an oil agent, despite being mainly composed of water-soluble components.
  • the technique which forms the said coating film and this coating film without stickiness can be provided.
  • FIG. 3 shows a three-component phase diagram in which blending ratios of (glyceryl diisostearate methacrylate / methoxymethoxymethacrylate PEG-23) copolymer, squalane and water in Examples 9 to 31 are plotted.
  • FIG. 3 shows a three-component phase diagram in which the blending ratio of (glyceryl diisostearate methacrylate / methoxymethoxymethacrylate PEG-23) copolymer, tri (caprylic acid / capric acid) glyceryl and water in Examples 32-62 is plotted.
  • FIG. 3 shows a three-component phase diagram in which blending ratios of (glyceryl diisostearate methacrylate / methoxymethoxymethacrylate PEG-23) copolymer, tri (caprylic acid / capric acid) glyceryl and water in Examples 32-62 is plotted.
  • FIG. 3 shows a three-component phase diagram in which blending ratios of (glyceryl diisostearate methacrylate / methoxymethoxy methacrylate PEG-23) copolymer, dimethicone and water in Examples 63 to 89 are plotted.
  • the three-component phase diagram of the total amount of 1,3-butylene glycol, glycerin, xanthan gum and (methoxy methacrylic acid PEG-23 / glyceryl diisostearate) copolymer contained in Examples 104 to 124 is shown.
  • the photomicrographs of the compositions of Examples 105, 106, 108, 111, 113, 114, 115, 119, 120, 122, 123 are shown.
  • the pie chart showing the result of the touch evaluation of the composition of Example 104 in Test Example 7 is shown.
  • the copolymer of the present invention that solves the first problem includes one or more structural units (a) derived from the hydrophobic monomer represented by the general formula (1), and the general formula (2).
  • One or more structural units (b) derived from the hydrophilic monomer represented are included as essential structural units.
  • the “structural unit derived from a monomer” refers to a structural unit formed by cleavage of a carbon-carbon unsaturated bond of a corresponding monomer by a polymerization reaction.
  • the hydrophobic monomer represented by the general formula (1) and the hydrophilic monomer represented by the general formula (2) will be described.
  • the copolymer of the present invention is a kind of structural unit derived from the hydrophobic monomer represented by the general formula (1) (hereinafter sometimes simply referred to as “structural unit (1)”). Alternatively, two or more kinds are contained as essential constituent units.
  • examples of the alkyl group represented by R1 include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclopropyl group.
  • R1 is preferably a hydrogen atom or a methyl group.
  • Examples of the branched acyl group having 6 to 22 carbon atoms that does not include the ring structure represented by R2 and R3 include a 2-methylpentanoyl group, a 3-methylpentanoyl group, a 4-methylpentanoyl group, 2-ethylbutanoyl group, 2-ethylbutanoyl group, 2,2-dimethylbutanoyl group, 3,3-dimethylbutanoyl group, 2-methylhexanoyl group, 4-methylhexanoyl group, 5-methylhexanoyl group Noyl group, 2,2-dimethylpentanoyl group, 4,4-dimethylpentanoyl group, 2-methylheptanoyl group, 2-ethylhexyl group, 2-propylpentanoyl group, 2,2-dimethylhexanoyl group, 2 , 2,3-trimethylpentanoyl group, 2-methyloctanoyl group, 3,
  • the hydrophobic monomer represented by the general formula (1) is a hydrophobic monomer represented by the general formula (3).
  • Such a branched acyl group having 10 to 22 carbon atoms which does not contain a ring structure and is represented by R8 and R9 in a preferred embodiment includes a 2-methylnonanoyl group, a 4-methylnonanoyl group, and an 8-methylnonanoyl group.
  • the acyl group having 6 to 9 carbon atoms having 2 or more branches and containing no ring structure represented by R8 and R9 includes a 2,2-dimethylbutanoyl group, 3, 3-dimethylbutanoyl group, 2,2-dimethylpentanoyl group, 4,4-dimethylpentanoyl group, 2,2-dimethylhexanoyl group, 2,2,3-trimethylpentanoyl group, 3,5,5 -A trimethylhexanoyl group etc. can be illustrated.
  • the carbon number of the acyl group of R8 and R9 in the general formula (3) is preferably 12 to 22, more preferably 14 to 20, and still more preferably 16 to 20. Further, the number of carbon atoms in the main chain of the acyl group of R8 and R9 in the general formula (3) is preferably 9 to 21, more preferably 12 to 20, and still more preferably 16 to 18.
  • the number of branches in the acyl group of R8 and R9 in the general formula (3) is preferably 1 to 3, more preferably 1 or 2, and still more preferably 1.
  • the position number of the carbon in the main chain to which the branched chain is bonded is preferably as large as possible. Specifically, the branched chain is bonded to the carbon at the end of the main chain, preferably from the 1st to 3rd carbon, more preferably the 1st or 2nd carbon, and even more preferably the 1st carbon. It is preferable.
  • R8 and R9 include 10-methylundecanoyl group, 10-methyldodecanoyl group, 11-methyldodecanoyl group, 10-ethylundecanoyl group, 12-methyltridecanoyl group, 12-methyl Tetradecanoyl group, 14-methylpentadecanoyl group, 16-methylheptadecanoyl group, 2,4,10,14-tetramethylpentanoyl group, 18-methylnonadecanoyl group, 3,7,11,15 Preferred examples include -tetra-methylhexadecanoyl group, 19-methyleicosanoyl group and the like.
  • the group derived from the trihydric alcohol represented by X or Y in the general formulas (1) and (3) is not particularly limited as long as the OH group is released from the trihydric alcohol.
  • a group in which an OH group is eliminated from a trihydric alcohol selected from the group consisting of trimethylolpropane and trimethylolethane can be suitably exemplified.
  • a monomer represented by the general formula (5) it is preferable to use a monomer represented by the general formula (5) as a hydrophobic monomer.
  • Examples of the hydrophobic monomer represented by the general formula (5) include compounds represented by the following formulas (12) to (14).
  • a compound represented by the following formula (12) in which a branched chain is added to the end of the acyl group is used.
  • the hydrophobic monomer represented by the general formula (1) constituting the copolymer of the present invention can be synthesized, for example, by the following method.
  • a) Ketalize trihydric alcohol As a specific synthesis method, for example, the method described in Production Example 1 of JP-A-2009-136749 can be exemplified.
  • the ketalized trihydric alcohol also has a commercial item, it is also possible to obtain the ester of the trihydric alcohol of the present invention by using the commercial product and the above steps b) and c).
  • Such commercial products include (S)-(+)-2,2-dimethyl-1,3-dioxalane-4-methanol, (R)-(+)-2,2-dimethyl-1,3- An example is dioxalane-4-methanol (both manufactured by Tokyo Chemical Industry Co., Ltd.).
  • there are commercially available products of mono (meth) acrylic acid esters of trihydric alcohols it is also possible to obtain the esters of the trihydric alcohols of the present invention by the above step c) using such commercially available products. Examples of such commercially available products include “Blemmer GLM” (glycerin monomethacrylate manufactured by Nippon Oil & Fats Co., Ltd.).
  • the ratio of the structural unit (a) to the total structural units is preferably 1 to 40% by mass, more preferably 5 to 35% by mass.
  • the copolymer of the present invention contains one or more structural units derived from the hydrophilic monomer represented by the general formula (2) as essential structural units.
  • examples of the alkyl group represented by R4 include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclopropyl group.
  • R4 is preferably a hydrogen atom or a methyl group.
  • alkylene group represented by R5 examples include ethylene group, propylene group, isopropylene group, 2-hydroxypropylene group, 1-hydroxy-2-methylethylene group, 2-hydroxy-1-methylethylene group and the like. Of these, ethylene group or propylene group is preferable, and ethylene group is more preferable.
  • examples of the aromatic group having 6 to 10 carbon atoms include a phenyl group, a benzyl group, a methylphenyl group, and an ethylphenyl group; an aliphatic carbon atom having 1 to 14 carbon atoms
  • Preferred examples of the hydrogen group include a methyl group, an ethyl group, a butyl group, a tertiary butyl group, a hexyl group, a cyclohexyl group, an octyl group, a 2-ethylhexyl group, and a lauryl group
  • Preferred examples of the 12 acyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, and a lauroyl group.
  • the group represented by R5 is preferably an aliphatic hydrocarbon group having 1 to 14
  • n in the general formula (2) is in the numerical range of 6 to 40.
  • Specific examples of the monomer represented by the general formula (2) in which R5 is a propylene group include polypropylene glycol (9) monoacrylate, polypropylene glycol (13) monoacrylate, and polypropylene glycol (9) monomethacrylate. And polypropylene glycol (13) monomethacrylate.
  • the number in parentheses represents N.
  • Many of these polymers are commercially available. Specific examples of such commercially available products include “Blemmer” AP-400, AP-550, AP-800, PP-500, PP-800 (all manufactured by NOF Corporation) and the like.
  • R5 is an ethylene group, specifically, polyethylene glycol (10) monoacrylate, polyethylene glycol (8) monomethacrylate, polyethylene glycol (23) monoacrylate.
  • the monomer represented by the general formula (6) is used as the hydrophilic monomer.
  • l is preferably 6-30, more preferably 8-30.
  • hydrophilic monomer can be obtained in high yield by esterification reaction of the corresponding polyethylene glycol, polyethylene glycol monoether, polyethylene glycol monoester with acrylic acid or methacrylic acid chloride or anhydride.
  • esterification reaction of the corresponding polyethylene glycol, polyethylene glycol monoether, polyethylene glycol monoester with acrylic acid or methacrylic acid chloride or anhydride.
  • Specific examples of such commercially available products include Blemmer, AE-400, PE-350, AME-400, PME-400, PME-1000, ALE-800, PSE-1300, etc. Etc.).
  • the structural unit derived from the hydrophilic monomer contained in the copolymer of the present invention may be only one type, but may contain two or more types of structural units in combination as long as the above conditions are satisfied.
  • the ratio of the structural unit (b) derived from the hydrophilic monomer to the total structural units is 30 to 95% by mass, preferably 40 to 90% by mass.
  • the copolymer of the present invention includes units derived from monomers usually used in a copolymer in addition to the above-mentioned structural unit 1 and structural unit 2 as long as the effects of the invention are not impaired. It can contain as arbitrary structural units.
  • optional structural units include acrylic acid amide, methacrylic acid amide, acrylic acid monoalkylamide, (meth) acrylic acid amide such as methacrylic acid monoalkylamide, methyl (meth) acrylate, ethyl (meth) acrylate, N-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-dodecyl methacrylate , (Meth) acrylic acid stearyl, (meth) acrylic acid isostearyl and other (meth) acrylic acid alkyl esters, (meth) acrylic acid cyclohexyl and other cyclic alkyl esters, 2-hydroxyethyl (meth) acrylate 2-hydroxypropyl (meth) acrylate, 4 -(Meth) acrylic acid
  • Examples thereof include structural units derived from monomers such as (meth) acrylic acid alkoxyalkyl esters, vinyl acetate, vinylpyrrolidone, styrene, ⁇ -methylstyrene, acrylonitrile and the like. Most of these monomers are commercially available.
  • the copolymer of the present invention is a copolymer containing the structural unit (a) and the structural unit (b) in its skeleton. Further, the copolymer of the present invention is usually a random copolymer in which structural units are randomly bonded, but may be a block copolymer or a graft copolymer.
  • the copolymer of the present invention has a weight average molecular weight of 20,000 to 110,000. By setting the weight average molecular weight within the above range, the copolymer of the present invention becomes elastic.
  • the weight average molecular weight of the copolymer of the present invention is more preferably 20,000 to 80,000, more preferably 30,000 to 80,000, more preferably 40,000 to 70,000, still more preferably 50,000 to 70,000, still more preferably 57,000 to 66,000.
  • a weight average molecular weight here means the weight average molecular weight of polystyrene conversion measured by GPC.
  • the method for producing the copolymer of the present invention is not particularly limited.
  • the copolymer can be obtained by a method in which monomers for deriving each structural unit are mixed in a solvent and a polymerization reaction is carried out according to a method usually used in the polymerization of acrylic monomers.
  • the weight average molecular weight of the copolymer can be adjusted by changing the reaction time and reaction temperature of the polymerization reaction. Specifically, the weight average molecular weight can be reduced by shortening the reaction time.
  • the copolymer of the present invention is preferably water-soluble because it is easy to handle.
  • the copolymer here is defined as a copolymer having a transmittance of 90% or more of a 20% by mass aqueous solution of the copolymer at 25 ° C.
  • a polymerization method in which the monomer mixture is radically polymerized in a mixed solvent of an aqueous solution and an aqueous solvent mixed with water at an arbitrary ratio at 25 ° C. is particularly preferable. .
  • a polymerization method using a buffer solution instead of water is more preferable.
  • the aqueous solution having a buffering action used in this method is not particularly limited as long as it is a commonly used buffer solution.
  • potassium chloride-hydrochloric acid solution, potassium hydrogen phthalate-hydrochloric acid solution, dihydrogen phosphate examples thereof include a potassium-disodium hydrogen phosphate solution, a potassium hydrogen citrate-citric acid solution, and a sodium carbonate-sodium hydrogen carbonate solution.
  • an aqueous solution of salts, acids, or bases that forms a buffer solution with the ions of the initiator may be used to form a buffer solution when the initiator is added.
  • examples of the aqueous solvent used in this method which are miscible with water at an arbitrary ratio at 25 ° C.
  • alcohols having 1 to 3 carbon atoms such as methyl alcohol, ethyl alcohol, n-propyl alcohol, and isopropyl alcohol.
  • examples thereof include ketones such as acetone and methyl ethyl ketone, diols such as ethylene glycol, polyethylene glycol, propylene glycol and 1,3 butylene glycol, ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, and tetrahydrofuran.
  • alcohols having 1 to 3 carbon atoms such as methanol, ethanol, n-propanol, and isopropanol are particularly preferable because the polymerization reaction easily proceeds.
  • the mass ratio of the structural unit (a) to the structural unit (b) constituting the copolymer is preferably 5:95 to 50:50, more preferably 10:90 to 45:55, and still more preferably 20:80 to 40:60, more preferably 25:75 to 35:65.
  • the molar ratio of the structural unit (a) to the structural unit (b) constituting the copolymer is preferably 8:92 to 62:38, more preferably 15:85 to 57:43, and still more preferably 29:71. 52:48, more preferably 35:65 to 46:54.
  • External preparation for skin containing the copolymer of the present invention has a feeling of elasticity and hardly causes stickiness.
  • the content of the copolymer of the present invention is preferably 0.5 to 30% by mass, more preferably 1 to 25% by mass.
  • the external preparation for skin of the present invention include external medicines such as ointments, cosmetics and the like.
  • cosmetics include skin care such as creams, milky lotions, lotions, beauty essences, sunscreen cosmetics, make-ups such as under makeup, foundations, eye colors and mascara, skin cleansers such as facial cleansers, hair tonics, hair Examples thereof include hair cosmetics such as liquid and hair spray.
  • the external preparation for skin of the present invention can contain, as an optional component, components that are usually used for external preparations for skin as long as the effects of the invention are not impaired.
  • optional components specifically, Macadamia nut oil, avocado oil, corn oil, olive oil, rapeseed oil, sesame oil, castor oil, safflower oil, cottonseed oil, jojoba oil, coconut oil, palm oil, liquid lanolin, hydrogenated coconut oil, hydrogenated oil, molasses, hydrogenated castor oil, Oils such as beeswax, candelilla wax, carnauba wax, ibotarou, lanolin, reduced lanolin, hard lanolin, jojoba wax, waxes, liquid paraffin, squalane, pristane, ozokerite, paraffin, ceresin, petrolatum, hydrocarbons such as microcrystalline wax, Higher fatty acids such as oleic acid, isostearic acid, lauric acid, myristic acid, palmitic acid
  • Oils such as silicone oils such as modified polysiloxanes, fatty acid soaps (sodium laurate, sodium palmitate, etc.), anionic surfactants such as potassium lauryl sulfate, alkylethanol triethanolamine ether, stearyltrimethylammonium chloride, chloride Cationic surfactants such as benzalkonium and laurylamine oxide, imidazoline-based amphoteric surfactants (2-cocoyl-2-imidazolinium hydroxide-1-cal Boxyethyloxy disodium salt, etc.), betaine surfactants (alkyl betaine, amide betaine, sulfobetaine, etc.), amphoteric surfactants such as acylmethyltaurine, sorbitan fatty acid esters (sorbitan monostearate, sorbitan sesquioleate, etc.) ), Glycerin fatty acids (such as glyceryl monostearate), propylene glycol fatty acid esters (such
  • the external preparation for skin of the present invention can be prepared by treating the above essential components and optional components by a conventional method.
  • the water-soluble copolymer has a structural unit (c) derived from a hydrophobic monomer and a structural unit (d) derived from a hydrophilic monomer. It is to include.
  • a hydrophobic monomer, a hydrophilic monomer, and a water-soluble copolymer that is a copolymer thereof will be described.
  • a structural unit derived from the hydrophobic monomer represented by the general formula (1), (7) or (8) (hereinafter simply referred to as “ A water-soluble copolymer containing one or more structural units (sometimes referred to as “structural unit (7)”) as essential structural units is used.
  • the “structural unit derived from a monomer” refers to a structural unit formed by cleavage of a carbon-carbon unsaturated bond of a corresponding monomer by a polymerization reaction.
  • the hydrophobic monomer represented by the general formula (1), (7) or (8) will be described.
  • R14 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R15 represents a ring having 13 to 30 carbon atoms.
  • a branched hydrocarbon group not containing a structure or a hydrocarbon group having 6 to 12 carbon atoms having two or more branches not containing a ring structure is represented.
  • examples of the alkyl group represented by R14 include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclopropyl group.
  • R14 is preferably a hydrogen atom or a methyl group.
  • Examples of the branched hydrocarbon group not containing a ring structure having 13 to 30 carbon atoms represented by R15 include 1-methyldodecanyl group, 11-methyldodecanyl group, 3-ethylundecanyl group, 3- Ethyl-4,5,6-trimethyloctyl, 1-methyltridecanyl, 1-hexyloctyl, 2-butyldecanyl, 2-hexyloctyl, 4-ethyl-1-isobutyloctyl, 1-methyl Pentadecanyl group, 2-hexyldecanyl group, 2-octyldecanyl group, 2-hexyldecanyl group, 16-methylheptadecanyl group, 9-methylheptadecanyl group, 7-methyl-2- (3 -Methylhexyl) decanyl group, 3,7,11,15-tetra-methylhexadecanyl group, 2-octyldode
  • examples of the hydrocarbon group having 6 to 12 carbon atoms having two or more branches and not including a ring structure represented by R15 include 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3, 3-dimethylbutyl group, 1,3-dimethylbutyl group, 1,2,2-trimethylpropyl group, 1,1-dimethylpentanyl group, 1-isopropylbutyl group, 1-isopropyl-2-methylpropyl group, 1 , 1-diethylpropyl group, 1-ethyl-1-isopropylpropyl group, 2-ethyl-4-methylpentyl group, 1-propyl-2,2-dimethylpropyl group, 1,1,2-trimethyl-pentyl group, 1-isopropyl-3-methylbutyl group, 1,2-dimethyl-1-ethylbutyl group, 1,3-dimethyl-1-ethylbutyl group, 1-ethyl-1-isopropyl-
  • R1 and R16 each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • R2, R3, R17, R18, and R19 may be the same or different and each represents a branched acyl group having 6 to 22 carbon atoms that does not contain a ring structure.
  • X represents a group in which an OH group is eliminated from a trivalent alcohol.
  • examples of the alkyl group represented by R1 and R16 include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclopropyl group.
  • R1 is preferably a hydrogen atom or a methyl group.
  • Examples of the branched acyl group having 6 to 22 carbon atoms that does not include the ring structure represented by R2, R3, R17, R18, and R19 include 2-methylpentanoyl group, 3-methylpentanoyl group, 4 -Methylpentanoyl group, 2-ethylbutanoyl group, 2-ethylbutanoyl group, 2,2-dimethylbutanoyl group, 3,3-dimethylbutanoyl group, 2-methylhexanoyl group, 4-methylhexanoyl group Group, 5-methylhexanoyl group, 2,2-dimethylpentanoyl group, 4,4-dimethylpentanoyl group, 2-methylheptanoyl group, 2-ethylhexyl group, 2-propylpentanoyl group, 2,2- Dimethylhexanoyl group, 2,2,3-trimethylpentanoyl group, 2-methyloctanoyl group,
  • R2, R3, R17, R18, and R19 may be the same or different and do not include a ring structure and have a branch.
  • Such a branched acyl group having 10 to 22 carbon atoms which does not contain a ring structure and is represented by R2, R3, R17, R18 and R19 in a preferred embodiment includes a 2-methylnonanoyl group, 4- Methylnonanoyl group, 8-methylnonanoyl group, 4-ethyloctanoyl group, 2-ethyloctanoyl group, 2-butylhexanoyl group, 2-tert-butylhexanoyl group, 2,2-diethylhexanoyl group), 2, 2-dimethyloctanoyl group, 3,7-dimethyloctanoyl group, neodecanoyl group), 7-methyldecanoyl group, 2-methyl-2-ethyloctanoyl group, 2-methylundecanoyl group, 10-methylun Decanoyl group, 2,2 dimethyldecanoyl group, 2-ethyldecano
  • the acyl group having 6 to 9 carbon atoms having 2 or more branches and containing no ring structure represented by R2, R3, R17, R18, R19 is 2,2-dimethyl.
  • the group derived from the trihydric alcohol represented by X in the general formula (1) is not particularly limited as long as the OH group is eliminated from the trihydric alcohol, but glycerin, trimethylolpropane, trimethylolethane.
  • the group derived from the tetrahydric alcohol represented by Y in the general formula (8) is not particularly limited as long as the OH group is released from the tetrahydric alcohol, but diglycerin, pentaerythritol, erythritol.
  • a group in which an OH group is eliminated from a tetrahydric alcohol selected from the group consisting of D-threitol and L-threitol can be suitably exemplified.
  • the hydrophobic monomer represented by the general formula (1) is a hydrophobic monomer represented by the following general formula (15).
  • R24 and R25 may be the same or different and each represents a branched, acyl group having 16 to 22 carbon atoms that does not contain a ring structure.
  • Z represents an OH group from a trivalent alcohol. Represents a leaving group.
  • the carbon number of the acyl group of R24 and R25 in the general formula (15) is 12 to 22, more preferably 14 to 20, and still more preferably 16 to 20.
  • the carbon number of the main chain of the acyl group of R24 and R25 in the general formula (15) is preferably 9 to 21, more preferably 12 to 20, and still more preferably 16 to 18.
  • the number of branches in the acyl group of R24 and R25 in the general formula (15) is preferably 1 to 3, more preferably 1 or 2, and still more preferably 1.
  • the position number of carbon in the main chain to which the branched chain is bonded is preferably as large as possible.
  • the branched chain is bonded to the carbon at the end of the main chain, preferably from the 1st to 3rd carbon, more preferably the 1st or 2nd carbon, and even more preferably the 1st carbon. It is preferable.
  • R24 and R25 include 10-methylundecanoyl group, 10-methyldodecanoyl group, 11-methyldodecanoyl group, 10-ethylundecanoyl group, 12-methyltridecanoyl group, 12-methyl Tetradecanoyl group, 14-methylpentadecanoyl group, 16-methylheptadecanoyl group, 2,4,10,14-tetramethylpentanoyl group, 18-methylnonadecanoyl group, 3,7,11,15 Preferred examples include -tetra-methylhexadecanoyl group, 19-methyleicosanoyl group and the like.
  • the group derived from the trihydric alcohol represented by Z in the general formula (15) is not particularly limited as long as the OH group is released from the trihydric alcohol, but glycerin, trimethylolpropane, trimethylolethane.
  • hydrophilic monomer As the hydrophilic monomer in the present invention, a polymerizable carboxylic acid and the compounds represented by the general formula (2), the general formulas (9), (10) and (11) are used. Can do.
  • the polymerizable carboxylic acid or a salt thereof specifically includes acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid and its sodium salt, potassium salt, Examples thereof include ammonium salts and amine salts. Among these, acrylic acid, methacrylic acid and salts thereof are particularly preferable because of high polymerizability.
  • a structural unit derived from a polymerizable carboxylic acid salt is introduced into the water-soluble copolymer of the present invention, the polymerizable carboxylic acid may be converted into a salt in advance, and a polymerization reaction may be performed.
  • a structural unit derived from a carboxylic acid may be derived into a water-soluble copolymer and then neutralized with a base to form a salt.
  • R4 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R5 may have a hydroxyl group.
  • R6 represents a hydrogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, an aliphatic hydrocarbon group having 1 to 14 carbon atoms, or an acyl group having 1 to 12 carbon atoms.
  • n represents an integer of 6 to 40.
  • examples of the alkyl group represented by R4 include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclopropyl group.
  • R4 is preferably a hydrogen atom or a methyl group.
  • alkylene group represented by R5 examples include ethylene group, propylene group, isopropylene group, 2-hydroxypropylene group, 1-hydroxy-2-methylethylene group, 2-hydroxy-1-methylethylene group and the like. Of these, ethylene group or propylene group is preferable, and ethylene group is more preferable.
  • examples of the aromatic group having 6 to 10 carbon atoms include a phenyl group, a benzyl group, a methylphenyl group, and an ethylphenyl group; an aliphatic carbon atom having 1 to 14 carbon atoms
  • Preferred examples of the hydrogen group include a methyl group, an ethyl group, a butyl group, a tertiary butyl group, a hexyl group, a cyclohexyl group, an octyl group, a 2-ethylhexyl group, and a lauryl group
  • Preferred examples of the 12 acyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, and a lauroyl group.
  • the group represented by R5 is preferably an aliphatic hydrocarbon group having 1 to 14
  • n in the general formula (2) is in the numerical range of 6 to 40.
  • Specific examples of the monomer represented by the general formula (2) in which R5 is a propylene group include polypropylene glycol (9) monoacrylate, polypropylene glycol (13) monoacrylate, and polypropylene glycol (9) monomethacrylate. And polypropylene glycol (13) monomethacrylate.
  • the number in parentheses represents N.
  • Many of these polymers are commercially available. Specific examples of such commercially available products include “Blemmer” AP-400, AP-550, AP-800, PP-500, PP-800 (all manufactured by NOF Corporation) and the like.
  • R5 is an ethylene group, specifically, polyethylene glycol (10) monoacrylate, polyethylene glycol (8) monomethacrylate, polyethylene glycol (23) monoacrylate.
  • hydrophilic monomer can be obtained in high yield by esterification reaction of the corresponding polyethylene glycol, polyethylene glycol monoether, polyethylene glycol monoester with acrylic acid or methacrylic acid chloride or anhydride.
  • esterification reaction of the corresponding polyethylene glycol, polyethylene glycol monoether, polyethylene glycol monoester with acrylic acid or methacrylic acid chloride or anhydride.
  • Specific examples of such commercially available products include Blemmer, AE-400, PE-350, AME-400, PME-400, PME-1000, ALE-800, PSE-1300, etc. Etc.).
  • hydrophilic monomer represented by general formula (9) As the hydrophilic monomer in the present invention, a hydrophilic monomer represented by general formula (9) may be used.
  • hydrophilic monomer represented by the general formula (9) examples include 2-acryloyloxyethyl phosphorylcholine (APC) and 2-methacryloyloxyethyl phosphorylcholine (MPC). These monomers can be synthesized by the following method described in Polymer Journal, Vol 22, No. 5, for example.
  • hydrophilic monomer represented by general formula (10) As the hydrophilic monomer in the present invention, a hydrophilic monomer represented by general formula (10) may be used.
  • hydrophilic monomer represented by the general formula (10) as the reducing sugar of the group obtained by removing hydrogen from the hydroxyl group at the 1-position of the reducing sugar represented by GO—, specifically, glucose, mannose,
  • Examples include one or more selected from the group consisting of monosaccharides such as galactose, arabinose, xylose and ribose, disaccharides such as maltose, lactose and cellobiose, trisaccharides such as maltotriose, and oligosaccharides such as malto-oligosaccharide
  • glucose is particularly preferable.
  • the monomer represented by the general formula (10) is preferably glucosyloxyethyl methacrylate (hereinafter abbreviated as GEMA) or glucosyloxyethyl acrylate (hereinafter abbreviated as GEA).
  • GEMA glucosyloxyethyl methacrylate
  • GEA glucosyloxyethyl acrylate
  • hydrophilic monomer represented by general formula (11) As the hydrophilic monomer in the present invention, a hydrophilic monomer represented by general formula (11) may be used.
  • the amino acid of the amino acid residue represented by R23 is not particularly limited as long as it is a commonly known amino acid. Specifically, glycine, alanine, glutamine, lysine, arginine Etc. are exemplified. Among these, the lysine residue is particularly preferable because the obtained water-soluble copolymer is excellent in the effect of restoring the skin barrier.
  • the polyamine in the polyamine residue represented by R23 means an amine having two or more amino groups that may be substituted with an alkyl group in the same molecule, and specifically includes diamine, triamine, tetraamine. Or the amine by which the hydrogen atom of these amino groups is substituted by the alkyl group is illustrated.
  • diamines are preferred because the feeling of use of the resulting external preparation for skin containing the water-soluble copolymer is particularly excellent.
  • Particularly preferred examples include ethylenediamine, 1 from the availability of raw materials for synthesis. , 4-diamino-n-butane, 1,6-diamino-n-hexane and the like.
  • amino alcohol in the amino alcohol residue represented by R23 means a compound having an amino group which may be substituted with an alkyl group in the same molecule and an alcoholic hydroxyl group.
  • the amino alcohol is not particularly limited as long as it is generally known, but specific examples include ethanolamine and triethylaminoethanol.
  • the sodium salt, potassium salt, ammonium salt, amine salt, etc. which neutralized the acid part with the base
  • examples thereof include hydrochlorides, sulfates, nitrates, phosphates, citrates, oxalates, carbonates, etc., in which the amino group is neutralized with an acid.
  • the structural unit derived from the salt of the monomer represented by the general formula (11) is introduced into the water-soluble copolymer of the present invention, the monomer represented by the general formula (11) is converted into a salt in advance to carry out the polymerization reaction.
  • the structural unit derived from the monomer represented by the general formula (11) may be derived into a water-soluble copolymer by a polymerization reaction, and then neutralized to form a salt.
  • Specific examples of the monomer represented by the general formula (11) and salts thereof include compounds 1 to 11 having the following structures and salts thereof.
  • the hydrophilic monomer represented by the general formula (11) is, for example, an esterification reaction using (meth) acrylic acid or (meth) acrylic acid chloride as shown in the following reaction formulas (1) and (2), amide It can be synthesized by a chemical reaction.
  • Reaction formula (1) Reaction formula (2) (In the reaction formula, R22 represents a hydrogen atom or a methyl group, R23 represents an amino acid residue, a polyamine residue or an aminoalcohol residue.
  • Q represents an oxygen atom or a group represented by NH.)
  • the hydrophilic polymer in the present invention the general formula (2), the general formula (9), the general formula (10), and the general formula (11) can be used.
  • the water-soluble copolymer contains the structural unit (2) derived from the general formula (2).
  • a water-soluble copolymer having the structural unit (1) and the structural unit (2) can be preferably used. More preferably, a water-soluble copolymer having the structural unit (15) and the structural unit (2) is used. Of such water-soluble copolymers, a (methoxy PEG-23 methacrylate / glyceryl methacrylate) is particularly preferably used. By containing such a water-soluble copolymer, the emulsion composition is low in irritation, less sticky, and excellent in emulsion stability.
  • (Methoxymethacrylic acid PEG-23 / glyceryl methacrylate) is a structural unit (c) in which R24 and R25 are 16-methylheptadecanoyl among the hydrophobic monomers represented by the general formula (15). It mainly contains a structural unit (c) derived from a hydrophobic monomer as a group. Further, among the hydrophilic monomers represented by the general formula (2), the structural unit (d) is derived from a hydrophilic monomer in which R4 is a methyl group, R5 is an ethylene group, R6 is a methyl group, and n is 23. The structural unit (d) is mainly included.
  • a highly hydrophobic surfactant is suitable for forming a water-in-oil emulsion composition
  • a highly hydrophilic surfactant is suitable for forming an oil-in-water emulsion composition
  • the water-soluble copolymer in the present invention is suitable for forming a water-in-oil type emulsion composition when the proportion of the structural unit (c) that is hydrophobic is high, and is hydrophilic.
  • the proportion of a certain structural unit (d) is high, it is suitable for forming an oil-in-water emulsion composition.
  • the emulsification form of the emulsion composition to be formed can be adjusted by appropriately adjusting the proportion and ratio of the structural unit (c) and the structural unit (d).
  • the proportion of the structural unit (c) in all the structural units in the water-soluble copolymer is preferably 1 to 50% by mass, more preferably 20 to 50% by mass, and 30 to 40% by mass.
  • the proportion of the structural unit (d) in all the structural units in the water-soluble copolymer is preferably 50 to 99% by mass, more preferably 50 to 80% by mass, and 60 to 70% by mass.
  • the mass ratio of the structural unit (c) and the structural unit (d) constituting the water-soluble copolymer is preferably 10:90 to 50:50, more preferably 20:80 to 50:50, Preferably, it is 30:70 to 40:60.
  • the molar ratio of the structural unit (c) to the structural unit (d) constituting the water-soluble copolymer is preferably 15:85 to 62:38, more preferably 29:71 to 62:38, and still more preferably 41. : 59-52: 48.
  • the average molecular weight of the water-soluble copolymer is preferably 20,000 to 110,000, more preferably 20,000 to 80,000, more preferably 30,000 to 80,000, more preferably 40,000 to 70,000, still more preferably 50,000 to 70,000, still more preferably. 57000-66000.
  • an average molecular weight means here the weight average molecular weight of polystyrene conversion measured by GPC.
  • Emulsified Composition The emulsified composition of the present invention is characterized by substantially not containing an emulsifier other than the above-mentioned water-soluble copolymer.
  • substantially free of an emulsifier other than the above-mentioned water-soluble copolymer means that the content of the emulsifier other than the above-mentioned water-soluble copolymer is 0.3% by mass or less, preferably 0.1% by mass or less. More preferably, it means 0.01% by mass or less, more preferably 0.001% by mass or less.
  • the content of the above water-soluble copolymer in the emulsion composition is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass.
  • the contents of the aqueous phase and the oil phase in the emulsion composition of the present invention can be appropriately adjusted by changing the ratio of the structural unit (c) and the structural unit (d) in the water-soluble copolymer.
  • the content of the oil phase and the water phase when a water-soluble copolymer containing the structural unit (c) and the structural unit (d) is used in a ratio suitable for forming the above-described oil-in-water emulsion composition, etc. Will be described.
  • the oil phase and the oil phase component, and the water phase and the water phase component are described as not including the water-soluble copolymer in the present invention.
  • the content of the oil phase component in the emulsion composition of the present invention is preferably 0.01 to 80% by mass, more preferably 0.1 to 70% by mass. By making content of an oil phase component into the said range, the emulsification stability of an emulsion composition can be improved.
  • an oil phase component is an oil agent and a lipophilic component, and means the component contained in an oil phase in an emulsion composition.
  • the mass ratio of the water-soluble copolymer and the oil phase component is preferably 1: 100 to 1: 0.2, more preferably 1:70 to 1: 0.3.
  • the mass ratio of the oil phase to the aqueous phase is preferably 0.1: 99.9 to 80:20, more preferably 1:99 to 65:35.
  • the components contained in the oil phase and the aqueous phase are not particularly limited.
  • the oil agent constituting the oil phase include liquid oils and fats, solid oils and fats, waxes, hydrocarbon oils, higher fatty acids, higher alcohols, synthetic ester oils, silicone oils, and the like.
  • liquid oils 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, southern castor oil, castor oil, linseed oil , Safflower oil, cottonseed oil, eno oil, meadow foam oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnagari oil, Japanese kiri oil, jojoba oil, germ oil, triglycerin, glycerin trioctanoate, Examples include glycerin triisopalmitate.
  • Solid fats and oils include cocoa butter, coconut oil, horse fat, hydrogenated coconut oil, palm oil, beef tallow, sheep fat, hardened beef tallow, palm kernel oil, pork fat, beef bone fat, owl kernel oil, hydrogenated oil, and cow leg fat. , Mole, hardened castor oil, and the like.
  • the waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibota wax, whale wax, montan wax, nuka wax, lanolin, kapok wax, lanolin acetate, liquid lanolin, sugar cane wax, lanolin fatty acid isopropyl, lauryl hexyl, reduced lanolin, jojojo Examples thereof include a 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, and the like.
  • hydrocarbon oils examples include liquid paraffin, ozokerite, pristane, paraffin, ceresin, squalene, petrolatum, and microcrystalline wax.
  • higher fatty acids examples include lauric acid, myristic acid, palmitic acid, stearic acid, behen (behenine) acid, 12-hydroxystearic acid, undecylenic acid, and toric acid.
  • higher alcohols examples include cetyl alcohol, stearyl alcohol, behenyl alcohol, batyl alcohol, myristyl alcohol, cetostearyl alcohol, and the like.
  • Synthetic ester oils include isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyloctanoate, cetyl lactate, myristyl lactate Lanolin acetate, isocetyl stearate, isocetyl isostearate, sucrose stearate, sucrose oleate, cholesteryl 12-hydroxystearylate, ethylene glycol di-2-ethylhexylate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, Neopentyl glycol dicaprate, diisostearyl malate, glycerin di-2-heptylundecanoate, tri-2-
  • silicone oils include chain polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane, and cyclic polysiloxanes such as decamethylpolysiloxane, dodecamethylpolysiloxane, and tetramethyltetrahydrogenpolysiloxane. Is mentioned.
  • One or more oil agents can be used.
  • additive components that are usually blended in cosmetics may be blended within a range that does not impair the effects of the present invention.
  • additive components include humectants such as polyethylene glycol, glycerin, 1,3-butylene glycol, erythritol, sorbitol, xylitol, and maltitol; lower alcohols such as ethanol; butylhydroxytoluene, tocopherol, and phytin.
  • Antioxidants such as benzoic acid, salicylic acid, sorbic acid, paraoxybenzoic acid alkyl ester, hexachlorophene; paraaminobenzoic acid (hereinafter abbreviated as “PABA”), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester N, N-diethoxy PABA ethyl ester, N, N-dimethyl PABA methyl ester, N, N-dimethyl PABA ethyl ester, N, N-dimethyl PABA butyl ester, N, N-dimethyl P Benzoic acid UV absorbers such as BA2-ethylhexyl ester; Anthranilic acid UV absorbers such as homomenthyl-N-acetylanthranilate; Amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate,
  • Drugs Barefoot, Clara, corn, orange, sage, yarrow, mallow, thyme, thyme, spruce, spruce, birch, horsetail, loofah, maronier, saxifrage Extracts of plants such as arnica, lily, mugwort, peonies, aloe, gardenia, sawara; pigments; porous and / or water-absorbing powders (eg starches derived from corn, potatoes, silicic acid, talc) , Powders of kaolin, aluminum magnesium silicate, calcium alginate, etc.); neutralizers; preservatives; fragrances; pigments and the like.
  • the emulsion composition of the present invention can be produced by preparing an aqueous phase component and an oil phase component each containing the above-mentioned water-soluble copolymer and stirring and mixing them in a conventional manner.
  • the emulsified composition of the present invention has low irritation and less stickiness, so it can be used as cosmetics such as emulsions, creams, serums, sunscreens, liquid foundations, skin external preparations, quasi drugs and pharmaceuticals. Is preferred.
  • Emulsifier also relates to an emulsifier comprising the above-mentioned water-soluble copolymer.
  • the description regarding the water-soluble copolymer and the emulsion composition described above can be applied to the emulsifier of the present invention.
  • This invention relates also to the method of manufacturing an emulsion composition using the emulsifier of this invention mentioned above.
  • the method of the present invention is characterized in that no emulsifier other than the emulsifier of the present invention is used.
  • the description regarding the water-soluble copolymer and the emulsion composition described above can be applied to the production method of the present invention.
  • the features of the skin cleanser of the present invention that solves the third and fourth problems are water-soluble having a structural unit (e) derived from a hydrophobic monomer and a structural unit (f) derived from a hydrophilic monomer. Including a copolymer.
  • a hydrophobic monomer, a hydrophilic monomer, and a water-soluble copolymer that is a copolymer thereof will be described.
  • a structural unit derived from the hydrophobic monomer represented by the general formula (1), (7) or (8) (hereinafter simply referred to as “ A water-soluble copolymer containing one or more structural units (sometimes referred to as “structural unit (7)”) as essential structural units is used.
  • the “structural unit derived from a monomer” refers to a structural unit formed by cleavage of a carbon-carbon unsaturated bond of a corresponding monomer by a polymerization reaction.
  • the hydrophobic monomer represented by the general formula (1), (7) or (8) will be described.
  • R14 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R15 represents a ring having 13 to 30 carbon atoms.
  • a branched hydrocarbon group not containing a structure or a hydrocarbon group having 6 to 12 carbon atoms having two or more branches not containing a ring structure is represented.
  • examples of the alkyl group represented by R14 include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclopropyl group.
  • R14 is preferably a hydrogen atom or a methyl group.
  • Examples of the branched hydrocarbon group not containing a ring structure having 13 to 30 carbon atoms represented by R15 include 1-methyldodecanyl group, 11-methyldodecanyl group, 3-ethylundecanyl group, 3- Ethyl-4,5,6-trimethyloctyl, 1-methyltridecanyl, 1-hexyloctyl, 2-butyldecanyl, 2-hexyloctyl, 4-ethyl-1-isobutyloctyl, 1-methyl Pentadecanyl group, 2-hexyldecanyl group, 2-octyldecanyl group, 2-hexyldecanyl group, 16-methylheptadecanyl group, 9-methylheptadecanyl group, 7-methyl-2- (3 -Methylhexyl) decanyl group, 3,7,11,15-tetra-methylhexadecanyl group, 2-octyldode
  • examples of the hydrocarbon group having 6 to 12 carbon atoms having two or more branches and not including a ring structure represented by R15 include 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3, 3-dimethylbutyl group, 1,3-dimethylbutyl group, 1,2,2-trimethylpropyl group, 1,1-dimethylpentanyl group, 1-isopropylbutyl group, 1-isopropyl-2-methylpropyl group, 1 , 1-diethylpropyl group, 1-ethyl-1-isopropylpropyl group, 2-ethyl-4-methylpentyl group, 1-propyl-2,2-dimethylpropyl group, 1,1,2-trimethyl-pentyl group, 1-isopropyl-3-methylbutyl group, 1,2-dimethyl-1-ethylbutyl group, 1,3-dimethyl-1-ethylbutyl group, 1-ethyl-1-isopropyl-
  • R1 and R16 each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • R2, R3, R17, R18, and R19 may be the same or different and each represents a branched acyl group having 6 to 22 carbon atoms that does not contain a ring structure.
  • X represents a group in which an OH group is eliminated from a trivalent alcohol.
  • examples of the alkyl group represented by R1 and R16 include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclopropyl group.
  • R1 is preferably a hydrogen atom or a methyl group.
  • Examples of the branched acyl group having 6 to 22 carbon atoms that does not include the ring structure represented by R2, R3, R17, R18, and R19 include 2-methylpentanoyl group, 3-methylpentanoyl group, 4 -Methylpentanoyl group, 2-ethylbutanoyl group, 2-ethylbutanoyl group, 2,2-dimethylbutanoyl group, 3,3-dimethylbutanoyl group, 2-methylhexanoyl group, 4-methylhexanoyl group Group, 5-methylhexanoyl group, 2,2-dimethylpentanoyl group, 4,4-dimethylpentanoyl group, 2-methylheptanoyl group, 2-ethylhexyl group, 2-propylpentanoyl group, 2,2- Dimethylhexanoyl group, 2,2,3-trimethylpentanoyl group, 2-methyloctanoyl group,
  • R2, R3, R17, R18, and R19 may be the same or different and do not include a ring structure and have a branch.
  • Such a branched acyl group having 10 to 22 carbon atoms which does not contain a ring structure and is represented by R2, R3, R17, R18 and R19 in a preferred embodiment includes a 2-methylnonanoyl group, 4- Methylnonanoyl group, 8-methylnonanoyl group, 4-ethyloctanoyl group, 2-ethyloctanoyl group, 2-butylhexanoyl group, 2-tert-butylhexanoyl group, 2,2-diethylhexanoyl group), 2, 2-dimethyloctanoyl group, 3,7-dimethyloctanoyl group, neodecanoyl group), 7-methyldecanoyl group, 2-methyl-2-ethyloctanoyl group, 2-methylundecanoyl group, 10-methylun Decanoyl group, 2,2 dimethyldecanoyl group, 2-ethyldecano
  • the acyl group having 6 to 9 carbon atoms having 2 or more branches and containing no ring structure represented by R2, R3, R17, R18, R19 is 2,2-dimethyl.
  • the group derived from the trihydric alcohol represented by X in the general formula (1) is not particularly limited as long as the OH group is eliminated from the trihydric alcohol, but glycerin, trimethylolpropane, trimethylolethane.
  • the group derived from the tetrahydric alcohol represented by Y in the general formula (8) is not particularly limited as long as the OH group is released from the tetrahydric alcohol, but diglycerin, pentaerythritol, erythritol.
  • a group in which an OH group is eliminated from a tetrahydric alcohol selected from the group consisting of D-threitol and L-threitol can be suitably exemplified.
  • the hydrophobic monomer represented by the general formula (1) is a hydrophobic monomer represented by the general formula (15).
  • the carbon number of the acyl group of R24 and R25 in the general formula (15) is 12 to 22, more preferably 14 to 20, and still more preferably 16 to 20.
  • the carbon number of the main chain of the acyl group of R24 and R25 in the general formula (15) is preferably 9 to 21, more preferably 12 to 20, and still more preferably 16 to 18.
  • the number of branches in the acyl group of R24 and R25 in the general formula (15) is preferably 1 to 3, more preferably 1 or 2, and still more preferably 1.
  • the position number of carbon in the main chain to which the branched chain is bonded is preferably as large as possible.
  • the branched chain is bonded to the carbon at the end of the main chain, preferably from the 1st to 3rd carbon, more preferably the 1st or 2nd carbon, and even more preferably the 1st carbon. It is preferable.
  • R24 and R25 include 10-methylundecanoyl group, 10-methyldodecanoyl group, 11-methyldodecanoyl group, 10-ethylundecanoyl group, 12-methyltridecanoyl group, 12-methyl Tetradecanoyl group, 14-methylpentadecanoyl group, 16-methylheptadecanoyl group, 2,4,10,14-tetramethylpentanoyl group, 18-methylnonadecanoyl group, 3,7,11,15 Preferred examples include -tetra-methylhexadecanoyl group, 19-methyleicosanoyl group and the like.
  • the group derived from the trihydric alcohol represented by Z in the general formula (15) is not particularly limited as long as the OH group is released from the trihydric alcohol, but glycerin, trimethylolpropane, trimethylolethane.
  • hydrophilic monomer As the hydrophilic monomer in the present invention, polymerizable carboxylic acid and compounds represented by the general formulas (2), (9), (10) and (11) can be used.
  • the polymerizable carboxylic acid or a salt thereof specifically includes acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid and its sodium salt, potassium salt, Examples thereof include ammonium salts and amine salts. Among these, acrylic acid, methacrylic acid and salts thereof are particularly preferable because of high polymerizability.
  • a structural unit derived from a polymerizable carboxylic acid salt is introduced into the water-soluble copolymer of the present invention, the polymerizable carboxylic acid may be converted into a salt in advance, and a polymerization reaction may be performed.
  • a structural unit derived from a carboxylic acid may be derived into a water-soluble copolymer and then neutralized with a base to form a salt.
  • R4 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R5 may have a hydroxyl group.
  • R6 represents a hydrogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, an aliphatic hydrocarbon group having 1 to 14 carbon atoms, or an acyl group having 1 to 12 carbon atoms.
  • n represents an integer of 6 to 40.
  • examples of the alkyl group represented by R4 include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclopropyl group.
  • R4 is preferably a hydrogen atom or a methyl group.
  • alkylene group represented by R5 examples include ethylene group, propylene group, isopropylene group, 2-hydroxypropylene group, 1-hydroxy-2-methylethylene group, 2-hydroxy-1-methylethylene group and the like. Of these, ethylene group or propylene group is preferable, and ethylene group is more preferable.
  • examples of the aromatic group having 6 to 10 carbon atoms include a phenyl group, a benzyl group, a methylphenyl group, and an ethylphenyl group; an aliphatic carbon atom having 1 to 14 carbon atoms
  • Preferred examples of the hydrogen group include a methyl group, an ethyl group, a butyl group, a tertiary butyl group, a hexyl group, a cyclohexyl group, an octyl group, a 2-ethylhexyl group, and a lauryl group
  • Preferred examples of the 12 acyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, and a lauroyl group.
  • the group represented by R5 is preferably an aliphatic hydrocarbon group having 1 to 14
  • n in the general formula (2) is in the numerical range of 6 to 40.
  • Specific examples of the monomer represented by the general formula (2) in which R5 is a propylene group include polypropylene glycol (9) monoacrylate, polypropylene glycol (13) monoacrylate, and polypropylene glycol (9) monomethacrylate. And polypropylene glycol (13) monomethacrylate.
  • the number in parentheses represents N.
  • Many of these polymers are commercially available. Specific examples of such commercially available products include “Blemmer” AP-400, AP-550, AP-800, PP-500, PP-800 (all manufactured by NOF Corporation) and the like.
  • R5 is an ethylene group, specifically, polyethylene glycol (10) monoacrylate, polyethylene glycol (8) monomethacrylate, polyethylene glycol (23) monoacrylate.
  • hydrophilic monomer can be obtained in high yield by esterification reaction of the corresponding polyethylene glycol, polyethylene glycol monoether, polyethylene glycol monoester with acrylic acid or methacrylic acid chloride or anhydride.
  • esterification reaction of the corresponding polyethylene glycol, polyethylene glycol monoether, polyethylene glycol monoester with acrylic acid or methacrylic acid chloride or anhydride.
  • Specific examples of such commercially available products include Blemmer, AE-400, PE-350, AME-400, PME-400, PME-1000, ALE-800, PSE-1300, etc. Etc.).
  • hydrophilic monomer represented by general formula (9) As the hydrophilic monomer in the present invention, a hydrophilic monomer represented by general formula (9) may be used.
  • hydrophilic monomer represented by the general formula (9) examples include 2-acryloyloxyethyl phosphorylcholine (APC) and 2-methacryloyloxyethyl phosphorylcholine (MPC). These monomers can be synthesized by the following method described in Polymer Journal, Vol 22, No. 5, for example.
  • hydrophilic monomer represented by general formula (10) As the hydrophilic monomer in the present invention, a hydrophilic monomer represented by general formula (10) may be used.
  • hydrophilic monomer represented by the general formula (10) as the reducing sugar of the group obtained by removing hydrogen from the hydroxyl group at the 1-position of the reducing sugar represented by GO—, specifically, glucose, mannose,
  • Examples include one or more selected from the group consisting of monosaccharides such as galactose, arabinose, xylose and ribose, disaccharides such as maltose, lactose and cellobiose, trisaccharides such as maltotriose, and oligosaccharides such as malto-oligosaccharide
  • glucose is particularly preferable.
  • the monomer represented by the general formula (10) is preferably glucosyloxyethyl methacrylate (hereinafter abbreviated as GEMA) or glucosyloxyethyl acrylate (hereinafter abbreviated as GEA).
  • GEMA glucosyloxyethyl methacrylate
  • GEA glucosyloxyethyl acrylate
  • the amino acid of the amino acid residue represented by R23 is not particularly limited as long as it is a commonly known amino acid. Specifically, glycine, alanine, glutamine, lysine, Arginine etc. are illustrated. Among these, the lysine residue is particularly preferable because the obtained water-soluble copolymer is excellent in the effect of restoring the skin barrier.
  • the polyamine in the polyamine residue represented by R23 means an amine having two or more amino groups that may be substituted with an alkyl group in the same molecule, and specifically includes diamine, triamine, tetraamine. Or the amine by which the hydrogen atom of these amino groups is substituted by the alkyl group is illustrated.
  • diamines are preferred because the feeling of use of the resulting external preparation for skin containing the water-soluble copolymer is particularly excellent.
  • Particularly preferred examples include ethylenediamine, 1 from the availability of raw materials for synthesis. , 4-diamino-n-butane, 1,6-diamino-n-hexane and the like.
  • amino alcohol in the amino alcohol residue represented by R23 means a compound having an amino group which may be substituted with an alkyl group in the same molecule and an alcoholic hydroxyl group.
  • the amino alcohol is not particularly limited as long as it is generally known, but specific examples include ethanolamine and triethylaminoethanol.
  • the sodium salt, potassium salt, ammonium salt, amine salt, etc. which neutralized the acid part with the base
  • examples thereof include hydrochlorides, sulfates, nitrates, phosphates, citrates, oxalates, carbonates, etc., in which the amino group is neutralized with an acid.
  • the structural unit derived from the salt of the monomer represented by the general formula (11) is introduced into the water-soluble copolymer of the present invention, the monomer represented by the general formula (11) is converted into a salt in advance to carry out the polymerization reaction.
  • the structural unit derived from the monomer represented by the general formula (11) may be derived into a water-soluble copolymer by a polymerization reaction, and then neutralized to form a salt.
  • Specific examples of the monomer represented by the general formula (11) and salts thereof include the above-mentioned compounds 1 to 11 and salts thereof.
  • the hydrophilic monomer represented by the general formula (11) is, for example, an esterification reaction using (meth) acrylic acid or (meth) acrylic acid chloride, amide as shown in the reaction formulas (1) and (2). It can be synthesized by a chemical reaction.
  • the hydrophilic polymer in the present invention the general formula (2), the general formula (9), the general formula (10), and the general formula (11) can be used.
  • the water-soluble copolymer contains the structural unit (2) derived from the general formula (2).
  • a water-soluble copolymer having the structural unit (1) and the structural unit (2) can be preferably used. More preferably, a water-soluble copolymer having the structural unit (15) and the structural unit (2) is used. Of such water-soluble copolymers, a (methoxy PEG-23 methacrylate / glyceryl methacrylate) is particularly preferably used. By containing such a water-soluble copolymer, it is possible to provide a skin cleanser with less tension after use.
  • (Methoxymethacrylic acid PEG-23 / glyceryl methacrylate) is a structural unit (e) in which, among the hydrophobic monomers represented by the general formula (15), R24 and R25 are 16-methylheptadecanoyl. It mainly contains a structural unit (e) derived from a hydrophobic monomer as a group.
  • the structural unit (f) is derived from a hydrophilic monomer in which R4 is a methyl group, R5 is an ethylene group, R6 is a methyl group, and n is 23.
  • the structural unit (f) is mainly included.
  • the proportion of the structural unit (e) in all the structural units in the water-soluble copolymer is preferably 1 to 60% by mass, more preferably 10 to 50% by mass, and 20 to 40% by mass.
  • the proportion of the structural unit (f) in all the structural units in the water-soluble copolymer is preferably 40 to 99% by mass, more preferably 50 to 90% by mass, and 60 to 80% by mass.
  • the mass ratio of the structural unit (e) to the structural unit (f) constituting the water-soluble copolymer is preferably 1:99 to 60:40, more preferably 10:90 to 50:50, It is preferably 20:80 to 40:60.
  • the molar ratio of the structural unit (e) to the structural unit (f) constituting the water-soluble copolymer is preferably 1:99 to 71:29, more preferably 15:85 to 62:38, and still more preferably 29. : 71 to 52:48, more preferably 35:65 to 45:55.
  • the average molecular weight of the water-soluble copolymer is preferably 20,000 to 110,000, more preferably 20,000 to 80,000, more preferably 30,000 to 80,000, more preferably 40,000 to 70,000, still more preferably 50,000 to 70,000, still more preferably. 57000-66000.
  • an average molecular weight means here the weight average molecular weight of polystyrene conversion measured by GPC.
  • the skin cleansing agent refers to a composition containing a cleaning component, and is used for the purpose of removing skin dirt such as sebum. As described above, the skin cleansing agent has an effect of removing sebum present in the skin, and thus has a problem that it causes a feeling of tension on the skin after use.
  • the skin cleanser of the present invention is characterized by containing the above-mentioned water-soluble copolymer. According to the present invention, it is possible to reduce the feeling of skin tightness after use without impairing or improving the cleaning power inherent to the skin cleansing material.
  • the dosage form of the skin cleansing material of the present invention can be applied without particular limitation as long as it is a dosage form normally used for skin cleaning materials.
  • Common skin cleansing agents include solid, powder, cream, liquid, and gel skin cleansing agents, but the present invention can be applied to any dosage form.
  • the content of the above-mentioned water-soluble copolymer in the skin cleanser whose dosage form is a liquid such as cream, liquid or gel is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, More preferably, it is 1 to 3% by mass.
  • Skin cleansing materials can be divided into those that are used by lathering and those that are used without lathering. Regardless of which type of skin cleansing material is applied, the present invention can reduce the feeling of skin tension after use without impairing the inherent cleaning power of the skin cleansing material.
  • the content of the above-mentioned water-soluble copolymer is 0.1% by mass or more, more preferably 0.5% by mass or more, more preferably from the viewpoint of improving the foaming quality. It is 0.8 mass% or more, More preferably, it is 1 mass% or more. Further, from the viewpoint of reducing the feeling of skin slimness after use, the content of the above-mentioned water-soluble copolymer is preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 3% by mass or less, Preferably it is 1 mass% or less.
  • a creamy skin cleansing agent is preferably mentioned.
  • the content of the above-mentioned water-soluble copolymer is preferably 0.1 to 10% by mass, more preferably 0.8%, from the viewpoint of improving ease of spreading to the skin. It is 5 to 5% by mass, more preferably 0.6 to 3% by mass, and further preferably 0.7 to 2% by mass.
  • a gel-like skin cleanser is preferably used as a type of skin cleanser used without foaming.
  • the surfactant that can be contained in the skin cleanser of the present invention is not particularly limited as long as it is usually used in a skin cleanser, and includes ionic surfactants and nonionic surfactants. Any of them can be used.
  • any of an anionic surfactant, a cationic surfactant, an amphoteric surfactant and a nonionic surfactant can be used.
  • anionic surfactant examples include fatty acid soaps such as fatty acid sodium, fatty acid potassium, and fatty acid triethanolamine, sodium lauryl sulfate, potassium lauryl sulfate, and triethanol lauryl sulfate, which may have a polyoxyethylene group.
  • Preferred examples include alkyl phosphorus ester salts and sulfosuccinic acid alkyl ester salts which may have an oxyethylene group.
  • anionic surfactant examples include alkyltrimethylammonium salt, alkylpyridinium salt, distearyldimethylammonium dialkyldimethylammonium chloride, poly (N, N′-dimethyl-3,5-methylenepiperidinium chloride), Alkyl quaternary ammonium salts, alkyl dimethyl benzyl ammonium salts, alkyl isoquinolinium salts, dialkyl morpholinium salts, POE-alkyl amines, alkyl amine salts, polyamine fatty acid derivatives, amyl alcohol fatty acid derivatives, benzalkonium chloride, benzethonium chloride Etc. can be preferably exemplified.
  • amphoteric surfactants examples include imidazoline-based amphoteric surfactants and betaine-based surfactants.
  • Nonionic surfactants include glycerin fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, polyoxyethylene alkylphenyl ether, Polyoxyethylene lanolin, lanolin alcohol, beeswax derivative, polyoxyethylene castor oil, hydrogenated castor oil, polyoxyethylene sterol, hydrogenated sterol, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene fatty acid ester , Polyoxyethylene alkyl ether fatty acid ester, polyoxyethylene hydrogenated castor oil fatty acid ester Polyoxyethylene trimethylol propane fatty acid ester, polyethylene glycol fatty acid esters, sucrose fatty acid esters, polyoxyethylene polyoxypropylene block copolymer, it can be preferably exemplified organic modified
  • the content of these surfactants is not particularly limited, and can be appropriately set depending on the type of the surfactant.
  • the skin cleansing agent in a form containing a fatty acid soap, a form containing a nonionic surfactant, and a gel-like form will be described more specifically.
  • the present invention is applied to a skin cleanser containing a fatty acid soap, so that the high-quality foaming and creamy foam quality of the skin cleansing agent is not impaired. The feeling of tightness of the skin can be reduced.
  • the form of the skin cleanser containing fatty acid soap may be solid, liquid or cream, but is preferably liquid or cream. In particular, it is preferable to use a form of a creamy skin cleanser used by whipping.
  • the fatty acid constituting the fatty acid soap is not particularly limited as long as it can be applied to the skin cleanser, and may be saturated or unsaturated, and has 8 to 24 carbon atoms, particularly 10 to 22 carbon atoms. Those are preferred. Specific examples of preferable ones include lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, hydroxystearic acid, hydroxydecenoic acid, coconut oil fatty acid, reduced coconut oil fatty acid, beef tallow fatty acid, reduced beef tallow fatty acid, palm Examples include nuclear fatty acids.
  • alkali agents that form salts with these higher fatty acids include alkali metal salts such as sodium and potassium, ammonium salts, monoethanolamine salts, diethanolamine salts, triethanolamine salts, 2-amino-2-methylpropanol, 2- Examples thereof include alkanolamine salts such as amino-2-methylpropanediol, and basic amino acid salts such as lysine and arginine.
  • the content of fatty acid contained in the skin cleanser is not particularly limited.
  • the fatty acid content is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and even more preferably 30 to 50% by mass.
  • the ratio of the above-mentioned water-soluble copolymer and fatty acid content is preferably 1: 500 to 1: 2, more preferably 1: 200 to 1: 3, More preferably, it is 1: 100 to 1: 5. Further, from the viewpoint of improving the foaming property, the ratio of the above-mentioned water-soluble copolymer and fatty acid content is preferably 1: 200 to 1: 2, more preferably 1: 100 to 1: 5, still more preferably 1. : 50 to 1:10.
  • the ratio of the above-mentioned water-soluble copolymer and fatty acid content is preferably 1: 500 to 1:10, more preferably 1: 200 to 1:20. More preferably, the ratio is 1: 100 to 1:50.
  • the present invention effectively provides a feeling of skin tension after use even when applied to a skin cleanser containing a nonionic surfactant. Can be reduced.
  • the nonionic surfactant those described above can be used without limitation.
  • the content of the water-soluble copolymer is preferably 0.1% by mass or more, and more preferably 0.5% by mass, from the viewpoint of reducing the feeling of tension after use. As mentioned above, More preferably, it is 1 mass% or more. Further, from the viewpoint of improving detergency, the content of the water-soluble copolymer is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, and further preferably 3%. It is at least mass%.
  • the ratio of the content of the above-mentioned water-soluble copolymer and nonionic surfactant is preferably 1:20 to 1: 0.5, more preferably 1. : 10 to 1: 0.7, more preferably 1: 5 to 1: 1. Further, from the viewpoint of improving the detergency, the ratio of the mass content of the water-soluble copolymer and the nonionic surfactant is preferably 1:10 to 1: 0.5, more preferably 1: 5 to 1. : 0.5, more preferably 1: 3 to 1: 0.6, and still more preferably 1: 1.5 to 1: 0.7.
  • the water-soluble copolymer and the nonionic surfactant described above are used.
  • the ratio of the contained mass is preferably 1:15 to 1: 0.7, more preferably 1:10 to 1: 1, and still more preferably 1: 7 to 1: 3.
  • the skin cleansing agent of the present invention can contain, in addition to the above-mentioned components, optional components that are usually used in external preparations for skin.
  • optional ingredients include macadamia nut oil, avocado oil, corn oil, olive oil, rapeseed oil, sesame oil, castor oil, safflower oil, cottonseed oil, jojoba oil, coconut oil, palm oil, liquid lanolin, and hardened coconut oil.
  • Vitamin B or its derivatives vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 or a derivative thereof, vitamin B such as vitamin B12, vitamin B15 or a derivative thereof; ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, and damage Vitamin E such as E acetate, vitamin D, vitamin H, pantothenic acid, pantethine, vitamins etc. pyrroloquinoline quinone and the like; and antibacterial agents such as phenoxyethanol preferred examples.
  • the skin cleanser of the present invention can be produced by treating each of the above components according to a conventional method.
  • the present invention is preferably applied to a facial cleanser. According to the present invention, it is possible to provide a facial cleanser that does not feel the feeling of skin tightness after face washing.
  • a feature of the sunscreen cosmetic of the present invention that solves the fifth problem is that it contains the above four components [1] to [4] as essential components.
  • the components [1] to [4] will be described in detail.
  • Component (A) Water-soluble copolymer [1] Hydrophobic monomer Component (A) is derived from the hydrophobic monomer represented by the general formula (1), (7) or (8). It is a water-soluble copolymer containing one or more structural units (hereinafter, sometimes simply referred to as “structural unit (7)”) as essential structural units.
  • structural unit (7) the “structural unit derived from a monomer” refers to a structural unit formed by cleavage of a carbon-carbon unsaturated bond of a corresponding monomer by a polymerization reaction.
  • the hydrophobic monomer represented by the general formula (1), (7) or (8) will be described.
  • R14 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R15 represents a ring having 13 to 30 carbon atoms.
  • a branched hydrocarbon group not containing a structure or a hydrocarbon group having 6 to 12 carbon atoms having two or more branches not containing a ring structure is represented.
  • examples of the alkyl group represented by R14 include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclopropyl group.
  • R14 is preferably a hydrogen atom or a methyl group.
  • Examples of the branched hydrocarbon group not containing a ring structure having 13 to 30 carbon atoms represented by R15 include 1-methyldodecanyl group, 11-methyldodecanyl group, 3-ethylundecanyl group, 3- Ethyl-4,5,6-trimethyloctyl, 1-methyltridecanyl, 1-hexyloctyl, 2-butyldecanyl, 2-hexyloctyl, 4-ethyl-1-isobutyloctyl, 1-methyl Pentadecanyl group, 2-hexyldecanyl group, 2-octyldecanyl group, 2-hexyldecanyl group, 16-methylheptadecanyl group, 9-methylheptadecanyl group, 7-methyl-2- (3 -Methylhexyl) decanyl group, 3,7,11,15-tetra-methylhexadecanyl group, 2-octyldode
  • examples of the hydrocarbon group having 6 to 12 carbon atoms having two or more branches and not including a ring structure represented by R15 include 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3, 3-dimethylbutyl group, 1,3-dimethylbutyl group, 1,2,2-trimethylpropyl group, 1,1-dimethylpentanyl group, 1-isopropylbutyl group, 1-isopropyl-2-methylpropyl group, 1 , 1-diethylpropyl group, 1-ethyl-1-isopropylpropyl group, 2-ethyl-4-methylpentyl group, 1-propyl-2,2-dimethylpropyl group, 1,1,2-trimethyl-pentyl group, 1-isopropyl-3-methylbutyl group, 1,2-dimethyl-1-ethylbutyl group, 1,3-dimethyl-1-ethylbutyl group, 1-ethyl-1-isopropyl-
  • R1 and R16 each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • R2, R3, R17, R18, and R19 may be the same or different and each represents a branched acyl group having 6 to 22 carbon atoms that does not contain a ring structure.
  • X represents a group in which an OH group is eliminated from a trivalent alcohol.
  • examples of the alkyl group represented by R1 and R16 include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclopropyl group.
  • R1 is preferably a hydrogen atom or a methyl group.
  • Examples of the branched acyl group having 6 to 22 carbon atoms that does not include the ring structure represented by R2, R3, R17, R18, and R19 include 2-methylpentanoyl group, 3-methylpentanoyl group, 4 -Methylpentanoyl group, 2-ethylbutanoyl group, 2-ethylbutanoyl group, 2,2-dimethylbutanoyl group, 3,3-dimethylbutanoyl group, 2-methylhexanoyl group, 4-methylhexanoyl group Group, 5-methylhexanoyl group, 2,2-dimethylpentanoyl group, 4,4-dimethylpentanoyl group, 2-methylheptanoyl group, 2-ethylhexyl group, 2-propylpentanoyl group, 2,2- Dimethylhexanoyl group, 2,2,3-trimethylpentanoyl group, 2-methyloctanoyl group,
  • R2, R3, R17, R18, and R19 may be the same or different and do not include a ring structure and have a branch.
  • Such a branched acyl group having 10 to 22 carbon atoms which does not contain a ring structure and is represented by R2, R3, R17, R18 and R19 in a preferred embodiment includes a 2-methylnonanoyl group, 4- Methylnonanoyl group, 8-methylnonanoyl group, 4-ethyloctanoyl group, 2-ethyloctanoyl group, 2-butylhexanoyl group, 2-tert-butylhexanoyl group, 2,2-diethylhexanoyl group), 2, 2-dimethyloctanoyl group, 3,7-dimethyloctanoyl group, neodecanoyl group), 7-methyldecanoyl group, 2-methyl-2-ethyloctanoyl group, 2-methylundecanoyl group, 10-methylun Decanoyl group, 2,2 dimethyldecanoyl group, 2-ethyldecano
  • the acyl group having 6 to 9 carbon atoms having 2 or more branches and containing no ring structure represented by R2, R3, R17, R18, R19 is 2,2-dimethyl.
  • the group derived from the trihydric alcohol represented by X in the general formula (1) is not particularly limited as long as the OH group is eliminated from the trihydric alcohol, but glycerin, trimethylolpropane, trimethylolethane.
  • the group derived from the tetrahydric alcohol represented by Y in the general formula (8) is not particularly limited as long as the OH group is released from the tetrahydric alcohol, but diglycerin, pentaerythritol, erythritol.
  • a group in which an OH group is eliminated from a tetrahydric alcohol selected from the group consisting of D-threitol and L-threitol can be suitably exemplified.
  • the hydrophobic monomer represented by the general formula (1) is a hydrophobic monomer represented by the general formula (15).
  • R24 and R25 in the general formula (15) are preferably a branched acyl group having 10 to 22 carbon atoms that does not include a ring structure.
  • the carbon number of the acyl group of R24 and R25 in the general formula (15) is 12 to 22, more preferably 14 to 20, and still more preferably 16 to 20.
  • the carbon number of the main chain of the acyl group of R24 and R25 in the general formula (15) is preferably 9 to 21, more preferably 12 to 20, and still more preferably 16 to 18.
  • the number of branches in the acyl group of R24 and R25 in the general formula (15) is preferably 1 to 3, more preferably 1 or 2, and still more preferably 1.
  • the position number of carbon in the main chain to which the branched chain is bonded is preferably as large as possible.
  • the branched chain is bonded to the carbon at the end of the main chain, preferably from the 1st to 3rd carbon, more preferably the 1st or 2nd carbon, and even more preferably the 1st carbon. It is preferable.
  • R24 and R25 include 10-methylundecanoyl group, 10-methyldodecanoyl group, 11-methyldodecanoyl group, 10-ethylundecanoyl group, 12-methyltridecanoyl group, 12-methyl Tetradecanoyl group, 14-methylpentadecanoyl group, 16-methylheptadecanoyl group, 2,4,10,14-tetramethylpentanoyl group, 18-methylnonadecanoyl group, 3,7,11,15 Preferred examples include -tetra-methylhexadecanoyl group, 19-methyleicosanoyl group and the like.
  • the group derived from the trihydric alcohol represented by Z in the general formula (15) is not particularly limited as long as the OH group is released from the trihydric alcohol, but glycerin, trimethylolpropane, trimethylolethane.
  • hydrophilic monomer examples include a polymerizable carboxylic acid, the general formula (2), and the general formulas (9), (10), and (11). The compound represented by these can be used.
  • the polymerizable carboxylic acid or a salt thereof specifically includes acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid and its sodium salt, potassium salt, Examples thereof include ammonium salts and amine salts. Among these, acrylic acid, methacrylic acid and salts thereof are particularly preferable because of high polymerizability.
  • a structural unit derived from a polymerizable carboxylic acid salt is introduced into the water-soluble copolymer of the present invention, the polymerizable carboxylic acid may be converted into a salt in advance, and a polymerization reaction may be performed.
  • a structural unit derived from a carboxylic acid may be derived into a water-soluble copolymer and then neutralized with a base to form a salt.
  • R4 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R5 may have a hydroxyl group.
  • R6 represents a hydrogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, an aliphatic hydrocarbon group having 1 to 14 carbon atoms, or an acyl group having 1 to 12 carbon atoms.
  • n represents an integer of 6 to 40.
  • examples of the alkyl group represented by R4 include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclopropyl group.
  • R4 is preferably a hydrogen atom or a methyl group.
  • alkylene group represented by R5 examples include ethylene group, propylene group, isopropylene group, 2-hydroxypropylene group, 1-hydroxy-2-methylethylene group, 2-hydroxy-1-methylethylene group and the like. Of these, ethylene group or propylene group is preferable, and ethylene group is more preferable.
  • examples of the aromatic group having 6 to 10 carbon atoms include a phenyl group, a benzyl group, a methylphenyl group, and an ethylphenyl group; an aliphatic carbon atom having 1 to 14 carbon atoms
  • Preferred examples of the hydrogen group include a methyl group, an ethyl group, a butyl group, a tertiary butyl group, a hexyl group, a cyclohexyl group, an octyl group, a 2-ethylhexyl group, and a lauryl group
  • Preferred examples of the 12 acyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, and a lauroyl group.
  • the group represented by R5 is preferably an aliphatic hydrocarbon group having 1 to 14
  • n in the general formula (2) is in the numerical range of 6 to 40.
  • Specific examples of the monomer represented by the general formula (2) in which R5 is a propylene group include polypropylene glycol (9) monoacrylate, polypropylene glycol (13) monoacrylate, and polypropylene glycol (9) monomethacrylate. And polypropylene glycol (13) monomethacrylate.
  • the number in parentheses represents N.
  • Many of these polymers are commercially available. Specific examples of such commercially available products include “Blemmer” AP-400, AP-550, AP-800, PP-500, PP-800 (all manufactured by NOF Corporation) and the like.
  • R5 is an ethylene group, specifically, polyethylene glycol (10) monoacrylate, polyethylene glycol (8) monomethacrylate, polyethylene glycol (23) monoacrylate.
  • hydrophilic monomer can be obtained in high yield by esterification reaction of the corresponding polyethylene glycol, polyethylene glycol monoether, polyethylene glycol monoester with acrylic acid or methacrylic acid chloride or anhydride.
  • esterification reaction of the corresponding polyethylene glycol, polyethylene glycol monoether, polyethylene glycol monoester with acrylic acid or methacrylic acid chloride or anhydride.
  • Specific examples of such commercially available products include Blemmer, AE-400, PE-350, AME-400, PME-400, PME-1000, ALE-800, PSE-1300, etc. Etc.).
  • hydrophilic monomer represented by general formula (9) As the hydrophilic monomer in the present invention, a hydrophilic monomer represented by the above general formula (9) may be used.
  • hydrophilic monomer represented by the general formula (9) examples include 2-acryloyloxyethyl phosphorylcholine (APC) and 2-methacryloyloxyethyl phosphorylcholine (MPC). These monomers can be synthesized by the following method described in Polymer Journal, Vol 22, No. 5, for example.
  • hydrophilic monomer represented by general formula (10) As the hydrophilic monomer in the present invention, a hydrophilic monomer represented by the above general formula (10) may be used.
  • hydrophilic monomer represented by the general formula (10) as the reducing sugar of the group obtained by removing hydrogen from the hydroxyl group at the 1-position of the reducing sugar represented by GO—, specifically, glucose, mannose,
  • Examples include one or more selected from the group consisting of monosaccharides such as galactose, arabinose, xylose and ribose, disaccharides such as maltose, lactose and cellobiose, trisaccharides such as maltotriose, and oligosaccharides such as malto-oligosaccharide
  • glucose is particularly preferable.
  • the monomer represented by the general formula (10) is preferably glucosyloxyethyl methacrylate (hereinafter abbreviated as GEMA) or glucosyloxyethyl acrylate (hereinafter abbreviated as GEA).
  • GEMA glucosyloxyethyl methacrylate
  • GEA glucosyloxyethyl acrylate
  • hydrophilic monomer represented by general formula (11) As the hydrophilic monomer in the present invention, a hydrophilic monomer represented by the above general formula (11) may be used.
  • the amino acid of the amino acid residue represented by R23 is not particularly limited as long as it is a commonly known amino acid. Specifically, glycine, alanine, glutamine, lysine, Arginine etc. are illustrated. Among these, the lysine residue is particularly preferable because the obtained water-soluble copolymer is excellent in the effect of restoring the skin barrier.
  • the polyamine in the polyamine residue represented by R23 means an amine having two or more amino groups that may be substituted with an alkyl group in the same molecule, and specifically includes diamine, triamine, tetraamine. Or the amine by which the hydrogen atom of these amino groups is substituted by the alkyl group is illustrated.
  • diamines are preferred because the feeling of use of the resulting external preparation for skin containing the water-soluble copolymer is particularly excellent.
  • Particularly preferred examples include ethylenediamine, 1 from the availability of raw materials for synthesis. , 4-diamino-n-butane, 1,6-diamino-n-hexane and the like.
  • amino alcohol in the amino alcohol residue represented by R23 means a compound having an amino group which may be substituted with an alkyl group in the same molecule and an alcoholic hydroxyl group.
  • the amino alcohol is not particularly limited as long as it is generally known, but specific examples include ethanolamine and triethylaminoethanol.
  • the sodium salt, potassium salt, ammonium salt, amine salt, etc. which neutralized the acid part with the base
  • examples thereof include hydrochlorides, sulfates, nitrates, phosphates, citrates, oxalates, carbonates, etc., in which the amino group is neutralized with an acid.
  • the structural unit derived from the salt of the monomer represented by the general formula (11) is introduced into the water-soluble copolymer of the present invention, the monomer represented by the general formula (11) is converted into a salt in advance to carry out the polymerization reaction.
  • the structural unit derived from the monomer represented by the general formula (11) may be derived into a water-soluble copolymer by a polymerization reaction, and then neutralized to form a salt.
  • Specific examples of the monomer represented by the general formula (11) and salts thereof include compounds 1 to 11 and salts thereof.
  • the hydrophilic monomer represented by the general formula (11) is, for example, an esterification reaction using (meth) acrylic acid or (meth) acrylic acid chloride, amide as shown in the reaction formulas (1) and (2). It can be synthesized by a chemical reaction.
  • the general formulas (2), (9), (10), and (11) can be used as the hydrophilic polymer in the present invention.
  • the water-soluble copolymer contains the structural unit 2 derived from the general formula (2).
  • a water-soluble copolymer having the structural unit (1) and the structural unit (2) can be preferably used. More preferably, a water-soluble copolymer having the structural unit (15) and the structural unit (2) is used. Of such water-soluble copolymers, a (methoxy PEG-23 methacrylate / glyceryl methacrylate) is particularly preferably used. By containing such a water-soluble copolymer, the emulsion composition is low in irritation, less sticky, and excellent in emulsion stability.
  • (Methoxymethacrylic acid PEG-23 / glyceryl methacrylate) is a structural unit (g) in which R24 and R25 are 16-methylheptadecanoyl among the hydrophobic monomers represented by the general formula (15). It mainly contains a structural unit (g) derived from a hydrophobic monomer as a group. Further, among the hydrophilic monomers represented by the general formula (2), the structural unit (h) is derived from a hydrophilic monomer in which R4 is a methyl group, R5 is an ethylene group, R6 is a methyl group, and n is 23. The structural unit (h) is mainly included.
  • the proportion of the structural unit (g) in all the structural units in the water-soluble copolymer is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, and 10 to 30% by mass.
  • the proportion of the structural unit (h) in all the structural units in the water-soluble copolymer is preferably 50 to 99% by mass, more preferably 60 to 95% by mass, and 70 to 90% by mass.
  • the mass ratio of the structural unit (g) to the structural unit (h) constituting the water-soluble copolymer is preferably 5:95 to 50:50, more preferably 10:90 to 45:55, The ratio is preferably 20:80 to 40:60, more preferably 25:75 to 35:65.
  • the molar ratio of the structural unit (g) to the structural unit (h) constituting the water-soluble copolymer is preferably 8:92 to 62:38, more preferably 15:85 to 57:43, and still more preferably 29. : 71 to 52:48, more preferably 35:65 to 46:54.
  • the average molecular weight of the water-soluble copolymer is preferably 20,000 to 110,000, more preferably 20,000 to 80,000, more preferably 30,000 to 80,000, more preferably 40,000 to 70,000, still more preferably 50,000 to 70,000, still more preferably. 57000-66000.
  • the content of the above water-soluble copolymer is not particularly limited, but is usually 0.001 to 15% by mass, preferably 0.01 to 10% by mass.
  • the sunscreen cosmetic of the present invention is obtained by ester condensation of one molecule of polyglycerol having a polymerization degree of 10 and 2 to 5 molecules of fatty acid having 16 or more carbon atoms. It contains polyglycerin fatty acid ester as component (B).
  • the fatty acid having 16 or more carbon atoms constituting the polyglycerol fatty acid ester of the component (B) may have a branched chain, and may be saturated or unsaturated. Preferred examples include oleic acid and isostearic acid.
  • the number of fatty acid molecules to be ester-bonded to one molecule of polyglycerol may be 2 to 5, and preferably 5 molecules.
  • polyglyceryl-10 pentastearate is particularly preferably used as component (B).
  • the content of the polyglycerin fatty acid ester of component (B) can usually be 0.1 to 10% by mass. Further, from the viewpoint of improving the emulsion stability, the content of the component (B) is 0.3% by mass or more, more preferably 0.5% by mass, and still more preferably 0.7% by mass or more. Furthermore, from the viewpoint of suppressing stickiness, the content of the component (B) is preferably 7% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less.
  • the sunscreen cosmetic of the present invention contains an ionic surfactant as the component (C).
  • the ionic surfactant is not particularly limited as long as it is used in cosmetics, and any of an anionic surfactant, a cationic surfactant and an amphoteric surfactant can be used.
  • anionic surfactant examples include fatty acid soaps such as fatty acid sodium, fatty acid potassium, and fatty acid triethanolamine, sodium lauryl sulfate, potassium lauryl sulfate, triethanolamine that may have a polyoxyethylene group.
  • Preferred examples thereof include alkyl phosphorus ester salts and sulfosuccinic acid alkyl ester salts which may have a polyoxyethylene group.
  • Examples of the cationic surfactant include alkyltrimethylammonium salt, alkylpyridinium salt, distearyldimethylammonium dialkyldimethylammonium salt, poly (N, N′-dimethyl-3,5-methylenepiperidinium chloride), alkyl Quaternary ammonium salt, alkyldimethylbenzylammonium salt, alkylisoquinolinium salt, dialkyl morpholinium salt, POE-alkylamine, alkylamine salt, polyamine fatty acid derivative, amyl alcohol fatty acid derivative, benzalkonium chloride, benzethonium chloride, etc. Can be preferably exemplified.
  • amphoteric surfactants examples include imidazoline-based amphoteric surfactants and betaine-based surfactants.
  • an anionic surfactant is preferably used as the component (C), and acyl lactate is more preferably used.
  • acyl lactate a sodium salt is preferable, and specific examples include sodium lauroyl lactate, isostearoyl sodium lactate, and stearoyl sodium lactate.
  • the content of the ionic surfactant is not particularly limited, and is usually 0.01 to 2.0% by mass, more preferably 0.1 to 1% by mass. Further, from the viewpoint of improving the emulsion stability, the content of the ionic surfactant is preferably 0.05% by mass or more, more preferably 0.07% by mass or more, and further preferably 0.1% by mass or more. To do. Furthermore, from the viewpoint of suppressing stickiness, the content of the ionic surfactant is preferably 1.5% by mass or less, more preferably 1% by mass or less, and further preferably 0.5% by mass or less.
  • composition (D). Ultraviolet scattering agent / ultraviolet absorber
  • the sunscreen cosmetic of the present invention contains an ultraviolet scattering agent and / or an ultraviolet absorber as the component (D).
  • ultraviolet scattering agent refers to a particulate metal oxide that functions to scatter ultraviolet rays, and the type thereof is not particularly limited as long as it can be blended in an emulsified cosmetic.
  • the metal oxide include titanium dioxide, zinc oxide, zirconium oxide, cerium oxide and the like.
  • the content of the ultraviolet scattering agent is not particularly limited, and is usually 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and further preferably 1 to 10% by mass.
  • the ultraviolet scattering agent has a particle size referred to as fine particles in the technical field.
  • the primary particle size by electron microscope observation is usually 5 nm or more, preferably 10 nm or more, and usually 100 nm or less, preferably 80 nm or less. belongs to. Since the ultraviolet scattering agent used in the present invention is excellent in the ultraviolet scattering effect, it preferably contains at least one selected from the group consisting of fine particle titanium dioxide and fine particle zinc oxide.
  • the ultraviolet light scattering agent used in the present invention can be prepared by a conventional method such as thermal decomposition of the corresponding metal salt in the gas phase, but since there are many commercial products, the commercial products are used as they are. You can also. Specific examples of such commercially available products include “MTY-110M3S” (manufactured by Teika), “MTY-02” (manufactured by Teica), “MT-100TV” ( (Taika Co., Ltd.), “MT-500HSA” (Taika Co., Ltd.), “MT-100T” (Taika Co., Ltd.), “MT-01” (Taika Co., Ltd.), “MT-10EX” ”(Manufactured by Teika),“ MT-05 ”(manufactured by Teika),“ MT-100Z ”(manufactured by Teica),“ MT-150EX ”(manufactured by Teica),“ MT -100AQ "(manufactured by Teika
  • MZ-300 (manufactured by Teika), “MZY-303S” (manufactured by Teica), “MZ-306X” (manufactured by Teica), “MZ-500” "(Manufactured by Teica),” MZY-505S “(manufactured by Teica),” MZ-506X “(manufactured by Teica),” MZ-510HPSX “(manufactured by Teica),” WSX -MZ-700 “(manufactured by Teika Co., Ltd.),” SAMT-UFZO-450 “(manufactured by Miyoshi Kasei Co., Ltd.),” SAMT-UFZO-500 “(manufactured by Miyoshi Kasei Co., Ltd.),” FZO-50 " (Manufactured by Ishihara Sangyo Co., Ltd.), “Maxlite ZS-032” (manufactured by Ishihara Sangy
  • the surface of the UV scattering agent is preferably coated with an inorganic compound such as silica or alumina, or an organic compound such as sodium polyacrylate, fatty acid metal soap, or silicone.
  • the ultraviolet scattering agent is preferably water-dispersible. Since the water-dispersible ultraviolet scattering agent is uniformly dispersed in the aqueous phase, the sunscreen cosmetic of the present invention having such a form has an excellent ultraviolet protection function.
  • a preferable example of the water-dispersible ultraviolet scattering agent is an ultraviolet scattering agent whose surface is coated with a hydrophilic compound.
  • a water dispersible ultraviolet scattering agent an ultraviolet scattering agent that has been surface-treated with sodium polyacrylate is preferable.
  • the sunscreen cosmetic of the present invention containing an ultraviolet light scattering agent surface-treated with sodium polyacrylate as the component (D) has excellent dispersibility and an excellent ultraviolet protection function.
  • the ultraviolet absorber is not particularly limited as long as it is an ultraviolet absorber that can be usually blended into an emulsified cosmetic, but in order to absorb ultraviolet rays having a wide wavelength range, it absorbs ultraviolet rays having a wavelength of 320 to 400 nm (A region). It is preferable to include a -A absorber and a UV-B absorber that absorbs ultraviolet rays having a wavelength of 290 to 320 nm (B region).
  • the content of the ultraviolet absorber is not particularly limited and is usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more, and usually 20% by mass or less, preferably 15%. It is 10 mass% or less, More preferably, it is 10 mass% or less.
  • UV-A absorbers include 2-hydroxy-4-methoxybenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, dimethoxybenzylidenedioxoimidazolidinepropionate 2-ethylhexyl, bis (reslucinyl) Examples include compounds such as triazine, methylenebisbenzotriazolyltetramethylbutylphenol, hexyl diethylaminohydroxybenzoyl benzoate, t-butylmethoxydibenzoylmethane and the like.
  • hexyl diethylaminohydroxybenzoyl benzoate and t-butylmethoxydibenzoylmethane are particularly preferred because of their excellent ultraviolet absorbing ability. Since these compounds have commercial products, commercial products can be used as they are. Specific commercial products include “Ubinal A Plus Granular” (hexyl diethylaminohydroxybenzoyl benzoate, manufactured by BASF) and “Pulsol 1789” (t-butylmethoxybenzoylmethane, manufactured by DSM).
  • the content of the UV-A absorber is usually 0.01% by mass or more, preferably 0.1% by mass or more, and usually 5% by mass or less, preferably 3% by mass or less.
  • UV-B absorbers include 2-methoxyhexyl paramethoxycinnamate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, dimethicodiethylbenzalmalonate, 2,4,6-trianilino.
  • Oxy) -1,3,5-triazine BASF
  • Ubinal M40 (2-hydroxy-4-methoxybenzophenone, BASF
  • Pulsol SLX Dimethicodiethylbenzalmalonate, DSM
  • Examples include “Parsol 340” (2-ethylhexyl 2-cyano-3,3-diphenylacrylate, manufactured by DSM), “Parsol HMS” (homogentyl salicylate, manufactured by DSM), and “Pulsol EMS” (octyl salicylate, manufactured by DSM).
  • the content of the UV-B absorber is usually 0.1% by mass or more, preferably 0.5% by mass or more, and usually 10% by mass or less, preferably 7% by mass or less.
  • compositions contained in an oil phase and a water phase are not specifically limited.
  • oil agent constituting the oil phase include liquid oils and fats, solid oils and fats, waxes, hydrocarbon oils, higher fatty acids, higher alcohols, synthetic ester oils, silicone oils, and the like.
  • liquid oils 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, southern castor oil, castor oil, linseed oil , Safflower oil, cottonseed oil, eno oil, meadow foam oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnagari oil, Japanese kiri oil, jojoba oil, germ oil, triglycerin, glycerin trioctanoate, Examples include glycerin triisopalmitate.
  • Solid fats and oils include cocoa butter, coconut oil, horse fat, hydrogenated coconut oil, palm oil, beef tallow, sheep fat, hardened beef tallow, palm kernel oil, pork fat, beef bone fat, owl kernel oil, hydrogenated oil, and cow leg fat. , Mole, hardened castor oil, and the like.
  • the waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibota wax, whale wax, montan wax, nuka wax, lanolin, kapok wax, lanolin acetate, liquid lanolin, sugar cane wax, lanolin fatty acid isopropyl, lauryl hexyl, reduced lanolin, jojojo Examples thereof include a 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, and the like.
  • hydrocarbon oils examples include liquid paraffin, ozokerite, pristane, paraffin, ceresin, squalene, petrolatum, and microcrystalline wax.
  • higher fatty acids examples include lauric acid, myristic acid, palmitic acid, stearic acid, behen (behenine) acid, 12-hydroxystearic acid, undecylenic acid, and toric acid.
  • higher alcohols examples include cetyl alcohol, stearyl alcohol, behenyl alcohol, batyl alcohol, myristyl alcohol, cetostearyl alcohol, and the like.
  • Synthetic ester oils include isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyloctanoate, cetyl lactate, myristyl lactate Lanolin acetate, isocetyl stearate, isocetyl isostearate, sucrose stearate, sucrose oleate, cholesteryl 12-hydroxystearylate, ethylene glycol di-2-ethylhexylate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, Neopentyl glycol dicaprate, diisostearyl malate, glycerin di-2-heptylundecanoate, tri-2-
  • silicone oils include chain polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane, and cyclic polysiloxanes such as decamethylpolysiloxane, dodecamethylpolysiloxane, and tetramethyltetrahydrogenpolysiloxane. Is mentioned.
  • One or more oil agents can be used.
  • the sunscreen cosmetic of the present invention may be blended with optional additives that are usually blended in cosmetics within a range that does not impair the effects of the present invention.
  • additives include humectants such as polyethylene glycol, glycerin, 1,3-butylene glycol, erythritol, sorbitol, xylitol, and maltitol; lower alcohols such as ethanol; butylhydroxytoluene, tocopherol, and phytin.
  • Antioxidants such as benzoic acid, salicylic acid, sorbic acid, paraoxybenzoic acid alkyl ester, hexachlorophene; organic acids such as acyl sarcosine acid (eg, lauroyl sarcosine sodium), glutathione, citric acid, malic acid, tartaric acid, lactic acid Vitamin A and its derivatives, vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 and its derivatives, vitamin B12, vitamin B15 and its derivatives Vitamins B, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, vitamin E such as vitamin E acetate, vitamin D, vitamin H, pantothenic acid, panthetin, nicotinic acid amide, nicotinic acid benzyl; ⁇ -oryzanol, allantoin, glycyrrhizic acid (salt),
  • the sunscreen cosmetic of the present invention can be produced, for example, by the following method.
  • the oil agent, component (B), and other oil phase components are mixed and dissolved by heating to prepare a mixture of oil phase components.
  • the ultraviolet scattering agent (component (D)) is contained, the ultraviolet scattering agent is added to the mixture and dispersed using a disper.
  • the water phase component and the component (C) are mixed, and the mixture of the oil phase component is added to the heated portion and emulsified with a homogenizer.
  • the sunscreen cosmetic of the present invention is produced by adding component (A) and, if necessary, a water-dispersible UV scattering agent (component (D)) and cooling with stirring and mixing. Can do.
  • a sea-island structure is that two types of incompatible polymers cause phase separation, and a continuous phase containing one polymer is dotted with a dispersed phase containing the other polymer. It refers to the structure.
  • the continuous phase in the sea-island structure is called the sea phase
  • the dispersed phase is called the island phase
  • the particles in the dispersed phase are called island particles.
  • the film of the present invention has a sea-island structure in which island particles containing an amphiphilic copolymer are dispersed in a sea phase containing an aqueous gel formed by a water-soluble polymer.
  • the amphiphilic copolymer contained in the island particles has the structural unit (i) and the structural unit (j) as essential structural units.
  • the structural unit (i) is one or more structural units derived from a hydrophobic monomer
  • the structural unit (j) is one or more structural units derived from a hydrophilic monomer.
  • the coating film of the present invention having such a structural characteristic has a milk-like feel including an oily agent, despite being mainly composed of an aqueous component.
  • the coating film of the present invention will be described in detail.
  • the amphiphilic copolymer contained in the island particles having a sea-island structure includes a structural unit (i) derived from the hydrophobic monomer and a structural unit derived from the hydrophilic monomer ( j) as an essential constituent unit.
  • the amphiphilic copolymer in the present invention it is preferable to use a copolymer containing structural units derived from a hydrophobic monomer and a hydrophilic monomer described in [1] and [2] below.
  • [1] Hydrophobic monomer in the present invention, a structural unit derived from the hydrophobic monomer represented by the general formula (1), (7) or (8) (hereinafter simply referred to as “structural unit (7)”). It is preferable to use an amphiphilic copolymer (also referred to as an acrylic acid-based amphiphilic copolymer) containing one or more of the essential constituent units.
  • the “structural unit derived from a monomer” refers to a structural unit formed by cleavage of a carbon-carbon unsaturated bond of a corresponding monomer by a polymerization reaction.
  • the hydrophobic monomer represented by the general formula (1), (7) or (8) will be described.
  • R14 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R15 represents a ring having 13 to 30 carbon atoms.
  • a branched hydrocarbon group not containing a structure or a hydrocarbon group having 6 to 12 carbon atoms having two or more branches not containing a ring structure is represented.
  • examples of the alkyl group represented by R14 include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclopropyl group.
  • R14 is preferably a hydrogen atom or a methyl group.
  • Examples of the branched hydrocarbon group not containing a ring structure having 13 to 30 carbon atoms represented by R15 include 1-methyldodecanyl group, 11-methyldodecanyl group, 3-ethylundecanyl group, 3- Ethyl-4,5,6-trimethyloctyl, 1-methyltridecanyl, 1-hexyloctyl, 2-butyldecanyl, 2-hexyloctyl, 4-ethyl-1-isobutyloctyl, 1-methyl Pentadecanyl group, 2-hexyldecanyl group, 2-octyldecanyl group, 2-hexyldecanyl group, 16-methylheptadecanyl group, 9-methylheptadecanyl group, 7-methyl-2- (3 -Methylhexyl) decanyl group, 3,7,11,15-tetra-methylhexadecanyl group, 2-octyldode
  • examples of the hydrocarbon group having 6 to 12 carbon atoms having two or more branches and not including a ring structure represented by R15 include 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3, 3-dimethylbutyl group, 1,3-dimethylbutyl group, 1,2,2-trimethylpropyl group, 1,1-dimethylpentanyl group, 1-isopropylbutyl group, 1-isopropyl-2-methylpropyl group, 1 , 1-diethylpropyl group, 1-ethyl-1-isopropylpropyl group, 2-ethyl-4-methylpentyl group, 1-propyl-2,2-dimethylpropyl group, 1,1,2-trimethyl-pentyl group, 1-isopropyl-3-methylbutyl group, 1,2-dimethyl-1-ethylbutyl group, 1,3-dimethyl-1-ethylbutyl group, 1-ethyl-1-isopropyl-
  • R1 and R16 each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • R2, R3, R17, R18, and R19 may be the same or different and each represents a branched acyl group having 6 to 22 carbon atoms that does not contain a ring structure.
  • X represents a group in which an OH group is eliminated from a trivalent alcohol.
  • examples of the alkyl group represented by R1 and R16 include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclopropyl group.
  • R3 is preferably a hydrogen atom or a methyl group.
  • Examples of the branched acyl group having 6 to 22 carbon atoms that does not include the ring structure represented by R2, R3, R17, R18, and R19 include 2-methylpentanoyl group, 3-methylpentanoyl group, 4 -Methylpentanoyl group, 2-ethylbutanoyl group, 2-ethylbutanoyl group, 2,2-dimethylbutanoyl group, 3,3-dimethylbutanoyl group, 2-methylhexanoyl group, 4-methylhexanoyl group Group, 5-methylhexanoyl group, 2,2-dimethylpentanoyl group, 4,4-dimethylpentanoyl group, 2-methylheptanoyl group, 2-ethylhexyl group, 2-propylpentanoyl group, 2,2- Dimethylhexanoyl group, 2,2,3-trimethylpentanoyl group, 2-methyloctanoyl group,
  • R2, R3, R17, R18, and R19 may be the same or different, do not include a ring structure, and have a branch.
  • Such a branched acyl group having 10 to 22 carbon atoms which does not contain a ring structure and is represented by R2, R3, R17, R18 and R19 in a preferred embodiment includes a 2-methylnonanoyl group, 4- Methylnonanoyl group, 8-methylnonanoyl group, 4-ethyloctanoyl group, 2-ethyloctanoyl group, 2-butylhexanoyl group, 2-tert-butylhexanoyl group, 2,2-diethylhexanoyl group), 2, 2-dimethyloctanoyl group, 3,7-dimethyloctanoyl group, neodecanoyl group), 7-methyldecanoyl group, 2-methyl-2-ethyloctanoyl group, 2-methylundecanoyl group, 10-methylun Decanoyl group, 2,2 dimethyldecanoyl group, 2-ethyldecano
  • the acyl group having 6 to 9 carbon atoms having 2 or more branches and containing no ring structure represented by R2, R3, R17, R18, R19 is 2,2-dimethyl.
  • the group derived from the trihydric alcohol represented by X in the general formula (1) is not particularly limited as long as the OH group is eliminated from the trihydric alcohol, but glycerin, trimethylolpropane, trimethylolethane.
  • the group derived from the tetrahydric alcohol represented by Y in the general formula (8) is not particularly limited as long as the OH group is released from the tetrahydric alcohol, but diglycerin, pentaerythritol, erythritol.
  • a group in which an OH group is eliminated from a tetrahydric alcohol selected from the group consisting of D-threitol and L-threitol can be suitably exemplified.
  • the hydrophobic monomer represented by the general formula (1) is a hydrophobic monomer represented by the general formula (15).
  • the carbon number of the acyl group of R24 and R25 in the general formula (15) is 12 to 22, more preferably 14 to 20, and still more preferably 16 to 20.
  • the carbon number of the main chain of the acyl group of R24 and R25 in the general formula (15) is preferably 9 to 21, more preferably 12 to 20, and still more preferably 16 to 18.
  • the number of branches in the acyl group of R24 and R25 in the general formula (15) is preferably 1 to 3, more preferably 1 or 2, and still more preferably 1.
  • the position number of carbon in the main chain to which the branched chain is bonded is preferably as large as possible.
  • the branched chain is bonded to the carbon at the end of the main chain, preferably from the 1st to 3rd carbon, more preferably the 1st or 2nd carbon, and even more preferably the 1st carbon. It is preferable.
  • R24 and R25 include 10-methylundecanoyl group, 10-methyldodecanoyl group, 11-methyldodecanoyl group, 10-ethylundecanoyl group, 12-methyltridecanoyl group, 12-methyl Tetradecanoyl group, 14-methylpentadecanoyl group, 16-methylheptadecanoyl group, 2,4,10,14-tetramethylpentanoyl group, 18-methylnonadecanoyl group, 3,7,11,15 Preferred examples include -tetra-methylhexadecanoyl group, 19-methyleicosanoyl group and the like.
  • the group derived from the trihydric alcohol represented by Z in the general formula (15) is not particularly limited as long as the OH group is released from the trihydric alcohol, but glycerin, trimethylolpropane, trimethylolethane.
  • hydrophilic monomer As the hydrophilic monomer in the present invention, polymerizable carboxylic acid and compounds represented by the general formulas (2), (9), (10) and (11) can be used.
  • the polymerizable carboxylic acid or a salt thereof specifically includes acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid and its sodium salt, potassium salt, Examples thereof include ammonium salts and amine salts. Among these, acrylic acid, methacrylic acid and salts thereof are particularly preferable because of high polymerizability.
  • a structural unit derived from a salt of a polymerizable carboxylic acid is introduced into the amphiphilic copolymer of the present invention, the polymerizable carboxylic acid may be converted into a salt in advance, and a polymerization reaction may be performed.
  • a structural unit derived from a basic carboxylic acid may be derived into an amphiphilic copolymer and then neutralized with a base to form a salt.
  • R4 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R5 may have a hydroxyl group.
  • R6 represents a hydrogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, an aliphatic hydrocarbon group having 1 to 14 carbon atoms, or an acyl group having 1 to 12 carbon atoms.
  • n represents an integer of 6 to 40.
  • examples of the alkyl group represented by R4 include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a cyclopropyl group.
  • R6 is preferably a hydrogen atom or a methyl group.
  • alkylene group represented by R5 examples include ethylene group, propylene group, isopropylene group, 2-hydroxypropylene group, 1-hydroxy-2-methylethylene group, 2-hydroxy-1-methylethylene group and the like. Of these, ethylene group or propylene group is preferable, and ethylene group is more preferable.
  • examples of the aromatic group having 6 to 10 carbon atoms include a phenyl group, a benzyl group, a methylphenyl group, and an ethylphenyl group; an aliphatic carbon atom having 1 to 14 carbon atoms
  • Preferred examples of the hydrogen group include a methyl group, an ethyl group, a butyl group, a tertiary butyl group, a hexyl group, a cyclohexyl group, an octyl group, a 2-ethylhexyl group, and a lauryl group
  • Preferred examples of the 12 acyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, and a lauroyl group.
  • the group represented by R5 is preferably an aliphatic hydrocarbon group having 1 to 14
  • n in the general formula (2) is in the numerical range of 6 to 40.
  • Specific examples of the monomer represented by the general formula (2) in which R5 is a propylene group include polypropylene glycol (9) monoacrylate, polypropylene glycol (13) monoacrylate, and polypropylene glycol (9) monomethacrylate. And polypropylene glycol (13) monomethacrylate.
  • the number in parentheses represents N.
  • Many of these polymers are commercially available. Specific examples of such commercially available products include “Blemmer” AP-400, AP-550, AP-800, PP-500, PP-800 (all manufactured by NOF Corporation) and the like.
  • R5 is an ethylene group, specifically, polyethylene glycol (10) monoacrylate, polyethylene glycol (8) monomethacrylate, polyethylene glycol (23) monoacrylate.
  • hydrophilic monomer can be obtained in high yield by esterification reaction of the corresponding polyethylene glycol, polyethylene glycol monoether, polyethylene glycol monoester with acrylic acid or methacrylic acid chloride or anhydride.
  • esterification reaction of the corresponding polyethylene glycol, polyethylene glycol monoether, polyethylene glycol monoester with acrylic acid or methacrylic acid chloride or anhydride.
  • Specific examples of such commercially available products include Blemmer, AE-400, PE-350, AME-400, PME-400, PME-1000, ALE-800, PSE-1300, etc. Etc.).
  • hydrophilic monomer represented by general formula (9) As the hydrophilic monomer in the present invention, a hydrophilic monomer represented by the above general formula (9) may be used.
  • hydrophilic monomer represented by the general formula (9) examples include 2-acryloyloxyethyl phosphorylcholine (APC) and 2-methacryloyloxyethyl phosphorylcholine (MPC). These monomers can be synthesized by the following method described in Polymer Journal, Vol 22, No. 5, for example.
  • hydrophilic monomer represented by general formula (9) As the hydrophilic monomer in the present invention, a hydrophilic monomer represented by general formula (10) may be used.
  • hydrophilic monomer represented by the general formula (10) as the reducing sugar of the group obtained by removing hydrogen from the hydroxyl group at the 1-position of the reducing sugar represented by GO—, specifically, glucose, mannose,
  • Examples include one or more selected from the group consisting of monosaccharides such as galactose, arabinose, xylose and ribose, disaccharides such as maltose, lactose and cellobiose, trisaccharides such as maltotriose, and oligosaccharides such as malto-oligosaccharide
  • glucose is particularly preferable.
  • the monomer represented by the general formula (10) is preferably glucosyloxyethyl methacrylate (hereinafter abbreviated as GEMA) or glucosyloxyethyl acrylate (hereinafter abbreviated as GEA).
  • GEMA glucosyloxyethyl methacrylate
  • GEA glucosyloxyethyl acrylate
  • hydrophilic monomer represented by general formula (11) As the hydrophilic monomer in the present invention, a hydrophilic monomer represented by general formula (11) may be used.
  • the amino acid of the amino acid residue represented by R23 is not particularly limited as long as it is a commonly known amino acid. Specifically, glycine, alanine, glutamine, lysine, Arginine etc. are illustrated. Of these, lysine residues are particularly preferred because the resulting amphiphilic copolymer is excellent in the skin barrier recovery effect.
  • the polyamine in the polyamine residue represented by R23 means an amine having two or more amino groups that may be substituted with an alkyl group in the same molecule, and specifically includes diamine, triamine, tetraamine. Or the amine by which the hydrogen atom of these amino groups is substituted by the alkyl group is illustrated.
  • diamine is preferable because the feeling of use of the external preparation for skin containing the obtained amphiphilic copolymer is particularly excellent, and as a particularly preferable specific example, ethylenediamine, Examples include 1,4-diamino-n-butane and 1,6-diamino-n-hexane.
  • amino alcohol in the amino alcohol residue represented by R23 means a compound having an amino group which may be substituted with an alkyl group in the same molecule and an alcoholic hydroxyl group.
  • the amino alcohol is not particularly limited as long as it is generally known, but specific examples include ethanolamine and triethylaminoethanol.
  • the sodium salt, potassium salt, ammonium salt, amine salt, etc. which neutralized the acid part with the base
  • examples thereof include hydrochlorides, sulfates, nitrates, phosphates, citrates, oxalates, carbonates, etc., in which the amino group is neutralized with an acid.
  • the structural unit derived from the salt of the monomer represented by the general formula (11) is introduced into the amphiphilic copolymer of the present invention, the monomer represented by the general formula (11) is previously converted into a salt, and the polymerization reaction is performed.
  • the structural unit derived from the monomer represented by the general formula (11) may be derived into an amphiphilic copolymer by a polymerization reaction, and then neutralized to form a salt.
  • Specific examples of the monomer represented by the general formula (11) and salts thereof include compounds 1 to 11 and salts thereof.
  • the hydrophilic monomer represented by the general formula (11) is, for example, an esterification reaction using (meth) acrylic acid or (meth) acrylic acid chloride, amide as shown in the reaction formulas (1) and (2). It can be synthesized by a chemical reaction.
  • the general formulas (2), (9), (10), and (11) can be used as the hydrophilic polymer in the present invention.
  • the amphiphilic copolymer comprises the structural unit (2) derived from the general formula (2).
  • an acrylic acid-based amphiphilic copolymer having the structural unit (1) and the structural unit (2) can be preferably used. More preferably, an acrylic acid-based amphiphilic copolymer having the structural unit (15) and the structural unit (2) is used. Of these acrylic acid-based amphiphilic copolymers, a (methoxy PEG-23 methacrylate / glyceryl methacrylate) is particularly preferably used. By containing such an acrylic acid-based amphiphilic copolymer, the moisture retention and flexibility of the coating can be improved.
  • (Methoxymethacrylate PEG-23 / glyceryl methacrylate diisostearate) copolymer is a structural unit (i) in which R24 and R25 are 16-methylheptadecanoyl among the hydrophobic monomers represented by the general formula (15). It mainly contains a structural unit (i) derived from a hydrophobic monomer as a group.
  • R4 is a methyl group
  • R5 is an ethylene group
  • R6 is a methyl group
  • n is 23.
  • the structural unit (j) is mainly included.
  • an existing copolymer can be used in addition to the above-mentioned copolymer.
  • the following existing copolymers can be used as the amphiphilic copolymer. That is, polyquaternium-51 (a copolymer containing 2-methacryloyloxyethyl phosphorylcholine and butyl methacrylate in a molar ratio of approximately 8: 2), polyquaternium-61 (2-methacryloyloxyethyl phosphorylcholine and stearyl methacrylate approximately 3: 7).
  • a glyceryl amidoethyl methacrylate / stearyl methacrylate copolymer (glyceryl-N- (2-methacryloyloxyethyl) carbamate and stearyl methacrylate in a molar ratio of approximately 6: 4), Copolymer having a weight average molecular weight of about 40,000), PEG / PPG / polybutylene glycol-8 / 5/3 glycerin, (hydrolyzed silk / PGpropylmethylsilanediol) crosspolymer (N- [2-hydroxy-3- [ 3 (Hydroxymethylsilyl) propoxy] propyl] hydrolyzed silylated copolymer), (eicosane diacid / tetradecanedioic acid) polyglyceryl-10 (eicosane diacid, tetradecanedioic acid dibasic acid and average degree of polymerization) 10 oligo
  • the ratio of the structural unit (i) to the total structural units in the amphiphilic copolymer is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, and 10 to 30% by mass.
  • the proportion of the structural unit (j) in all the structural units in the amphiphilic copolymer is preferably 50 to 99% by mass, more preferably 60 to 95% by mass, and 70 to 90% by mass.
  • the mass ratio of the structural unit (i) and the structural unit (j) constituting the amphiphilic copolymer is preferably 5:95 to 50:50, more preferably 10:90 to 45:55, More preferably, it is 20:80 to 40:60, and more preferably 25:75 to 35:65.
  • the molar ratio of the structural unit (i) to the structural unit (j) constituting the amphiphilic copolymer is preferably 8:92 to 62:38, more preferably 15:85 to 57:43, More preferably, it is 29:71 to 52:48, and more preferably 35:65 to 46:54.
  • the average molecular weight of the amphiphilic copolymer is preferably 20,000 to 110,000, more preferably 20,000 to 80,000, more preferably 30,000 to 80,000, more preferably 40,000 to 70,000, still more preferably 50,000 to 70,000, still more preferably. Is 57000-66000.
  • an average molecular weight means here the weight average molecular weight of polystyrene conversion measured by GPC.
  • the aqueous gel is formed of a water-soluble polymer and / or a salt thereof and water hydrated in the water-soluble polymer.
  • the water-soluble polymer and / or salt thereof forming the aqueous gel is not particularly limited as long as the phase containing the amphiphilic copolymer can be dispersed as island particles, but is preferably an acrylic acid-based water-soluble polymer or water-soluble polymer.
  • One or more water-soluble polymers selected from the group consisting of peptides and water-soluble polysaccharides and / or salts thereof can be used.
  • a non-crosslinked acrylic acid polymer or an acrylic acid copolymer which may be crosslinked can be particularly preferably exemplified.
  • the non-crosslinked acrylic acid polymer is preferably exemplified by sodium polyacrylate, and the cross-linked acrylic acid copolymer may be sodium polyacrylate, (acrylates / alkyl acrylate (C10 -30))
  • Cross polymers can be preferably exemplified.
  • a preferable example of the water-soluble polypeptide is sodium polyglutamate.
  • a xanthan gum and a white jellyfish polysaccharide can be illustrated preferably.
  • xanthan gum is used as the water-soluble polysaccharide.
  • the coating of the present invention has a sea-island structure in which an island phase containing an amphiphilic copolymer is dispersed in a sea phase containing an aqueous gel.
  • the area ratio of the sea phase to the island phase is preferably 2: 8 to 10: 1, more preferably 3: 7 to 9: 1, and further preferably 6: 4 to 7. : 3.
  • the coating film of the present invention in which the area ratio of the sea phase to the island phase is in the above range is excellent in elasticity, less sticky, and excellent in moisture retention and flexibility.
  • the average major axis / minor axis ratio of the island particles is preferably 0.6 or more, more preferably 0.7 or more, still more preferably 0.8 or more, and further preferably 0.9 or more. It is.
  • the average major axis / minor axis ratio can be measured by observing the composition under a microscope. Specifically, the composition can be obtained by observing the composition under a microscope, measuring the major axis / minor axis ratio of 100 island particles, and arithmetically averaging them.
  • the ratio of the major axis to the minor axis ratio of all island particles contained in the coating is less than 0.6, more preferably less than 0.7, and more preferably less than 0.8.
  • the abundance ratio is 10% or less.
  • the proportion of the island particles having a major axis / minor axis ratio of less than 0.8 is 5% or less, more preferably 1% or less, in all of the island particles contained in the composition. is there.
  • the film of the present invention in such an embodiment is excellent in moisture retention and flexibility.
  • the number particle size distribution of island particles having an average particle diameter of 0.5 to 10 ⁇ m, more preferably island particles having an average particle diameter of 1 to 5 ⁇ m is 80% or more. In a further preferred embodiment of the present invention, the number particle size distribution of island particles having an average particle diameter of 1 to 5 ⁇ m is 85% or more, more preferably 90% or more.
  • the average particle size of the island particles can be measured by observing the composition with a microscope. Specifically, the composition can be obtained by measuring the major axis and minor axis of the island particles by microscopic observation and arithmetically averaging them.
  • the coating film of the present invention can contain any component usually used in a skin external preparation.
  • Such components include oils / waxes, hydrocarbons, higher fatty acids, higher alcohols, synthetic ester oils, silicone oils, surfactants, polyhydric alcohols, moisturizing ingredients, thickening agents.
  • oils and waxes include macadamia nut oil, avocado oil, corn oil, olive oil, rapeseed oil, sesame oil, castor oil, safflower oil, cottonseed oil, jojoba oil, coconut oil, palm oil, liquid lanolin, hardened coconut oil, hardened Oil, mole, hardened castor oil, beeswax, candelilla wax, carnauba wax, ibotarou, lanolin, reduced lanolin, hard lanolin, jojoba wax, etc.
  • hydrocarbons include liquid paraffin, squalane, pristane, ozokerite, paraffin, ceresin, petrolatum, and microcrystalline wax.
  • higher fatty acids include oleic acid, isostearic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, etc.
  • higher alcohols include cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, octyldodecanol, myristyl alcohol, cetostearyl alcohol, and the like.
  • Synthetic ester oils include, for example, cetyl isooctanoate, isopropyl myristate, hexyldecyl isostearate, diisopropyl adipate, di-2-ethylhexyl sebacate, cetyl lactate, diisostearyl malate, ethylene di-2-ethylhexanoate Glycol, neopentyl glycol dicaprate, glycerin di-2-heptylundecanoate, glycerol tri-2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, tetra-2-ethylhexane Acid pentane erythritol, etc.
  • silicone oils include chain polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, cyclic polysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexanesiloxane, amino Examples thereof include silicone oils such as modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, and fluorine-modified polysiloxane.
  • chain polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane
  • cyclic polysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexanes
  • Surfactants may be either anionic surfactants or nonionic surfactants.
  • anionic surfactants include fatty acid soap (sodium laurate, sodium palmitate, etc.), potassium lauryl sulfate, alkyl sulfate triethanolamine ether, and the like.
  • Nonionic surfactants include, for example, sorbitan fatty acid esters (such as sorbitan monostearate and sorbitan sesquioleate), glycerin fatty acids (such as glyceryl monostearate), and propylene glycol fatty acid esters (such as propylene glycol monostearate).
  • Hardened castor oil derivative glycerin alkyl ether, POE sorbitan fatty acid esters (POE sorbitan monooleate, polyoxyethylene sorbitan monostearate, etc.), POE sorbite fatty acid esters (POE-sorbite monolaurate, etc.), POE glycerin Fatty acid esters (POE-glycerol monoisostearate, etc.), POE fatty acid esters (polyethylene glycol monooleate, POE distearate, etc.), POE alkyl Ethers (POE2-octyldodecyl ether, etc.), POE alkylphenyl ethers (POE nonylphenyl ether, etc.), Pluronic types, POE / POP alkyl ethers (POE / POP2-decyltetradecyl ether, etc.), Tetronics, POE castor oil / hardened castor oil derivative
  • polyhydric alcohols examples include polyethylene glycol, erythritol, xylitol, propylene glycol, dipropylene glycol, isoprene glycol, 1,2-pentanediol, 2,4-hexylene glycol, 1,2-hexanediol, 1,2 -Octanediol, etc.
  • moisturizing ingredients include sodium pyrrolidonecarboxylate, lactic acid, sodium lactate and the like
  • thickeners include guar gum, quince seed, carrageenan, galactan, gum arabic, pectin, mannan, starch, curdlan, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, methyl hydroxypropyl cellulose, chondroitin sulfate, dermatan sulfate, glycogen, heparan.
  • Examples include chitosan, carboxymethyl chitin, agar, polyvinyl alcohol, polyvinyl pyrrolidone, carboxyvinyl polymer, polyethylene glycol, bentonite and the like.
  • Examples of powders include mica, talc, kaolin, synthetic mica, calcium carbonate, magnesium carbonate, anhydrous silicic acid (silica), aluminum oxide, barium sulfate, etc., whose surface may be treated.
  • the inorganic pigments for example, bengara, yellow iron oxide, black iron oxide, cobalt oxide, ultramarine, bitumen, titanium oxide, zinc oxide, etc., whose surface may be treated, are mentioned,
  • organic pigments the surface may be treated, pearl agents such as titanium mica, fish phosphorus foil, bismuth oxychloride, red 202, red 228, red 226, which may be raked, Yellow No. 4, Blue No. 404, Yellow No. 5, Red No. 505, Red No. 230, Red No.
  • organic powders include polyethylene powder, polymethyl methacrylate, nylon powder, and organopolysiloxane elastomer.
  • UV absorbers examples include paraaminobenzoic acid UV absorbers, anthranilic acid UV absorbers, salicylic acid UV absorbers, cinnamic acid UV absorbers, benzophenone UV absorbers, sugar UV absorbers, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 4-methoxy-4′-t-butyldibenzoylmethane and the like,
  • lower alcohols include ethanol, isopropanol, phenoxyethanol, and the like.
  • vitamins examples include vitamin A or derivatives thereof, vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 or derivatives thereof, vitamin B such as vitamin B12, vitamin B15 or derivatives thereof, ⁇ -tocopherol, etc.
  • Preferred examples include vitamin E such as ⁇ -tocopherol, ⁇ -tocopherol and vitamin E acetate, vitamin D, vitamin H, pantothenic acid, pantethine, pyrroloquinoline quinone and the like.
  • the polymer having a bio-similar structure examples include polymethacryloyl lysine and polyglycosyl ethyl methacrylate.
  • the content of oils such as oils / waxes, hydrocarbons, higher fatty acids, higher alcohols, synthetic ester oils and silicone oils is preferably 10% by mass or less, more preferably 5%. % By mass or less, more preferably 2.5% by mass or less, further preferably 2% by mass or less, more preferably 1% by mass or less, and further preferably 0.5% by mass or less.
  • an oil agent is not contained.
  • the film having the sea-island structure of the present invention is mainly composed of an aqueous component, it can exhibit a feeling of use like milk containing an oil agent. Therefore, the film having the sea-island structure of the present invention can be in an oil-free form.
  • the content of the surfactant is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 2.5% by mass or less, further preferably 2% by mass or less, and further preferably. Is 1% by mass or less, more preferably 0.5% by mass or less.
  • surfactant is not contained.
  • the coating film of the present invention can form a stable sea-island structure without containing a surfactant. Therefore, the coating film having the sea-island structure of the present invention can be in a surfactant-free form.
  • composition for forming a film The present invention also relates to a composition capable of forming on the skin a film having the above-described sea-island structure of the present invention by applying to the skin.
  • the composition of the present invention contains the above-mentioned amphiphilic copolymer and water-soluble polymer and / or salt thereof, and water.
  • the water in the composition evaporates, causing phase separation between the amphiphilic copolymer and the water-soluble polymer.
  • the coating of the present invention is formed on the skin.
  • water and polyol in the composition are taken into the aqueous gel formed by the water-soluble polymer.
  • the matter regarding the film of this invention described in the item of said ⁇ 1> is applicable.
  • the content of the amphiphilic copolymer is preferably 0.01 to 10% by mass, more preferably 0.05 to 7% by mass, still more preferably 0.1 to 5% by mass, and still more preferably. Is 0.5-3 mass%. According to the composition of the present invention in which the content of the amphiphilic copolymer is in the above range, a film having excellent elasticity and little stickiness can be formed on the skin.
  • the proportion of the water-soluble polymer in the entire composition is preferably 0.001 to 10% by mass, more preferably 0.005 to 5% by mass, and still more preferably 0.01 to 1% by mass. More preferably, it is 0.05 to 0.5% by mass. According to the composition of the present invention in which the content of the water-soluble polymer is in the above range, a film excellent in moisture retention and flexibility can be formed on the skin.
  • the mass ratio of the content of the water-soluble polymer and the amphiphilic copolymer is preferably 1: 100 to 1: 2, more preferably 1:50 to 1: 5, and even more preferably.
  • the ratio is 1:30 to 1:10, more preferably 1:25 to 1:15.
  • a polyol that promotes / suppresses the separation of the sea phase and the island phase. That is, in a preferred embodiment of the present invention, the phase separation between the aqueous gel and the amphiphilic copolymer (hereinafter also referred to as an accelerating polyol) and / or the phase separation between the aqueous gel and the amphiphilic copolymer is suppressed.
  • a polyol hereinafter referred to as an inhibitory polyol
  • both an accelerating polyol and an inhibitory polyol are included. According to the composition of the present invention containing such a polyol, a film having a highly uniform sea-island structure can be formed on the skin.
  • a polyol that raises the cloud point of the aqueous solution by mixing with an aqueous solution of a nonionic surfactant having a polyether chain in the hydrophilic portion can be preferably exemplified.
  • Preferred examples of such an accelerating polyol include 1,3-butylene glycol and polyethylene glycol.
  • the content of the accelerating polyol in the entire composition of the present invention is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, still more preferably 3 to 20% by mass, and still more preferably. Is 5 to 15% by mass.
  • Preferred examples of the inhibitory polyol include a polyol that lowers the cloud point of the aqueous solution by mixing it with an aqueous solution of a nonionic surfactant having a polyether chain in the hydrophilic portion.
  • Preferred examples of such inhibitory polyols include glycerin, diglycerin, sorbitol and maltitol. By using such a polyol, it becomes possible to form a film with higher uniformity.
  • the content of the inhibitory polyol in the entire composition of the present invention is preferably 0.5 to 30% by mass, more preferably 1 to 25% by mass, further preferably 5 to 20% by mass, and further preferably 8 to 15% by mass. %.
  • the cloud point refers to a temperature at which phase separation occurs due to a temperature change in a transparent or translucent liquid, resulting in opaqueness, and in particular, an aqueous solution of a nonionic surfactant is heated.
  • Whether the cloud point of an aqueous solution of a nonionic surfactant having a polyether chain in the hydrophilic part is raised or lowered can be specifically confirmed by the following method. An aqueous solution of a nonionic surfactant having a polyether chain in the hydrophilic portion is heated, and a temperature at which the aqueous solution starts to become cloudy, that is, a cloud point is recorded.
  • the polyol is added to the aqueous solution and mixed, and the cloud point is recorded in the same manner.
  • the added polyol is evaluated as “raised the cloud point of the aqueous solution”.
  • the added polyol is evaluated as “lowered the cloud point of the aqueous solution”.
  • nonionic surfactant having a polyether chain in the hydrophilic portion used for the above-described cloud point measurement a nonionic surfactant having polyethylene glycol in the hydrophilic portion can be preferably exemplified.
  • the mass ratio of the accelerating polyol and the inhibiting polyol is preferably 10: 1 to 1:10, more preferably 6: 1 to 1: 5, further preferably 4: 1 to 1: 3, Preferably it is 3.5: 1 to 1: 2.5, more preferably 1.6: 1 to 1: 1.
  • the ratio of the total mass of the accelerating polyol and the inhibitory polyol and the mass content of the amphiphilic copolymer is 5: 1 to 20: 1, more preferably 7: 1 to 15: 1, still more preferably 8: 1 to 12: 1.
  • the ratio of the total mass of the accelerating polyol and the inhibitory polyol and the total mass of the amphiphilic copolymer and the water-soluble polymer is 5: 1 to 20: 1, more preferably 7: 1 to 15: 1, more preferably 8: 1 to 12: 1.
  • the content of the accelerating polyol in the total amount of the three components of the accelerating polyol, the inhibiting polyol and the amphiphilic copolymer is preferably 10 to 80% by mass, more preferably 20 to 70% by mass. %, More preferably 30 to 70% by mass, still more preferably 40 to 60% by mass, and still more preferably 40 to 55% by mass.
  • the content of the inhibitory polyol in the total amount of the three components of the accelerator polyol, the inhibitory polyol and the amphiphilic copolymer is preferably 10 to 80% by mass, more preferably 20 to 20%. It is 70% by mass, more preferably 30 to 60% by mass, still more preferably 35 to 50% by mass.
  • the content of the amphiphilic copolymer in the total amount of the three components of the accelerating polyol, the inhibiting polyol and the amphiphilic copolymer is preferably 1 to 50% by mass, more preferably 3%. -20% by mass, more preferably 5-15% by mass, and still more preferably 8-12% by mass.
  • the content of the accelerating polyol is 20 to 70% by mass in the total amount of the three components of the accelerating polyol, the inhibitory polyol and the amphiphilic copolymer, and the content of the inhibitory polyol is 20 to 20%. 70% by mass and the content of the amphiphilic copolymer is 5 to 20% by mass.
  • the content of the accelerating polyol, the content of the inhibitory polyol, and the content of the amphiphilic copolymer in the total amount of the three components of the accelerating polyol, the inhibitory polyol, and the amphiphilic copolymer it becomes possible to adjust the major axis / minor axis ratio and the average particle size of the island particles in the coating formed by the composition of the present invention to the preferred ranges described in the above item ⁇ 1-3>.
  • composition of the present invention can be produced by stirring and mixing raw materials at room temperature.
  • the content of water in the composition of the present invention is preferably 60 to 99% by mass, more preferably 70 to 95% by mass, and still more preferably 80 to 90% by mass.
  • the present invention also relates to a method for forming the film of the present invention on the skin.
  • the method of the present invention is characterized by applying the composition of the present invention to the skin.
  • phase separation occurs between the aqueous gel formed by the water-soluble polymer and the amphiphilic copolymer.
  • a film having the sea-island structure of the present invention can be formed on the skin.
  • an aqueous solution containing a polyol that promotes phase separation between the amphiphilic copolymer and the aqueous gel and / or a polyol that suppresses phase separation between the aqueous gel and the amphiphilic copolymer By using such an aqueous solution, a film having excellent uniformity can be formed on the skin.
  • the content of oils such as oils / waxes, hydrocarbons, higher fatty acids, higher alcohols, synthetic ester oils, silicone oils, etc. is preferably 2% by mass or less. More preferably, it is 1 mass% or less, More preferably, it is 0.5 mass% or less. Moreover, in preferable embodiment of this invention, an oil agent is not contained.
  • content of surfactant becomes like this. Preferably it is 2 mass% or less, More preferably, it is 1 mass% or less, More preferably, you may be 0.5 mass% or less. Moreover, in preferable embodiment of this invention, surfactant is not contained.
  • compositions and the coating in the method of the present invention are as described in the above items ⁇ 1> and ⁇ 2>.
  • Trimethylolpropane monoacrylate synthesis step (1) In a eggplant-shaped flask equipped with a calcium tube, a condenser tube and a Dean-Stark trap, 145.7 g of trimethylolpropane, 300 ml of acetone, 3 g of p-toluenesulfonic acid monohydrate and 300 mL of petroleum ether were added, and the mixture was heated to reflux in an oil bath set at 50 ° C. After 12 hours, after confirming that water was no longer generated, the reaction mixture was cooled to room temperature. Next, 3 g of sodium acetate was added and the mixture was further stirred for 30 minutes, and then petroleum ether and acetone were distilled off by an evaporator. The obtained crude product was distilled under reduced pressure to obtain ketalized trimethylolpropane (intermediate 2).
  • Step (2) 104.8 g of Intermediate 2 obtained in Step (1), 258.0 g of methyl acrylate, and 3.7 g of tetramethoxy titanium were charged into a 3 L four-necked flask. Then, the reaction liquid was stirred, and a transesterification reaction was performed at 105 to 110 ° C. for 2.5 hours while introducing nitrogen gas into the liquid. After completion of the reaction, ketalized trimethylolpropane acrylate ester (intermediate 3) was obtained by fractionation by distillation under reduced pressure.
  • Step (3) In a 3 L four-necked flask, 90.2 g of water, 28.4 ml of cation exchange resin RCP160M (Mitsubishi Chemical), 115.3 g of Intermediate 3 obtained in Step (2) were charged. Then, the reaction solution was stirred, and a ketal deketone reaction was carried out at 24 ° C. for 27 hours while introducing nitrogen gas into the solution. After completion of the reaction, the cation exchange resin was filtered off from the reaction solution, and the filtered reaction solution was washed 6 times with 100 ml of hexane to remove unreacted raw materials, and then 200 ml of ethyl acetate was added to the aqueous layer to obtain a product. Extracted. Then, ethyl acetate and water were distilled off from this ethyl acetate extract under reduced pressure (800 Pa) at 40 ° C. or lower to obtain trimethylolpropane monoacrylate.
  • RCP160M Mitsubishi Chemical
  • Production Example 4 Production Example 1 of Hydrophobic Monomer Represented by Formula (1)
  • a reaction vessel equipped with a stirrer and a condenser tube 28.4 g of 16-methylheptadecanoic acid (manufactured by Sigma-Aldrich), 35.7 g of thionyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 200 ml of benzene were stirred and mixed. . While continuing stirring, refluxing was performed for 4 hours, and then purification by vacuum distillation was performed to obtain 16-methylheptadecanoic acid chloride.
  • Production Example 5 Production Example 2 of Hydrophobic Monomer Represented by General Formula (1)
  • a reaction vessel equipped with a stirrer and a condenser tube 25.6 g of 2-hexyldecanoic acid (manufactured by Sigma-Aldrich), 35.7 g of thionyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), and 200 ml of benzene were stirred and mixed. Refluxing was performed for 4 hours while continuing stirring, and then purification by vacuum distillation was performed to obtain 2-hexyldecanoic acid chloride.
  • Production Example 6 Production Example 3 of Hydrophobic Monomer Represented by Formula (1) Part 3
  • 28.4 g of 9-methylheptadecanoic acid manufactured by Sigma-Aldrich
  • 35.7 g of thionyl chloride manufactured by Tokyo Chemical Industry Co., Ltd.
  • 200 ml of benzene were stirred and mixed.
  • refluxing was performed for 4 hours, and then purification by vacuum distillation was performed to obtain 9-methylheptadecanoic acid chloride.
  • a solution prepared by dissolving 2.0 g of ammonium persulfate in 20 ml of water was added thereto, and further reacted at 65 ° C. for 10 hours while continuing stirring (reacted for 16 hours under the same conditions to synthesize a copolymer of Comparative Example 1). .
  • the pH was adjusted to 7.0 using an aqueous sodium hydroxide solution, and isopropyl alcohol was removed with a rotary evaporator to obtain an aqueous solution of the copolymer of Example 1 (treated under the same conditions as in Comparative Example 1). An aqueous solution of the copolymer was obtained).
  • the aqueous copolymer solution of Examples 1 to 6 is the same as the aqueous copolymer solution of Comparative Example 1.
  • the inventive copolymers of Examples 1, 5 and 6 have a very strong feeling of elasticity.
  • the above results indicate that the copolymer containing the structural unit (a) and the structural unit (b) having a weight average molecular weight of 20000 to 110000, particularly preferably 57000 to 66000 is excellent in elasticity.
  • a gel cosmetic was prepared by adding 0.5% by mass of xanthan gum to a 2% by mass aqueous solution of the copolymer of Example 1 or the copolymer of Comparative Example 1. This gel cosmetic was applied to the skin of three professional sensory evaluators as in Test Example 1, and evaluated for non-stickiness, elasticity, and moist feeling. The evaluation was performed according to the following evaluation criteria based on the feeling of use when an emulsion (standard cosmetic) containing trimethylolpropane triisostearate was applied to the skin. Table 4 and FIG. 1 show average values of evaluation values by three evaluators.
  • the gel cosmetic of Example 1 was significantly more elastic than the gel cosmetic of Comparative Example 1, and was excellent in non-stickiness and moist feeling. .
  • This result shows that the copolymer containing the structural unit (a) and the structural unit (b) having a weight average molecular weight of 20000 to 110000 is excellent in non-stickiness and moist feeling as well as elasticity.
  • glyceryl diisostearate methacrylate which is a hydrophobic monomer
  • methoxy methacrylic acid methoxy PEG-23 which is a hydrophilic monomer
  • a (glyceryl diisostearate methacrylate / methoxymethacrylic acid methoxy PEG-23) copolymer having an average molecular weight of 61,000 copolymerized at a mass ratio was used.
  • polyoxypropylene polymerization degree 60
  • polyoxyethylene average polymerization degree 11
  • PEG / PPG-60 / 11 glycerin Adecanol M-3228 which is an ether of glycerin
  • a product was produced (Comparative Examples 2, 4, 6).
  • an emulsion composition was produced using polyoxyethylene hydrogenated castor oil as a surfactant (Comparative Examples 3, 5, and 7).
  • FIG. 2 shows a three-component phase diagram in which the blending ratios of (glyceryl diisostearate methacrylate / methoxy methacrylate PEG-23) copolymer, squalane and water in Examples 9 to 31 are plotted.
  • FIG. 3 shows a three-component phase diagram in which the blending ratios of (glyceryl diisostearate methacrylate / methoxymethoxymethacrylate methacrylate-23) copolymer, tri (caprylic acid / capric acid) glyceryl and water in Examples 32-62 are plotted. .
  • FIG. 4 shows a three-component phase diagram in which the blending ratios of (glyceryl diisostearate methacrylate / methoxymethacrylic acid methoxy PEG-23) copolymer, dimethicone and water in Examples 63 to 89 are plotted.
  • the emulsified compositions of Examples 9 to 89 showed a stable emulsified form even after being stored at room temperature for 3 months. That is, (glyceryl diisostearate methacrylate / methoxy methacrylic acid PEG-23) copolymer allows non-polar hydrocarbon oil squalane, polar hydrocarbon oil tri (caprylic / capric) glyceryl, and silicone Even when any oil agent was used, a stable emulsion composition could be produced.
  • the compositions of Comparative Examples 2, 4 and 6 containing PEG / PPG-60 / 11 glycerin, which is a water-soluble copolymer cannot be emulsified even if they are stirred and mixed. Completely separated. This result shows that according to the water-soluble copolymer which is the emulsifier of the present invention, a stable emulsion composition can be produced using various oil agents.
  • the emulsified composition was prepared in any formulation having a content of (glyceryl diisostearate methacrylate / methoxy methacrylic acid PEG-23) copolymer of 1 to 30% by mass. could be manufactured. Further, as shown in Tables 5 to 7, an emulsified composition could be produced even when the oil phase content was 10 to 70% by mass.
  • Examples 9 to 89 and Comparative Examples 3, 5, and 7 were applied to the skin.
  • the emulsified compositions of Examples 9 to 89 had no irritation and less stickiness compared to the emulsified compositions of Comparative Examples 3, 5, and 7.
  • This result shows that the emulsified composition emulsified with the water-soluble copolymer which is the emulsifier of the present invention is superior in usability compared with a general emulsified composition emulsified with a surfactant.
  • the emulsified composition of the example in which the content of the (glyceryl diisostearate methacrylate / methoxymethoxy methacrylate-23) copolymer is 15% by mass, more preferably 1% by mass, has a better feeling of use. It was.
  • ⁇ Production Example 7> The face wash of Examples 90 to 92 and Comparative Examples 8 and 9 were produced according to the formulation shown below. That is, each of the components (a) and (b) was heated to 80 ° C., and (b) was added to the mixture under stirring and stirred, followed by cooling to obtain a face wash.
  • As the water-soluble copolymer glyceryl diisostearate methacrylate, which is a hydrophobic monomer, and methoxy PEG-methacrylate methacrylate, which is a hydrophilic monomer, are copolymerized at a molar ratio of approximately 3: 7, and an average molecular weight of 61000. (Glyceryl diisostearate methacrylate / methoxy methacrylic acid PEG-23) copolymer was used.
  • the face wash of Examples 91 and 92 showed foaming superior to the face wash of Comparative Example 8. This result indicates that the foaming of the fatty acid soap can be improved by setting the content of the (glyceryl diisostearate methacrylate / methoxymethoxy methacrylate-23) copolymer to 0.8 mass% or more.
  • the face wash of Comparative Example 9 had a strong slimy feeling on the skin after face washing.
  • the face wash of Examples 90 to 92 had almost no sliminess after the face washes.
  • the face wash of Examples 90 and 91 is superior to the face wash of Example 92 in that there is no sliminess.
  • the content of the (glyceryl diisostearate methacrylate / methoxymethoxymethacrylate methacrylate-23) copolymer is 3% by mass or less, so that the skin becomes firm after use of the skin cleansing agent without causing a slimy feeling. This shows that the feeling can be reduced.
  • Test Example 5 As in Test Example 4, a skilled evaluator washes the face with a gel cleanser and used the following evaluation criteria to determine the cleansing power, ease of spreading to the skin during use, and lack of skin feeling after washing. (Evaluation criteria for the absence of feeling of tension are the same as in Test Example 4). The results are shown in Table 9. -Detergency ⁇ ... Detergency is very strong ⁇ ... Detergency is strong ⁇ ... Detergency is weak x ...
  • the gel cleansers of Comparative Examples 10 and 11 had a strong feeling of firmness on the skin after the face washes, while the face washes of Examples 93 to 96 had almost no sense of tension after the face washes.
  • the (glyceryl diisostearate methacrylate / methoxymethacrylate methacrylate PEG-23) copolymer reduced the feeling of skin firmness caused by the nonionic surfactant.
  • the gel cleanser of Examples 94 and 95 is superior to the gel cleanser of Example 93 in reducing the feeling of skin tightness after use.
  • the gel cleanser of Examples 93 to 96 is superior in detergency as compared with the gel cleanser of Comparative Examples 10 to 12. This result indicates that the (glyceryl diisostearate methacrylate / methoxy methacrylic acid methoxy PEG-23) copolymer can improve the detergency of a skin cleanser containing a nonionic surfactant. Furthermore, the gel cleanser of Example 95 is superior in detergency compared to the gel cleanser of Examples 93 and 94.
  • the detergency of the skin cleanser containing the nonionic surfactant is improved by setting the content of the (glyceryl diisostearate methacrylate / methoxy methacrylic acid methoxy PEG-23) copolymer to 2% by mass or more. It shows that you can.
  • the gel cleanser of Example 94 is superior in ease of spreading to the skin as compared with the gel cleanser of Examples 93 and 95.
  • the content of the (glyceryl diisostearate methacrylate / methoxy methacrylic acid methoxy PEG-23) copolymer is set to 0.6 to 3% by mass, thereby improving the ease of spreading to the skin when using the gel cleanser. It shows that it can be improved.
  • the gel cleanser of Example 91 and the gel cleanser of Example 93 have the same nonionic surfactant content, but are of different types.
  • these two types of gel face wash showed the same effect in terms of detergency, ease of spreading on the skin, and no feeling of tension.
  • This result shows that the advantageous effect of including the (glyceryl diisostearate methacrylate / methoxymethoxy methacrylate-23) copolymer in the skin cleanser does not depend on the type of surfactant contained in the skin cleanser. Show.
  • Test Examples 4 and 5 indicate that according to the present invention, it is possible to reduce the firmness of the skin after using the skin cleanser.
  • the present invention after use while improving or improving the advantageous effects inherent to the skin cleanser such as good foaming, creamy foam quality, detergency, and ease of spreading to the skin. It shows that the feeling of tightness of the skin can be reduced.
  • oil-in-water sunscreen cosmetics of Examples 98 to 103 and Comparative Examples 13 to 15 were produced by the following method.
  • (A) was mixed and dissolved by heating to prepare a mixture of oil phase components, and dispersed with hydrophobized fine particles of titanium oxide using a disper.
  • (A) was added to the heated (I) and emulsified with a homogenizer.
  • sunscreen cosmetics were produced by adding (c) and (d) and cooling with stirring and mixing.
  • glyceryl diisostearate methacrylate which is a hydrophobic monomer
  • methoxy methacrylic acid methacrylate PEG-23 which is a hydrophilic monomer
  • the oil-in-water sunscreen cosmetics of Examples 97 to 102 containing all the components (A) to (D) have good emulsification stability, no stickiness, and moisturizing feeling. Had.
  • the sunscreen cosmetic of Comparative Example 13 that does not contain the component (A) was quite sticky.
  • the sunscreen cosmetics of the comparative example 14 which does not contain a component (B), and the sunscreen cosmetics of the comparative example 15 which does not contain a component (C) were inferior in emulsion stability.
  • the sunscreen cosmetic of Example 97 containing sodium stearyl lactate as the component (C) is compared with the sunscreen cosmetic of Example 100 containing sodium cocoglyceryl sulfate as the component (C). And excellent in emulsion stability.
  • This result has shown that the oil-in-water type sunscreen cosmetics which contain sodium acyl lactate as a component (C) are excellent in emulsification stability.
  • the sunscreen cosmetic of Example 97 containing polyglycerin-10 pentastearate as the component (B) has the composition of Example 101 containing polyglyceryl tristearate as the component (B).
  • Emulsification stability is superior compared to sunscreen cosmetics. This result shows that the oil-in-water sunscreen cosmetic containing polyglycerin-10 pentastearate as the component (B) is excellent in emulsion stability.
  • the sunscreen cosmetics of Example 97 containing sodium polyacrylate-coated fine particle titanium dioxide as the ultraviolet scattering agent of component (D) are those of Example 102 not containing the coated fine particle titanium dioxide. Excellent moisturizing feeling compared to sunscreen cosmetics.
  • an oil-in-water sunscreen cosmetic containing an ultraviolet scattering agent surface-treated with sodium polyacrylate as the component (D), that is, a water-dispersible ultraviolet scattering agent has an excellent moisturizing feeling. It is shown that.
  • the sunscreen cosmetic of Example 102 is more stable in emulsification than the sunscreen cosmetics of Example 98 and Example 99, in which the content of component (B) is 0.3% by mass and 7% by mass, respectively. It is excellent in the property and the absence of stickiness.
  • the content of the component (B) is preferably 0.5% by mass or more from the viewpoint of improving the emulsion stability, and is preferably 5% by mass or less from the viewpoint of suppressing stickiness. It is shown that.
  • the sunscreen cosmetics of Example 97 are compared with the sunscreen cosmetics of Example 98 and Example 99 in which the content of the component (C) is 0.05% by mass and 1.5% by mass, respectively. Excellent emulsification stability and no stickiness.
  • the content of the component (C) is preferably 0.07% by mass or more from the viewpoint of improving the emulsion stability, and is preferably 1% by mass or less from the viewpoint of suppressing stickiness. It is shown that.
  • amphiphilic copolymer an average molecular weight obtained by copolymerizing glyceryl diisostearate methacrylate, which is a hydrophobic monomer, and methoxy PEG-23 methacrylate, which is a hydrophilic monomer, at a molar ratio of approximately 3: 7. 61,000 (glyceryl diisostearate methacrylate / methoxy methacrylic acid PEG-23) copolymer was used.
  • a fluorescent probe “NBD-COCl” was chemically introduced to facilitate observation of the sea-island structure with a microscope (glyceryl diisostearate methacrylate / methoxy methacrylic acid PEG-23).
  • a composition was prepared using the copolymer.
  • Example 7 Observation of the sea-island structure of the coating About 0.5 g of the composition of Examples 103 to 123 was applied to a range of about 1.5 cm ⁇ 1.5 cm on a slide glass and left at 40 ° C. for 3 days. A film was formed on the slide glass by evaporating the water in the composition. The structures of the coatings of Examples 103 to 123 thus formed were observed with a confocal laser scanning microscope. As a result, each composition formed a sea-island structure.
  • FIG. 6 shows micrographs of the compositions of Examples 105, 106, 108, 111, 113, 114, 115, 119, 120, 122, and 123.
  • Example 8 Sensory evaluation For the film formed on the skin after the composition of Example 103 was used by 48 evaluators and applied to the skin, a moist feeling, a feeling of elasticity, a soft feeling, a soft feeling, a plump The feeling and stickiness were evaluated on a 7-point scale as shown in FIG.
  • commercially available lotions and emulsions were used for comparison. The results are shown in FIG.
  • a lotion the general thing containing water mainly and containing a polyol, a known water-soluble polymer, antiseptic
  • As the emulsion an oil-in-water emulsified cosmetic containing mineral oil, macadamia nut oil and the like as an oil phase component was used.
  • the coating film formed by the composition of Example 103 had a remarkably low stickiness as compared with the emulsion, and was similar to the lotion.
  • composition of the present invention is mainly composed of an aqueous component
  • a film having a milk-like feel can be formed on the skin.
  • the composition of the present invention shows that it is possible to achieve both moisture retention and flexibility, which is difficult to achieve with cosmetics mainly composed of water-soluble ingredients. Further, this result shows that since the composition of the present invention is mainly composed of an aqueous component, there are few disadvantages such as stickiness seen in cosmetics containing an oil agent.
  • the coating film formed by the compositions of Examples 124 and 125 was observed with a microscope in the same manner as in Test Example 8. As a result, as in the coating films of Examples 103 to 114, no aggregation of island particles was observed, and the number particle size distribution of fine island particles having an average particle diameter of 1 to 5 ⁇ m was 80% or more. This result shows that even when polyquaternium-61 and (glyceryl amidoethyl methacrylate / stearyl methacrylate) copolymer are used as the amphiphilic copolymer, a film having a good sea-island structure can be formed. Yes.
  • copolymer of the present invention that solves the first problem can be applied to cosmetics.
  • the present invention for solving the second problem can be applied to emulsified cosmetics.
  • the present invention that solves the third and fourth problems can be applied to a facial cleanser.
  • the present invention that solves the fifth problem can be applied to sunscreen cosmetics.
  • the present invention that solves the sixth problem can be applied to oil-free cosmetics.
  • Example 103 Example 104 3
  • Example 105 4 Example 106 5
  • Example 107 6 Example 108 7
  • Example 109 8 Example 110 9
  • Example 111 10 Example 112 11
  • Example 113 12 Example 114 13
  • Example 115 14 Example 116 15
  • Example 117 16 Example 118 17
  • Example 119 18 Example 120 19
  • Example 121 20 Example 122 21

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