WO2023033127A1 - Emulsion composition, and skin topical agent and cosmetic containing said composition - Google Patents

Emulsion composition, and skin topical agent and cosmetic containing said composition Download PDF

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Publication number
WO2023033127A1
WO2023033127A1 PCT/JP2022/033044 JP2022033044W WO2023033127A1 WO 2023033127 A1 WO2023033127 A1 WO 2023033127A1 JP 2022033044 W JP2022033044 W JP 2022033044W WO 2023033127 A1 WO2023033127 A1 WO 2023033127A1
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group
component
mass
compound
emulsified composition
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PCT/JP2022/033044
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French (fr)
Japanese (ja)
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歌穂 森
秋穂 大森
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富士フイルム和光純薬株式会社
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Publication of WO2023033127A1 publication Critical patent/WO2023033127A1/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/32—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers, poly(meth)acrylates, or polyvinyl pyrrolidone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/44—Oils, fats or waxes according to two or more groups of A61K47/02-A61K47/42; Natural or modified natural oils, fats or waxes, e.g. castor oil, polyethoxylated castor oil, montan wax, lignite, shellac, rosin, beeswax or lanolin
    • 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
    • A61K8/18—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
    • A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/10—Dispersions; Emulsions
    • A61K9/107—Emulsions ; Emulsion preconcentrates; Micelles
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00—Drugs for dermatological disorders
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/52—Natural or synthetic resins or their salts

Definitions

  • the present invention relates to an emulsified composition, an external preparation for skin and a cosmetic containing the composition.
  • oil-in-water (O/W) emulsified compositions in which oil droplets are dispersed in water are widely used as emulsions, gel creams, etc., as formulations with high added value.
  • the moist and rich feeling after application (spreading) which is a characteristic touch of emulsion compositions, is imparted by the oily component, and the degree of richness depends on the type of oily component and the balance between the oily component and the emulsifier. It is determined.
  • the (perfluorohexylethyl acrylate/acrylic acid) crosspolymer described in International Publication No. 2017/170961 has the characteristic of being able to maintain high viscosity even in the presence of an electrolyte.
  • the present invention has been made in view of the above-mentioned situation, and has both a fresh feeling when applied and a rich feeling after application (spreading) as a feeling of use, and an oil-in-water type (O) that can coexist with electrolytes in the composition. /W).
  • the present inventors have made intensive studies on such emulsified compositions. We found that by adjusting the blending ratio of the polymer and the oily component and the blending amount of the oily component in the emulsified composition, it is possible to improve the disintegration of the oil droplets during application, thereby providing an emulsified composition with a desired feeling of use. , have completed the present invention.
  • the present invention consists of the following configurations.
  • An oil-in-water (O/W) emulsified composition containing an oily component in emulsified particles, wherein the emulsified composition contains a component A and an oily component, and the content of the component A is It is 0.4 to 250% by mass with respect to the oily component, and the emulsified composition does not substantially contain a surfactant, or when it contains a surfactant, the content of the surfactant is 90% by mass or less of the component A and 3% by mass or less of the oily component, and the content of the oily component in the emulsion composition is 1 to 65% by mass. thing.
  • O/W oil-in-water
  • the surfactant is an anionic surfactant or a nonionic surfactant, and the content of the anionic surfactant or nonionic surfactant is 30% relative to the component A;
  • oily component is at least one selected from the group consisting of hydrocarbons, ester oils, higher alcohols, silicone oils, waxes and animal and vegetable oils.
  • the emulsified composition according to any one of.
  • the emulsified composition of the present invention is an oil-in-water oil that has excellent stability over time in a uniform emulsified state and a glossy appearance, and has both a high freshness when applied to the skin and a moist and rich feeling after application (spreading). It is an emulsion composition of the type (O/W).
  • the external skin preparations and cosmetics containing the emulsified composition of the present invention are excellent in the stability of the emulsified state over time, have a glossy appearance, and have freshness and richness when used. be.
  • the emulsified composition of the present invention is an oil-in-water (O/W) emulsified composition containing an oily component in emulsified particles, comprising component A and an oily component, wherein the content of component A is It is 0.4 to 250% by mass with respect to the oily component, and the emulsified composition does not substantially contain a surfactant, or when it contains a surfactant, the content of the surfactant is 90% by mass or less of component A and 3% by mass or less of the oily component, and the content of the oily component in the emulsion composition is 1 to 65% by mass. is.
  • O/W oil-in-water
  • component A according to the present invention acrylic acid ester (a) / compound (b) copolymer-
  • the component A according to the present invention that is, the copolymer according to the present invention is at least the acrylic ester (a)-derived structural unit and the compound, which are composed of the acrylic ester (a) and the compound (b). It means a copolymer having structural units derived from (b).
  • the acrylic acid ester (a)/compound (b) copolymer comprises an acrylic acid ester represented by the above general formula [1], a polymerizable unsaturated group, a carboxyl group, a sulfo group and a phosphorus
  • the alkyl group having 1 to 6 carbon atoms represented by R 1 in general formula [1] is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 carbon atom.
  • the alkyl group may be linear, branched or cyclic, with linear or branched being preferred.
  • alkyl groups include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, cyclopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, 2-methylpentyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, cyclohexyl group,
  • a hydrogen atom is preferable as R 1 in the general formula [1].
  • n in the general formula [1] is preferably an integer of 2 to 3, more preferably 2.
  • acrylic acid ester represented by the general formula [1] include perfluorohexylethyl (meth)acrylate, perfluorohexylpropyl (meth)acrylate, and perfluoro(meth)acrylate. Hexyl butyl etc. are mentioned. These acrylic acid esters may be commercially available ones, or may be appropriately synthesized by a method known per se.
  • (meth)acrylic acid means acrylic acid and/or methacrylic acid. The same applies to (meth)acrylic acid esters and (meth)acrylic acid salts.
  • perfluorohexylethyl (meth)acrylate is preferred, and perfluorohexylethyl acrylate is more preferred.
  • a compound having a polymerizable unsaturated group and any functional group selected from the group consisting of a carboxyl group, a sulfo group and a phosphoric acid group in the molecule is, for example, a carbon-carbon double bond, a carbon - A compound having a polymerizable unsaturated group such as a carbon triple bond and any functional group selected from the group consisting of a carboxyl group, a sulfo group and a phosphoric acid group in the molecule, wherein the polymerizable unsaturated group is a compound that reacts with the acrylic acid ester represented by the general formula [1] to form an acrylic acid ester (a)/compound (b) copolymer.
  • Specific examples of such compound (b) include compounds represented by general formulas [2] to [5].
  • the alkyl group having 1 to 6 carbon atoms represented by R 2 to R 5 in general formulas [2] to [5] is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 carbon atom.
  • the alkyl group may be linear, branched or cyclic, with linear or branched being preferred. Specific examples of such an alkyl group include the same groups as specific examples of the alkyl group having 1 to 6 carbon atoms represented by R 1 in general formula [1], and preferred specific examples and more preferred specific examples are also given. are identical.
  • Hydrogen atoms are preferred as R 2 to R 5 in general formulas [2] to [5].
  • An oxygen atom is preferable as A in the general formula [3].
  • the alkylene group having 1 to 6 carbon atoms which may have a hydroxyl group represented by T 1 in the general formula [3] is an alkylene group having 1 to 4 carbon atoms which may have a hydroxyl group.
  • the alkylene group may be linear, branched or cyclic, with linear or branched being preferred.
  • the number of hydroxyl groups may be one or more.
  • alkylene group optionally having a hydroxyl group include, for example, a methylene group, a hydroxymethylene group, a dimethylene group (ethylene group), a hydroxydimethylene group (hydroxyethylene group), a trimethylene group, -hydroxytrimethylene group, 2-hydroxytrimethylene group, isopropylene group, hydroxyisopropylene group, tetramethylene group, hydroxytetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1,1-dimethyl dimethylene group, cyclobutylene group, pentamethylene group, cyclopentylene group, hexamethylene group, cyclohexylene group and the like.
  • alkylene groups which may have a hydroxyl group, a dimethylene group (ethylene group), a trimethylene group, a 2-hydroxytrimethylene group and a 1,1-dimethyldimethylene group are preferred.
  • the bond represented by T 2 in the general formula [4] is a “sulfur atom” that does not have an atom in T 2 and is bonded to T 2 , and a “R 4 "bonded carbon atom” means directly bonded without going through T2 .
  • the alkylene group having 1 to 6 carbon atoms represented by T 2 in general formula [4] is preferably an alkylene group having 1 to 4 carbon atoms, and more preferably an alkylene group having 1 carbon atom.
  • the alkylene group may be linear, branched or cyclic, with linear ones being preferred.
  • Specific examples of such alkylene groups include, for example, methylene group, dimethylene group (ethylene group), trimethylene group, isopropylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1, 1-dimethyldimethylene group, cyclobutylene group, pentamethylene group, cyclopentylene group, hexamethylene group, cyclohexylene group and the like.
  • straight-chain alkylene groups having 1 to 4 carbon atoms are preferred, and methylene groups are more preferred.
  • the alkylene group having 1 to 6 carbon atoms represented by T 3 in general formula [5] is preferably an alkylene group having 1 to 4 carbon atoms, and more preferably an alkylene group having 2 carbon atoms. Further, the alkylene group may be linear, branched or cyclic, with linear ones being preferred. Specific examples of such an alkylene group include the same groups as the specific examples of the alkylene group having 1 to 6 carbon atoms represented by T 2 in general formula [4]. Among these alkylene groups, a linear alkylene group having 1 to 4 carbon atoms is preferable, and a dimethylene group (ethylene group) is more preferable.
  • Specific examples of the compound represented by general formula [2] include acrylic acid and methacrylic acid.
  • Specific examples of the compound represented by the general formula [3] include 2-(acryloyloxy)ethanesulfonic acid, 2-(methacryloyloxy)ethanesulfonic acid, 3-(acryloyloxy)propanesulfonic acid, 3-( methacryloyloxy)propanesulfonic acid, 2-acryloyloxy-2-methylpropanesulfonic acid, 2-methacryloyloxy-2-methylpropanesulfonic acid, 3-acryloyloxy-2-hydroxypropanesulfonic acid, 3-methacryloyloxy-2- Hydroxypropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid and the like.
  • Specific examples of the compound represented by general formula [4] include vinylsulfonic acid, allylsulfonic acid, and the like.
  • Specific examples of the compound represented by general formula [5] include 2-(acryloyloxy)ethyl phosphate, 2-(methacryloyloxy)ethyl phosphate, and the like.
  • the compounds represented by the general formula [2] are preferred, acrylic acid and methacrylic acid are more preferred, and acrylic acid is even more preferred.
  • These compounds (b) may be commercially available ones, or may be appropriately synthesized by a method known per se.
  • the ratio (mass ratio) of the acrylic acid ester (a) and the compound (b) is less than 6.0/94.0, sufficient viscosity is obtained in the presence of the electrolyte when the emulsified composition is prepared. It may become difficult to use without obtaining it. Further, when the ratio (mass ratio) of the acrylic acid ester (a) and the compound (b) exceeds 30.0/70.0, when the emulsified composition is prepared, a low concentration (for example, 0.5%) is obtained.
  • a high viscosity for example, 2 to 5% by mass
  • the emulsion composition containing the copolymer (component A) according to the present invention contains a high concentration (for example, 2 to 5% by mass) of the electrolyte It can be suitably used for external skin preparations and cosmetics in which
  • the emulsified composition containing the copolymer (component A) according to the present invention is characterized by high viscosity and is used as an external skin preparation or cosmetic. It can be suitably used for
  • the ratio (molar ratio) of the acrylic acid ester (a) and the compound (b) is less than 1.1/98.9, when the emulsified composition is prepared, sufficient viscosity is obtained in the presence of the electrolyte. It may become difficult to use without obtaining it.
  • the ratio (molar ratio) of the acrylic acid ester (a) and the compound (b) exceeds 6.9/93.1
  • a low concentration for example, 0.1
  • the viscosity increase significantly in the presence of an electrolyte (5% by mass or less)
  • the concentration of the electrolyte increases, the viscosity decreases rapidly, and the viscosity changes greatly depending on the concentration of the electrolyte, making it difficult to use.
  • the emulsion composition containing the copolymer (component A) according to the present invention in which the ratio (molar ratio) of the compound (b) and the compound (b) is within the range described above, has a high concentration (for example, 2 to 5% by mass) of the electrolyte It can be suitably used for external skin preparations and cosmetics in which
  • a higher viscosity is likely to be maintained in the presence of a high-concentration (for example, 2 to 5% by mass) electrolyte, so the acrylic acid ester (a ) and the compound (b) in the ratio (molar ratio) of the present invention is within the range described above (component A). It can be suitably used for
  • the copolymer according to the present invention may further contain (c) a compound having two or more ethylenically unsaturated groups as a constituent component, in addition to the acrylic acid ester (a) and the compound (b). That is, the copolymer according to the present invention further containing the compound (c) is at least the acrylic ester (a)-derived copolymer having the acrylic ester (a), the compound (b), and the compound (c) as constituent components. and a structural unit derived from the compound (b) and a structural unit derived from the compound (c).
  • an acrylic ester (a)/compound (b)/compound (c) copolymer further containing (c) a compound having two or more ethylenically unsaturated groups as a constituent component is preferred.
  • the compound having two or more ethylenically unsaturated groups is a compound having two or more ethylenically unsaturated groups in the molecule that can react with the acrylic acid ester (a) and the compound (b), It is a compound that plays the role of a so-called cross-linking agent.
  • Specific examples of such compound (c) include compounds represented by general formulas [6] to [16].
  • k in the general formula [6] is preferably an integer of 1 to 4, more preferably 1.
  • a hydrogen atom is preferable as R 6 and R 6′ in general formula [7].
  • the alkylene group having 1 to 20 carbon atoms represented by T 4 in general formula [7] is preferably an alkylene group having 1 to 10 carbon atoms. Further, the alkylene group may be linear, branched or cyclic, with linear ones being preferred.
  • alkylene groups include, for example, methylene group, dimethylene group (ethylene group), trimethylene group, isopropylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1, 1-dimethyldimethylene group, cyclobutylene group, pentamethylene group, cyclopentylene group, hexamethylene group, cyclohexylene group, heptamethylene group, cycloheptylene group, octamethylene group, cyclooctylene group, nonamethylene group, cyclononylene group, decamethylene group, cyclodecylene group, undecamethylene group, cycloundecylene group, dodecamethylene group, cyclododecylene group, tridecamethylene group, cyclotridecylene group, tetradecamethylene group, cyclotetradecylene group, pentadecamethylene group, cyclopenta decylene group, hexamethylene
  • the alkylene group having 1 to 6 carbon atoms represented by T 4 ' in general formula [7-1] and T 4 '' and T 4 '' in general formula [7-2] includes Alkylene groups are preferred. Further, the alkylene group may be linear, branched or cyclic, with linear ones being preferred. Specific examples of such an alkylene group include the same groups as the specific examples of the alkylene group having 1 to 6 carbon atoms represented by T 2 in general formula [4]. Among these alkylene groups, straight-chain alkylene groups having 1 to 3 carbon atoms are preferred.
  • p in the general formula [7-1] is preferably an integer of 2 to 6, more preferably an integer of 4 to 6.
  • p' in general formula [7-2] is preferably an integer of 1 to 7, more preferably an integer of 1 to 5, and even more preferably an integer of 1 to 3.
  • the alkylene groups having 1 to 3 carbon atoms represented by T 5 , T 5 ', T 5 '', T 6 , T 6 ', T 6 '' and T 7 in the general formula [8] include Alkylene groups are preferred.
  • the alkylene group may be linear or branched, with linear ones being preferred. Specific examples of such an alkylene group include, for example, a methylene group, a dimethylene group (ethylene group), a trimethylene group, an isopropylene group and the like. Among these alkylene groups, a methylene group is preferred.
  • the alkylene group having 1 to 6 carbon atoms represented by T 8 , T 8 ', T 9 and T 9 ' in the general formula [9] is preferably an alkylene group having 1 to 3 carbon atoms, and an alkylene group having 1 carbon atom. is more preferred. Further, the alkylene group may be linear, branched or cyclic, with linear ones being preferred. Specific examples of such an alkylene group include the same groups as the specific examples of the alkylene group having 1 to 6 carbon atoms represented by T 2 in general formula [4]. Among these alkylene groups, T 8 and T 8 ' are preferably methylene groups, and T 9 and T 9 ' are preferably linear alkylene groups having 1 to 3 carbon atoms.
  • At least two of R 7 to R 14 in general formula [10] may be vinyl groups or vinylcarbonyl groups, preferably 5 to 8 are vinyl groups or vinylcarbonyl groups, and 5 to 7 are vinyl groups or A vinyl carbonyl group is more preferred.
  • the alkylene group having 1 to 6 carbon atoms represented by T 10 , T 11 and T 11 ′ in general formula [11] may be linear, branched or cyclic. Specific examples of such an alkylene group include the same groups as the specific examples of the alkylene group having 1 to 6 carbon atoms represented by T 2 in general formula [4].
  • T 10 is preferably a cyclopentylene group and a cyclohexylene group, more preferably a cyclohexylene group
  • T 11 and T 11 ' are a methylene group and a dimethylene group ( ethylene group) is preferred, and a methylene group is more preferred.
  • aromatic hydrocarbon groups include, for example, a divalent aromatic hydrocarbon group (arylene group) having 6 to 10 carbon atoms such as a phenylene group and a naphthylene group; aromatic hydrocarbon group; benzene, tetravalent aromatic hydrocarbon group derived from naphthalene, and the like.
  • the alkylene group having 1 to 6 carbon atoms represented by T 12 in general formula [12] is preferably an alkylene group having 1 to 3 carbon atoms.
  • the alkylene group may be linear, branched or cyclic, and preferably linear. Specific examples of such an alkylene group include the same groups as the specific examples of the alkylene group having 1 to 6 carbon atoms represented by T 2 in general formula [4]. Among these alkylene groups, straight-chain alkylene groups having 1 to 3 carbon atoms are preferred.
  • the alkylene group having 1 to 6 carbon atoms represented by T 13 in the general formula [13] is preferably an alkylene group having 1 to 3 carbon atoms.
  • the alkylene group may be linear, branched or cyclic, and preferably linear. Specific examples of such an alkylene group include the same groups as the specific examples of the alkylene group having 1 to 6 carbon atoms represented by T 2 in general formula [4]. Among these alkylene groups, straight-chain alkylene groups having 1 to 3 carbon atoms are preferred.
  • an arylene group having 6 carbon atoms is preferred.
  • Specific examples of such arylene groups include, for example, a phenylene group and a naphthylene group. Among these arylene groups, a phenylene group is preferred.
  • v in general formula [15] is preferably an integer of 0 to 2, more preferably 0.
  • the alkylene group having 1 to 6 carbon atoms represented by T 16 in general formula [16] is preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an alkylene group having 1 carbon atom.
  • the alkylene group may be linear, branched or cyclic, and preferably linear. Specific examples of such an alkylene group include the same groups as the specific examples of the alkylene group having 1 to 6 carbon atoms represented by T 2 in general formula [4]. Among these alkylene groups, straight-chain alkylene groups having 1 to 3 carbon atoms are preferred, and methylene groups are more preferred.
  • Specific examples of the compound represented by general formula [7] include 1,10-decanediol diacrylate.
  • dialkylene glycol diallyl ether such as diethylene glycol diallyl ether, dipropylene glycol diallyl ether, and dibutylene glycol diallyl ether; triethylene glycol diallyl ether, tripropylene glycol diallyl. ether, trialkylene glycol diallyl ether such as tributylene glycol diallyl ether; polyalkylene glycol diallyl ether such as polyethylene glycol diallyl ether, polypropylene glycol diallyl ether, polybutylene glycol diallyl ether;
  • Specific examples of the compound represented by general formula [16] include N,N'-methylenebisacrylamide and the like.
  • 1,10-decanediol diacrylate, pentaerythritol triallyl ether, diethylene glycol diallyl ether and N, N'-methylenebisacrylamide is preferred, and diethylene glycol diallyl ether is more preferred.
  • These compounds (c) may be commercially available ones, or may be appropriately synthesized by a method known per se.
  • the ratio of the compound (c) in the copolymer according to the present invention is usually 0.0001 to 1.5 parts by mass, preferably 100 parts by mass in total of the acrylic acid ester (a) and the compound (b). is 0.02 to 1.5 parts by mass, more preferably 0.04 to 1.25 parts by mass, still more preferably 0.05 to 1.01 parts by mass, most preferably 0.20 to It is 0.70 parts by mass.
  • the total amount of acrylic acid ester (a) and compound (b) is 100 parts by mass, and the amount of compound (c) used exceeds 1.5 parts by mass with respect to 100 parts by mass, the emulsified composition When preparing a product, it may not be possible to obtain sufficient viscosity in the presence of an electrolyte, making it difficult to use.
  • the ratio of the compound (c) in the copolymer according to the present invention is within the range of 0.05 to 1.01 parts by mass with respect to a total of 100 parts by mass of the acrylic acid ester (a) and the compound (b).
  • the high viscosity (for example, 2 to 5% by mass) of the electrolyte is likely to be maintained in the presence of a high concentration, so the proportion of the compound (c) is the above-mentioned parts by mass.
  • Emulsified compositions containing the copolymer (component A) according to the present invention within the range can be suitably used for external skin preparations and cosmetics in which high concentration (for example, 2 to 5% by mass) electrolytes coexist. can.
  • the ratio of the compound (c) in the copolymer according to the present invention is within the range of 0.20 to 0.70 parts by mass with respect to the total 100 parts by mass of the acrylic acid ester (a) and the compound (b).
  • a higher viscosity is likely to be maintained in the presence of a high-concentration (for example, 2 to 5% by mass) electrolyte, so the proportion of the compound (c) is the above parts by mass.
  • the emulsion composition containing the copolymer (component A) according to the present invention within the range of can be suitably used for external skin preparations and cosmetics characterized by high viscosity.
  • the ratio of the compound (c) in the copolymer according to the present invention is usually 0.00005 to 1.0 mol, preferably 0, per 100 mol in total of the acrylic acid ester (a) and the compound (b). 0.0005 to 0.70 mol, more preferably 0.0005 to 0.60 mol, still more preferably 0.0005 to 0.50 mol, most preferably 0.05 to 0.30 mol. be.
  • the total amount of acrylic acid ester (a) and compound (b) is 100 mol
  • the amount of compound (c) used exceeds 1.0 mol per 100 mol, an emulsified composition is prepared.
  • sufficient viscosity may not be obtained, making it difficult to use.
  • the ratio of compound (c) is preferably 0.00005 to 0.70 mol, more preferably 0.0005 to 0 0.70 mol, more preferably 0.0005 to 0.50 mol, particularly preferably 0.0005 to 0.40 mol, most preferably 0.0005 to 0.30 mol.
  • the copolymer according to the present invention may contain compound (d) as a constituent component other than acrylic acid ester (a), compound (b) and compound (c) described above. That is, the copolymer according to the present invention may be an acrylic acid ester (a)/compound (b)/compound (c)/compound (d) copolymer.
  • Examples of such compound (d) include those other than acrylate (a), compound (b) and compound (c), and include, for example, carbon-carbon double bonds, carbon-carbon triple bonds, and other polymerizable A compound having an unsaturated group in the molecule, wherein the polymerizable unsaturated group can react with the polymerizable unsaturated group in the acrylic acid ester (a), the compound (b), or the compound (c) is a compound.
  • Specific examples of such compound (d) include (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate. These compounds (d) may be commercially available ones, or may be appropriately synthesized by a method known per se.
  • the carboxyl group, sulfo group or phosphoric acid group in the structural unit derived from compound (b) may be neutralized with an alkaline compound. That is, copolymers in which the carboxyl group, sulfo group or phosphoric acid group in the constituent units derived from compound (b) are in the form of salts are also included in the copolymers of the present invention.
  • the degree of neutralization of the copolymer of the present invention is usually 0-100%, preferably 30-100%, more preferably 60-100%.
  • neutralization degree refers to the degree to which acid groups (carboxyl groups, sulfo groups or phosphoric acid groups) in the copolymer are neutralized by an alkaline compound. 100% is defined as the case where all the acid groups in the copolymer are neutralized with an alkaline compound to form a salt.
  • alkaline compound is not particularly limited as long as it can neutralize an acid group, and examples thereof include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; magnesium hydroxide and calcium hydroxide.
  • alkaline earth metal hydroxides such as; amines such as amine, tromethamine, cocamidemethylmonoethanolamine; and ammonia.
  • alkali metal hydroxides are preferred, and sodium hydroxide is more preferred.
  • component A one type of copolymer may be used alone in the emulsion composition, or two or more types of copolymers may be used in combination.
  • Copolymers according to the present invention that have the following properties are useful. 1% by mass of acrylic ester (a) / compound (b) copolymer and 2% by mass of magnesium phosphate-L-ascorbyl n-hydrate (moisture content: 16 to 20% by mass), pH is 7.5, the viscosity at 20° C. is 9,000 mPa ⁇ s or more.
  • the copolymer according to the present invention is composed of (a) an acrylic acid ester represented by the general formula [1], and (b) a polymerizable unsaturated group, a carboxyl group, a sulfo group, and a phosphoric acid group.
  • a compound having any selected functional group in the molecule if necessary, (c) a compound having two or more ethylenically unsaturated groups as monomers, each monomer being acrylic acid
  • the proportion of the compound (c) is obtained by polymerizing so that it is 0.0001 to 1.5 parts by mass with respect to a total of 100 parts by mass of the acrylic acid ester (a) and the compound (b).
  • acrylic acid ester (a)/compound (b) copolymers having the properties described above are preferred.
  • the viscosity was measured using a B-type rotational viscometer and rotor No. 4 at a temperature of 20° C. and a rotation speed of 3 rpm.
  • Viscosity at 20° C. of pH 7.5 aqueous solution containing 1% by mass of the copolymer of the present invention and 2% by mass of L-ascorbylmagnesium phosphate n-hydrate is preferably 9,000 mPa s or more, more preferably 11,000 mPa s or more, even more preferably 13,000 mPa s or more, and 15,000 mPa s or more. It is particularly preferred, and most preferably 17,000 mPa ⁇ s or more.
  • the upper limit of the viscosity may vary depending on the application of the emulsion composition containing the copolymer (component A) of the present invention, but is, for example, 200,000 mPa ⁇ s or less. Since the copolymer according to the present invention has such properties, when an emulsified composition containing the copolymer according to the present invention (component A) is blended into a cosmetic, the viscosity can be increased with a small addition amount, and the feeling of use is improved. A cosmetic having excellent applicability and a unique feel can be obtained.
  • a high concentration for example, 2 to 5% by mass
  • electrolyte the copolymer according to the present invention
  • component A The emulsified composition containing can be used in various cosmetics formulated with a high concentration (eg, 2 to 5% by mass) of electrolyte.
  • copolymer (component A) according to the present invention has such properties is not clear, but it is due to the use of a specific amount of (a) acrylic acid ester represented by general formula [1]. It is presumed that The fluorine atoms in the acrylic acid ester (a) in the copolymer according to the present invention form associations between polymer chains due to electrostatic interaction with the electrolyte in an aqueous solution, thereby increasing the viscosity and increasing the electrolyte It is presumed that the effect of viscosity reduction due to is reduced.
  • the method for producing the above-described copolymer according to the present invention is not particularly limited.
  • an acrylic ester represented by the general formula [1] (b) a polymerizable unsaturated group, (c) a compound having two or more ethylenically unsaturated groups, and optionally a compound (d ) are stirred in a solvent under an inert gas atmosphere and polymerized using a polymerization initiator to produce the copolymer of the present invention.
  • the copolymer according to the present invention can be produced by the method described in International Publication No. WO2017/170961.
  • Examples of the method for neutralizing the copolymer according to the present invention include methods commonly performed in this field using the above-described alkaline compound.
  • the oily component according to the present invention is not particularly limited as long as it is an oily substance capable of forming an oil-in-water (O/W) emulsified composition.
  • Semi-solid oil, liquid oil, volatile oil, etc. can be used regardless of properties.
  • oily substances that can be blended in external skin preparations and cosmetics are preferred.
  • Specific examples of such oily components include hydrocarbons, ester oils, higher alcohols, fatty acids, silicone oils, waxes, and animal and vegetable oils.
  • hydrocarbons include liquid paraffin, liquid isoparaffin, olefin oligomer, squalane, olive squalane, rice squalane, dioctylcyclohexane, polybutene, hydrogenated polyisobutene, isododecane, isohexadecane, ozokerite, pristane, paraffin wax, and ceresin. wax, microcrystalline wax, petrolatum, polyethylene wax, Fischer-Tropsch wax and the like.
  • ester oils include dialkyl carbonate, alkyl benzoate, octyl paramethoxycinnamate, lanolin acetate, cetyl octanoate, cetyl isooctanoate, cetyl 2-ethylhexanoate, 2-ethylhexyl isononanoate, and isononanoic acid.
  • higher alcohols include cetyl alcohol, stearyl alcohol, isostearyl alcohol, and oleyl alcohol.
  • fatty acids include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, behenic acid, undecylenic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, coconut oil fatty acids and the like.
  • silicone oils include dimethylpolysiloxane, methylphenylpolysiloxane, methylcetylpolysiloxane, diphenylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane (cyclomethicone), and dodecamethylcyclohexasiloxane.
  • waxes include, for example, beeswax, high acid value beeswax, carnauba wax, candelilla wax, gay wax, shellac, mink wax, lanolin, liquid lanolin, rice bran wax, Japanese wax, cotton wax, bayberry wax, wart wax, montan wax, kabok wax, and jojo wax. Barlow, sugarcane wax, lanolin fatty acid isopropyl, reduced lanolin, hard lanolin and the like.
  • animal and vegetable oils include avocado oil, linseed oil, almond oil, olive oil, Chinese ginseng oil, sesame oil, rice germ oil, wheat germ oil, germ oil, rice bran oil, safflower oil, soybean oil, and corn oil.
  • jojoba oil macadamia nut oil, cottonseed oil, coconut oil, hydrogenated coconut oil, castor oil, sunflower oil, rapeseed oil, meadowfoam oil, evening primrose oil, shea oil, tall oil, mink oil, camellia oil, persic oil, sasanqua oil, Eno oil, peanut oil, tea seed oil, kaya oil, sinagiri oil, Japanese paulownia oil, palm oil, palm kernel oil, coconut oil, peanut oil, hazelnut oil, walnut oil, grape seed oil, turtle oil, fish oil, etc. Refined oil, hardened (hydrogenated) oil, and the like can be mentioned.
  • oily components one type of oily component may be used alone, or two or more types of oily components may be used in combination.
  • commercially available products may be used as these oily components.
  • hydrocarbons, ester oils, higher alcohols, silicone oils, waxes, and animal and vegetable oils that are liquid at room temperature are preferred.
  • hydrocarbons, ester oils, higher alcohols, silicone oils, waxes, and animal and vegetable oils that are liquid at room temperature are preferred.
  • the oil-in-water (O/W) emulsion composition of the present invention comprises water.
  • water is not particularly limited as long as it is used for external skin preparations and cosmetics. Water etc. are mentioned.
  • the content of the component A according to the present invention in the emulsion composition that is, the content of the copolymer according to the present invention in the emulsion composition is not particularly limited as long as the desired effect is exhibited.
  • the content of component A is preferably 0.1% by mass or more from the viewpoint of the emulsifying effect of the oily component, and the content of component A is 5% by mass or less from the viewpoint of obtaining a good feeling during use. is preferred.
  • the content of the oily component according to the present invention in the emulsified composition is usually 1-65% by mass, preferably 4-65% by mass, more preferably 6-50% by mass. From the viewpoint of the luster and richness of the emulsified composition, the content of the oily component is preferably 1% by mass or more. The amount is preferably 65 mass % or less.
  • the content of Component A relative to the oily component in the emulsified composition is usually 0.4-250% by mass, preferably 0.6-120% by mass, more preferably 1-90% by mass, still more preferably 1-10% by mass. % by mass. From the viewpoint that the emulsion composition can maintain a uniform state without separation, the content of component A relative to the oily component is preferably 0.4% by mass or more, and from the viewpoint of gloss and richness of the emulsion composition. , the content of component A with respect to the oil component is preferably 250% by mass or less.
  • the content of water in the emulsified composition may be such that the content of component A and the oily component is in the range described above, usually 1 to 99.9% by mass, preferably 10 to 95.9%. % by mass, more preferably 30 to 95.9% by mass.
  • a uniform oil-in-water (O/W) emulsified composition that has a glossy appearance and a fresh and rich feeling when used by adjusting the contents of the component A and the oil component within the ranges described above. can be obtained.
  • the emulsified composition of the present invention does not substantially contain a surfactant, or if it contains a surfactant, the content of the surfactant is 90% by mass or less with respect to component A, and an oily It is preferably 3% by mass or less with respect to the component.
  • the term "substantially free” means that the emulsified composition of the present invention contains no As the content in the medium, it means less than 0.001% by mass.
  • the surfactant according to the present invention is not particularly limited as long as it is a substance (cationic, anionic, amphoteric, nonionic surfactant) that can be blended in, for example, external skin preparations and cosmetics.
  • Anionic surfactants and nonionic surfactants are preferred.
  • anionic surfactants include sodium polyoxyethylene lauryl ether sulfate, ammonium polyoxyethylene lauryl ether sulfate, triethanolamine polyoxyethylene lauryl ether sulfate, and polyoxyethylene alkyl (C12-13) ether sulfate.
  • Polyoxyethylene alkyl ether sulfates such as sodium, polyoxyethylene alkyl (C12-13) ammonium ether sulfate, polyoxyethylene alkyl (C12-13) ether sulfate triethanolamine; sodium lauryl sulfate, ammonium lauryl sulfate, triethanol lauryl sulfate Alkyl sulfates such as amines; Sodium polyoxyethylene lauryl ether acetate, sodium polyoxyethylene tridecyl ether acetate, sodium polyoxyethylene coconut oil fatty acid acetate and other sodium polyoxyethylene alkyl ether acetates; dioctyl sodium sulfosuccinate, sulfosuccinic acid Disodium Lauryl, Dialkyl Sulfosuccinate, Disodium Lauryl Polyoxyethylene Sulfosuccinate, Disodium Polyoxyethylene Alkyl (C12-13) Sulfosuccinate, Disodium Polyoxyethylene Alky
  • nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene behenyl ether, and polyoxyethylene octyldodecyl ether.
  • polyoxyethylene alkyl ethers such as polyoxyethylene decyltetradecyl ether
  • polyoxyethylenes such as polyoxyethylene polyoxypropylene decyl ether, polyoxyethylene polyoxypropylene cetyl ether, polyoxyethylene polyoxypropylene decyltetradecyl ether
  • Polyoxypropylene alkyl ethers lauric acid monoethanolamide, myristic acid monoethanolamide, palmitic acid monoethanolamide, stearic acid monoethanolamide, isostearic acid monoethanolamide, oleic acid monoethanolamide, coconut oil fatty acid monoethanolamide, etc.
  • lauric acid diethanolamide myristic acid diethanolamide, palmitic acid diethanolamide, stearic acid diethanolamide, isostearic acid diethanolamide, oleic acid diethanolamide, coconut oil fatty acid diethanolamide, palm kernel oil fatty acid diethanolamide, etc.
  • Diethanolamides Isopropanolamides such as lauric acid isopropanolamide, myristate isopropanolamide, palmitic acid isopropanolamide, stearic acid isopropanolamide, isostearic acid isopropanolamide, oleic acid isopropanolamide, coconut oil fatty acid isopropanolamide; polyoxyethylene lauric acid monoethanolamide, polyoxyethylene myristic monoethanolamide, polyoxyethylene palmitic monoethanolamide, polyoxyethylene stearic monoethanolamide, polyoxyethylene isostearic monoethanolamide, polyoxyethylene oleic monoethanolamide, poly Polyoxyethylene monoethanolamides such as oxyethylene coconut oil fatty acid monoethanolamide; Stearylamides such as PPG-2-hydroxyethyl cocoisostearamide; Alkyl glucosides such as capryl glucoside, decyl glucoside and lauryl glucoside; Lauryl dimethyl ah
  • Polyoxyethylene glycerin fatty acid esters Polyoxyethylene castor oils such as polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil; Alkylamidoamines such as diethylaminoethylamide stearate and dimethylaminopropylamide stearate; Polyoxyethylene Polyoxyethylene cholesteryl ethers such as phytosterol; polyoxyethylene lanolin alcohols such as polyoxyethylene lanolin alcohol ether, polyoxyethylene lanolin alcohol acetate, polyoxyethylene hydrogenated lanolin alcohol ether, polyoxyethylene cholesterol ether; polyether modification modified polysiloxanes such as polysiloxane and polyvinylpyrrolidone-modified methylpolysiloxane; sugar derivatives such as maltitol hydroxy fatty acid alkyl ethers, alkylated polysaccharides and sucrose fatty acid esters;
  • surfactants one type of surfactant may be used alone, or two or more types of surfactants may be used in combination.
  • commercial products may be used as these surfactants.
  • the emulsified composition of the present invention contains a surfactant
  • the surfactant is an anionic surfactant
  • the content thereof is preferably 50% by mass or less relative to component A. , 30% by mass or less.
  • the emulsified composition of the present invention contains a surfactant
  • the surfactant is a nonionic surfactant
  • the content thereof should be 60% by mass or less with respect to component A. It is preferably 30% by mass or less, and more preferably 30% by mass or less.
  • the content of the surfactant is more preferably 2% by mass or less, more preferably 1% by mass or less, relative to the oily component. It is preferably 0.1% by mass or less, and particularly preferably 0.1% by mass or less.
  • the lower limit of the surfactant content is 0.001% by mass as the content of the surfactant in the emulsified composition.
  • the emulsified composition of the present invention is substantially free of surfactants.
  • the emulsified composition of the present invention is not only useful in terms of safety such as less irritation to the skin, but also has a glossy appearance, freshness and richness. It can be an emulsion composition comprising It is speculated that such properties are due to the use of the component A of the present invention, that is, the acrylic acid ester (a)/compound (b) copolymer as an emulsifier.
  • the acrylic acid ester (a)/compound (b) copolymer can provide an emulsified composition with a larger emulsified particle size than when an oily component is emulsified using a general surfactant. As a result, an emulsified composition having properties such as luster and richness can be obtained.
  • the emulsified composition of the present invention may contain additives in addition to the component A, oil component, surfactant and water described above.
  • additives are not particularly limited as long as they are commonly used in emulsified compositions, and examples thereof include pH adjusters, electrolytes, thickeners, and the like.
  • pH adjusters include carbonic acid, acetic acid, lactic acid, gluconic acid, succinic acid, glutaric acid, adipic acid, malic acid, tartaric acid, maleic acid, fumaric acid, itaconic acid, citric acid, benzoic acid, and salicylic acid.
  • Amino acids include organic sulfonic acids such as ethanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, m-xylenesulfonic acid; aminosulfonic acids such as taurine; inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.
  • Acid agents trimethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methylpropanol, 2-amino-2-methyl-1,3-propanediol, diisopropanolamine, tromethamine, cocamidomethyl Amines such as monoethanolamine; ammonia and ammoniums such as ammonia, ammonium carbonate, monoammonium dihydrogen phosphate, and stearyltrimethylammonium chloride; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; Examples include alkali agents such as inorganic bases of alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide.
  • pH adjuster one type of pH adjuster may be used alone, or two or more types of pH adjusters may be used in combination. Moreover, these pH adjusters should just use a commercial thing.
  • the emulsified composition of the present invention preferably has a weakly acidic to alkaline pH of 4-12, more preferably a pH of 5-10, and even more preferably a pH of 6-9.
  • the pH of the emulsified composition may be appropriately adjusted depending on the use of the external skin preparation or cosmetic containing the emulsified composition.
  • electrolytes include carbonic acid, acetic acid, lactic acid, gluconic acid, succinic acid, glutaric acid, adipic acid, malic acid, tartaric acid, maleic acid, fumaric acid, itaconic acid, citric acid, benzoic acid, salicylic acid, and gallic acid.
  • Acids phthalic acid, diethylbarbituric acid, hyaluronic acid, DL-pyrrolidonecarboxylic acid, ascorbic acid, pantothenic acid, carboxylic acids such as thioglycolic acid; amino acids such as glycine, alanine, valine, leucine, serine, glutamic acid, aspartic acid organic sulfonic acids such as ethanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid and m-xylenesulfonic acid; aminosulfonic acids such as taurine; acid agents such as inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid ; trimethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methylpropanol, 2-amino-2-methyl-1,3-propanediol, diisopropano
  • electrolytes one type of electrolyte may be used alone, or two or more types of electrolytes may be used in combination. Moreover, these electrolytes should just use a commercial thing.
  • sodium bicarbonate, sodium carbonate, and magnesium carbonate are preferred from the standpoint of stably blending in external skin preparations and cosmetics containing the emulsified composition of the present invention, and from the viewpoint of water retention and moisturizing properties when applied to the skin.
  • magnesium hydroxide, calcium hydroxide, magnesium chloride, calcium chloride, magnesium citrate, calcium citrate, and benzoin may be used depending on the type of external skin preparation or cosmetic containing the emulsified composition of the present invention.
  • Polyelectrolytes such as magnesium acid, calcium benzoate, magnesium carbonate, calcium carbonate, magnesium phosphate, calcium phosphate, magnesium-L-ascorbyl phosphate may be preferred.
  • the emulsified composition of the present invention can form an emulsified composition with a desired feel.
  • the content of the electrolyte is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, relative to the emulsion composition. is more preferable, and 0.1 to 5% by mass is even more preferable.
  • the content of the electrolyte is preferably 10 to 500% by mass, more preferably 100 to 400% by mass, relative to component A. , 200 to 300% by mass.
  • a cosmetic composition e.g., milky lotion, etc.
  • a property of preventing dripping by increasing the viscosity of component A by adjusting the content of the electrolyte in the range of 200 to 300% by mass with respect to component A. can be done.
  • the emulsified composition of the present invention has a high viscosity in the presence of a high-concentration (for example, 2 to 5% by mass) electrolyte, is excellent in usability and spreadability, and has a unique tactile sensation.
  • a high-concentration for example, 2 to 5% by mass
  • thickeners include carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, cationized cellulose, gum arabic, carrageenan, agar, mannan, guar gum, quince seed (quince), tamarind gum, and locust bean.
  • a water-soluble compound described in JP-A-2021-123592 can be used as a thickening agent.
  • the thickening agent mentioned here also includes the pH adjusting agent and the electrolyte having the functions described above.
  • hydroxyethyl cellulose, agar, xanthan gum, carboxyvinyl polymer, and alkyl-modified carboxyvinyl polymer may be preferred depending on the intended use and desired viscosity.
  • thickeners one type of thickener may be used alone, or two or more types of thickeners may be used in combination. Moreover, these thickeners should just use a commercial thing.
  • the content of the thickener is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, relative to the emulsion composition. %, more preferably 0.01 to 3% by mass.
  • the emulsified composition of the present invention can be made into a highly viscous composition in the presence of a thickener, and can be suitably used for external skin preparations and cosmetics that require high viscosity.
  • the method for producing an emulsified composition of the present invention includes the steps of preparing an aqueous phase containing the component A, and preparing an oil phase containing the oily component. and mixing and emulsifying the water phase and the oil phase.
  • a sodium hydroxide aqueous solution is added so that the pH of the solution becomes near neutral, and the solution is stirred as appropriate to obtain solution 1.
  • aqueous phase preparation step an oil phase containing an oily component is prepared.
  • the emulsified composition contains a surfactant
  • a water-soluble surfactant may be added to the water phase
  • an oil-soluble surfactant may be added to the oil phase, depending on the properties of the emulsion composition.
  • the aqueous phase and the oil phase are mixed, and the aqueous phase and the oil phase are stirred and emulsified using a homomixer, a disper, a rotation-revolution mixer, or the like until the desired emulsified particle size is achieved ( emulsification step), the emulsified composition of the present invention can be prepared.
  • the method of mixing the water phase and the oil phase in the emulsification step is not particularly limited, and the oil phase may be added to the water phase and mixed, or the water phase may be added to the oil phase and mixed.
  • the temperature during the aqueous phase preparation step, the oil phase preparation step and the emulsification step is not particularly limited, but it is generally desirable to set the temperature above the melting point of the oily component used in the production method of the present invention and below 100°C.
  • the stirring speed during the emulsification process is not particularly limited as long as it is a stirring speed at which the water phase and the oil phase can be emulsified.
  • the stirring speed during the water phase preparation step and the oil phase preparation step is not particularly limited as long as it is a speed at which each component contained in the water phase or the oil phase can be mixed, dissolved, and dispersed.
  • the emulsification time during the emulsification process is not particularly limited, but it is preferably 1 to 60 minutes when manufacturing with a batch emulsifier, and 1 minute or less when manufacturing with a continuous emulsifier.
  • the pressure during the emulsification process may be not only normal pressure but also reduced pressure or increased pressure. Stirring under reduced pressure or increased pressure may result in effective emulsification because bubbles are less likely to mix.
  • the emulsification process according to the production method of the present invention is not limited to the method described above, and various methods can be adopted.
  • a mechanical emulsification method, a D phase emulsification method, a phase inversion emulsification method, a liquid crystal emulsification method, and an amino acid gel emulsification method can be mentioned.
  • a mechanical emulsification method for example, a high-pressure homogenizer, colloid mill, nanomizer, microfluidizer, stirrer with propeller, homomixer, homodisper, rotation-revolution mixer, magnetic stirrer and the like can be used.
  • the rotation speed is usually 500 rpm or more, preferably 800 rpm or more, more preferably 1,200 rpm or more, and usually 20,000 rpm or less.
  • the external skin preparation and cosmetic of the present invention contain the emulsified composition of the present invention, and the emulsified composition is blended with other optional ingredients generally used as external skin preparations and cosmetics.
  • the emulsified composition of the present invention can be directly used as an external skin preparation.
  • the content of the emulsified composition of the present invention in the external skin preparation and cosmetic of the present invention is usually 1-100% by mass, preferably 30-100% by mass.
  • ingredients to be blended in the external preparation for skin and cosmetics of the present invention can be used without particular limitation as long as they are additives commonly used in this field.
  • Specific examples of such ingredients include thickeners, hair dyes, hair styling agents, UV inhibitors, whitening agents, anti-aging agents, moisturizers, softeners, antioxidants, and preservatives.
  • antibacterial agents such as cooling agents, powders, polymer ingredients other than the copolymer according to the present invention, etc. mentioned.
  • the method for preparing the external preparation for skin and the cosmetic of the present invention is not particularly limited as long as it is a method (compounding method) commonly practiced in this field, and the emulsified composition of the present invention and, if necessary, other optional ingredients are combined.
  • the external preparation for skin and the cosmetic of the present invention may be prepared by blending by a general method.
  • the external preparation for skin and the cosmetic of the present invention thus obtained have a pH suitable for the intended use.
  • the pH of the external preparation for skin and the cosmetic of the present invention is preferably weakly acidic to alkaline of pH 4-12, more preferably pH 5-10.
  • the above-described pH adjuster may be used.
  • Examples of applications of the external preparation for skin of the present invention include liquids for external use, gels for external use, creams, ointments, liniments, lotions, poultices, plasters, sprays, aerosols, foams, and the like. .
  • compositions of the present invention can reduce the amount of surfactant blended. is preferably used for
  • the emulsified composition of the present invention can be used for various purposes other than external skin preparations and cosmetics.
  • pharmaceuticals antibacterial agents, antifungal agents, caries preventatives, anticalculus agents, antiplaque agents, poultices, ointments, etc.
  • soil water retention agents antistatic agents, medical waste solidifying agents, petroleum Drilling fluids, oil-related water treatment applications, paints (oil-based paints, antiseptic paints, ship bottom paints, emulsion paints, exterior wall paints, heat-radiating paints, heat-shielding paints, antifouling coating agents, matting agents, etc.), inks ( Oil-based paint, emulsion paint, spray ink, inkjet ink, UV curing ink), writing utensils (oil-based ballpoint pen, gel ink ballpoint pen, emulsion ballpoint pen, friction ballpoint pen, felt-tip pen, brush pen, line marker, highlighter, oil-based paint, acrylic paint )
  • Colored resin composition (resin particles ), the emulsified composition of the present invention can also be used as a dispersant.
  • Additives that are commonly used in these fields may be used as additives for these applications, and the amount to be added may be appropriately set based on the amount that can be normally added.
  • Oleyl alcohol manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. Co., Ltd. Oleic acid: FUJIFILM Wako Pure Chemical Co., Ltd. -Surfactant- Polyoxyethylene lauryl ether; Emulgen 105: manufactured by Kao Corporation Sodium lauryl sulfate: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. -Electrolyte- Phosphate-L-ascorbyl magnesium n-hydrate (moisture content: 16-20% by mass): manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. -pH adjuster- 2 mol / L sodium hydroxide aqueous solution: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.
  • the mixed solution was bubbled for 30 minutes in a nitrogen gas atmosphere to deaerate oxygen contained in the solution.
  • the solution was then heated to 55° C. over 30 minutes while being stirred at a rotation speed of 200 rpm, and the solution was further stirred for 1 hour while maintaining the same temperature.
  • the solution was then heated to 75° C. over 1 hour and 30 minutes, and the solution was stirred at 200 rpm for an additional 2 hours while maintaining the same temperature.
  • the solution is cooled to room temperature, the copolymer (polymer) precipitated by cooling is collected by filtration, and the filtered copolymer is dried under reduced pressure at 90 to 110° C. for 8 hours to obtain the present invention. 41.85 g of component (A) was obtained (yield: 93%).
  • *0.14 represents the molar amount of diethylene glycol diallyl ether when the total of perfluorohexylethyl acrylate and acrylic acid is 100 mol.
  • the mixed solution was bubbled for 30 minutes in a nitrogen gas atmosphere to deaerate oxygen contained in the solution.
  • the solution was then heated to 75° C. over 30 minutes while being stirred at a rotation speed of 200 rpm, and the solution was further stirred for 3 hours while maintaining the same temperature.
  • the solution was then heated to 95° C. over 30 minutes, and the solution was stirred at 200 rpm for an additional hour while maintaining the same temperature.
  • the solution is cooled to room temperature, the copolymer (polymer) precipitated by cooling is collected by filtration, and the filtered copolymer is dried under reduced pressure at 90 to 110° C. for 8 hours to obtain the present invention. 42.39 g of component (A) was obtained (yield: 94%).
  • *0.23 represents the molar amount of diethylene glycol diallyl ether when the total of perfluorohexylethyl acrylate and acrylic acid is 100 mol.
  • *0.23 represents the molar amount of diethylene glycol diallyl ether when the total of perfluorohexylethyl acrylate and acrylic acid is 100 mol.
  • the amount of acrylic acid used in Synthesis Example 1 was changed to 40.24 g (0.56 mol)
  • the amount of perfluorohexylethyl acrylate used was changed to 4.76 g (0.011 mol)
  • diethylene glycol was added.
  • Diallyl ether was changed to pentaerythritol triallyl ether, the amount used was changed to 0.15 g (0.57 mmol), and the amount of di(4-tert-butylcyclohexyl)peroxydicarbonate used was changed to 0.082 g (0.57 mmol).
  • the component (A) according to the present invention was obtained in the same manner as in Synthesis Example 1.
  • *0.10 represents the molar amount of pentaerythritol triallyl ether when the total of perfluorohexylethyl acrylate and acrylic acid is 100 mol.
  • Example 1- Preparation of emulsified composition of the present invention (1) Under normal temperature conditions, 0.5 g of (perfluorohexylethyl acrylate/acrylic acid) crosspolymer was added to 20.5 g of ion-exchanged water, and the mixture was stirred at a rotation speed of 550 rpm to obtain a uniform dispersion.
  • 0.5 g of (perfluorohexylethyl acrylate/acrylic acid) crosspolymer was added to 20.5 g of ion-exchanged water, and the mixture was stirred at a rotation speed of 550 rpm to obtain a uniform dispersion.
  • the obtained dispersion was neutralized by adding a 2 mol/L sodium hydroxide aqueous solution so that the pH of the dispersion became 7.5, and then a rotation-revolution mixer (Awatori Mixer ARE-310 : manufactured by Thinky Co., Ltd.) and stirred at a rotation speed of 2,000 to 2,200 rpm for 20 minutes to obtain a solution 1.
  • a rotation-revolution mixer (Awatori Mixer ARE-310 : manufactured by Thinky Co., Ltd.) and stirred at a rotation speed of 2,000 to 2,200 rpm for 20 minutes to obtain a solution 1.
  • the oil phase B is added to the water phase A, and kneaded for 20 minutes at a rotation speed of 2,000 to 2,200 rpm using a rotation-revolution mixer (Awatori Mixer ARE-310: manufactured by Thinky Co., Ltd.). , to obtain an oil-in-water (O/W) emulsified composition.
  • a rotation-revolution mixer (Awatori Mixer ARE-310: manufactured by Thinky Co., Ltd.).
  • Examples 2 to 17 Preparation of emulsified composition of the present invention (2) to (17)
  • the emulsification of the present invention was performed in the same manner as in Example 1, except that the components shown in Table 1 were used so that the proportions (mass%) of each component were as shown in Table 1.
  • Compositions (2) to (17) were obtained.
  • the surfactants in the table were added to the solution after adding the solution containing magnesium L-ascorbyl phosphate n-hydrate to the solution 1 in the aqueous phase preparation step to prepare the aqueous phase A. bottom.
  • Table 1 shows the name of each component and the ratio of each component (mass% of each component when the total amount of the composition is 100) in Examples 2 to 17.
  • Examples 18 to 34 Preparation of emulsified composition of the present invention (18) to (34)
  • the emulsification of the present invention was prepared in the same manner as in Example 1, except that the components shown in Table 2 were used so that the proportions (mass%) of each component were as shown in Table 2.
  • Compositions (18) to (34) were obtained.
  • the surfactants in the table were added to the solution after adding the solution containing magnesium L-ascorbyl phosphate n-hydrate to the solution 1 in the aqueous phase preparation step to prepare the aqueous phase A. bottom.
  • Table 2 shows the name of each component and the ratio of each component (mass% of each component when the total amount of the composition is 100) in Examples 18 to 34.
  • Examples 35 to 41 Preparation of emulsified composition of the present invention (35) to (41)
  • the emulsification of the present invention was prepared in the same manner as in Example 1, except that the components shown in Table 3 were used so that the proportions (mass%) of each component were as shown in Table 3.
  • Compositions (35) to (41) were obtained.
  • the surfactants in the table were added to the solution after adding the solution containing magnesium L-ascorbyl phosphate n-hydrate to the solution 1 in the aqueous phase preparation step to prepare the aqueous phase A. bottom.
  • Table 3 shows the name of each component and the ratio of each component (mass% of each component when the total amount of the composition is 100) in Examples 35 to 41.
  • Examples 42 to 43 Preparation of emulsified composition of the present invention (42) to (43)
  • the emulsification of the present invention was prepared according to the same method as in Example 1, except that the components shown in Table 4 were used so that the proportions (% by mass) of each component were as shown in Table 4.
  • Compositions (42) to (43) were obtained.
  • the name of each component and the ratio of each component (mass% of each component when the total amount of the composition is 100) in Examples 42 to 43 are shown in Table 4 together with the results of Example 18 and Example 35. .
  • the most fresh, non-sticky, and spreadable product is rated as “5: excellent”, and as the degree becomes weaker, "4: slightly excellent", “3: normal”, “2: Slightly inferior”, and “1: inferior” for lack of freshness, stickiness, and poor spreadability.
  • iii. Body Feeling The "body feeling” after application (spreading) of the emulsified composition immediately after emulsification was evaluated in 1-point increments, with the highest evaluation being 5 points and the lowest evaluation being 1 point.
  • the most rich, moist, moisturizing feeling is given as "5: excellent", and as the degree becomes weaker, "4: slightly excellent", “3: normal” and “2: Slightly inferior".
  • Emulsified compositions (1) to (43) (emulsified compositions of the present invention) of Examples 1 to 43 have stability over time in a uniform emulsified state, and have a glossy appearance and a smooth appearance when applied to the skin. It was excellent in freshness and moist and rich feeling after application (spreading).
  • the emulsified compositions (1) to (7) of Comparative Examples 1 to 7 (emulsified compositions for comparison) could not maintain a uniform emulsified state, and not only did not have an excellent glossy appearance, It was not possible to achieve both freshness and richness.
  • the emulsified composition of the present invention can be used as an external preparation for skin and a cosmetic having excellent properties, it has excellent stability over time in an emulsified state, has a glossy appearance, and has a fresh and rich feeling in use.

Abstract

The purpose of the present is to provide an oil-in-water (O/W) emulsion composition which the user perceives as fresh at the time of application and as thick after application (after spreading out), and which can coexist with electrolytes in the composition.　The present invention relates to: an oil-in-water (O/W) emulsion composition which contains an oil-base component in the emulsion particles, wherein the emulsion composition includes a component A and the oil-base component, the content of component A is 0.4-250 mass% with respect to the oil-base component, the emulsion composition contains substantially no surfactant, and in the case of containing surfactant, the content of said surfactant is less than or equal to 90 mass% with respect to component A and less than or equal to 3 mass% with respect to the oil-base component, and the content of the oil-base component in the emulsion composition is 1-65%; a skin topical agent and a cosmetic that contain said emulsion composition; and a production method of said emulsion composition. Component A: an acrylic acid ester (a) / compound (b) copolymer which comprises as constituent components an acrylic acid ester (a) that is represented in general formula [1] and a compound (b) that has, in the molecule, a polymerizable unsaturated group and a functional group that is selected from among a carboxyl group, a sulfo group and a phosphate group, wherein the ratio (mass ratio) of the acrylic acid ester (a) and the compound (b) is (a)/(b) = 6.0/94.0-30.0/70.0. General formula [1]: (in the formula, R1 represents a hydrogen atom or an alkyl group with 1-6 carbons, and m represents an integer 2-4.)

Description

乳化組成物、該組成物を含有する皮膚外用剤および化粧料Emulsion composition, skin external preparation and cosmetic containing said composition
　本発明は、乳化組成物、該組成物を含有する皮膚外用剤および化粧料に関する。 The present invention relates to an emulsified composition, an external preparation for skin and a cosmetic containing the composition.
　化粧料分野において、油滴が水に分散した水中油型（Ｏ／Ｗ）の乳化組成物は、高付加価値を有する製剤として、乳液、ジェルクリーム等に幅広く利用されている。乳化組成物に特徴的な感触である、塗布（塗り広げた）後のしっとりとしたコク感は、油性成分によって付与され、コク感の程度は油性成分の種類や油性成分と乳化剤とのバランスによって決定される。 In the field of cosmetics, oil-in-water (O/W) emulsified compositions in which oil droplets are dispersed in water are widely used as emulsions, gel creams, etc., as formulations with high added value. The moist and rich feeling after application (spreading), which is a characteristic touch of emulsion compositions, is imparted by the oily component, and the degree of richness depends on the type of oily component and the balance between the oily component and the emulsifier. It is determined.
　高いコク感を得る方法として、油性成分を多量に使用したり、油性成分に固形油や半固形油を使用して乳化する方法が知られている（例えば、特許文献１等）。しかしながら、これらの方法で安定的に乳化させるには、多量の乳化剤の使用が必要であるため、皮膚に対する刺激から肌荒れの原因となり得る可能性がある。また、固形油の乳化による過度の増粘や乳化剤の併用による油滴の過度の安定化により、塗布時のみずみずしさが低下するといった懸念もある。 As a method for obtaining a high richness, a method of using a large amount of an oily component or emulsifying using a solid oil or a semi-solid oil as the oily component is known (for example, Patent Document 1, etc.). However, stably emulsifying by these methods requires the use of a large amount of emulsifier, which may cause skin irritation and rough skin. In addition, there is a concern that excessive thickening due to emulsification of solid oil and excessive stabilization of oil droplets due to combined use of an emulsifier may reduce freshness during application.
　このような問題点を解決する方法として、コク感につながる濃厚な感触を与える増粘剤と皮膚に対する刺激が小さい高分子乳化剤を使用する方法がある。特に、アルキル変性カルボキシビニルポリマーは、増粘作用と乳化作用を併せ持つことから、広く使用されている。しかしながら、塩化ナトリウムやアスコルビン酸誘導体等の電解質や界面活性剤を共存させると、減粘したり、乳化作用が低下するという問題がある。 As a way to solve these problems, there is a method of using a thickener that gives a rich feel that leads to a rich feeling and a polymer emulsifier that has little irritation to the skin. In particular, alkyl-modified carboxyvinyl polymers are widely used because they have both thickening and emulsifying effects. However, coexistence of an electrolyte such as sodium chloride or an ascorbic acid derivative and a surfactant poses problems such as reduced viscosity and reduced emulsifying action.
特開平９－２５５５２９号公報JP-A-9-255529
　一方で、国際公開第２０１７／１７０９６１号に記載の（アクリル酸パーフルオロへキシルエチル／アクリル酸）クロスポリマーは、電解質を共存させても高粘度を保持できるという特徴を有することから、本発明者らは、該クロスポリマーを乳化組成物に使用する検討を行ってきた。その結果、該クロスポリマーは、意外にも乳化剤としての作用を有していることが分かった。 On the other hand, the (perfluorohexylethyl acrylate/acrylic acid) crosspolymer described in International Publication No. 2017/170961 has the characteristic of being able to maintain high viscosity even in the presence of an electrolyte. have investigated the use of the crosspolymer in emulsion compositions. As a result, it was found that the crosspolymer unexpectedly has an action as an emulsifier.
　しかしながら、乳化組成物中に該クロスポリマーを単に配合しただけでは、乳化組成物の経時安定性が保たれないという問題や、乳化組成物の外観や塗布時の感触に問題があることが分かった。 However, it has been found that simply blending the crosspolymer into the emulsified composition causes problems in that the stability of the emulsified composition over time cannot be maintained, and in the appearance of the emulsified composition and the feel of the composition when applied. .
　本発明は、上述した状況に鑑み成されたものであり、使用感として塗布時のみずみずしさと塗布（塗り広げた）後のコク感を併せ持ち、組成物中に電解質を共存できる水中油型（Ｏ／Ｗ）の乳化組成物を提供することを目的とする。 The present invention has been made in view of the above-mentioned situation, and has both a fresh feeling when applied and a rich feeling after application (spreading) as a feeling of use, and an oil-in-water type (O) that can coexist with electrolytes in the composition. /W).
　本発明者らは、このような乳化組成物について鋭意研究を重ねた結果、増粘剤および高分子乳化剤として、国際公開第２０１７／１７０９６１号に記載のクロスポリマーを特定量使用するとともに、該クロスポリマーと油性成分の配合比や乳化組成物中の油性成分の配合量等を調整することで、塗布時の油滴崩壊性の向上により、所望の使用感を有する乳化組成物を提供できることを見出し、本発明を完成させるに至った。 The present inventors have made intensive studies on such emulsified compositions. We found that by adjusting the blending ratio of the polymer and the oily component and the blending amount of the oily component in the emulsified composition, it is possible to improve the disintegration of the oil droplets during application, thereby providing an emulsified composition with a desired feeling of use. , have completed the present invention.
　本発明は、以下の構成よりなる。
　（１）乳化粒子中に油性成分を含む水中油型（Ｏ／Ｗ）の乳化組成物であって、前記乳化組成物は、成分Ａと油性成分とを含み、前記成分Ａの含有量が、前記油性成分に対して０．４～２５０質量％であり、前記乳化組成物は界面活性剤を実質的に含まないか、界面活性剤を含む場合には、該界面活性剤の含有量が、前記成分Ａに対して９０質量％以下、かつ、前記油性成分に対して３質量％以下であり、前記乳化組成物中における前記油性成分の含有量が、１～６５質量％である、乳化組成物。
成分Ａ：（ａ）一般式［１］で示されるアクリル酸エステル、ならびに（ｂ）重合性不飽和基と、カルボキシル基、スルホ基およびリン酸基からなる群から選ばれるいずれかの官能基とを分子内に有する化合物を構成成分とし、前記アクリル酸エステル（ａ）と前記化合物（ｂ）との割合（質量比）が、（ａ）／（ｂ）＝６．０／９４．０～３０．０／７０．０である、アクリル酸エステル（ａ）／化合物（ｂ）共重合体。
一般式［１］：
Figure JPOXMLDOC01-appb-I000007
（式中、Ｒ１は、水素原子または炭素数１～６のアルキル基を表し、ｍは、２～４の整数を表す。） The present invention consists of the following configurations.
(1) An oil-in-water (O/W) emulsified composition containing an oily component in emulsified particles, wherein the emulsified composition contains a component A and an oily component, and the content of the component A is It is 0.4 to 250% by mass with respect to the oily component, and the emulsified composition does not substantially contain a surfactant, or when it contains a surfactant, the content of the surfactant is 90% by mass or less of the component A and 3% by mass or less of the oily component, and the content of the oily component in the emulsion composition is 1 to 65% by mass. thing.
Component A: (a) an acrylic acid ester represented by the general formula [1], and (b) a polymerizable unsaturated group and any functional group selected from the group consisting of a carboxyl group, a sulfo group and a phosphoric acid group in the molecule, and the ratio (mass ratio) of the acrylic acid ester (a) and the compound (b) is (a)/(b) = 6.0/94.0 to 30 Acrylic acid ester (a)/compound (b) copolymer, which is .0/70.0.
General formula [1]:
Figure JPOXMLDOC01-appb-I000007
(In the formula, R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and m represents an integer of 2 to 4.)
　（２）前記界面活性剤が、アニオン性界面活性剤または非イオン性界面活性剤である、前記（１）に記載の乳化組成物。 (2) The emulsified composition according to (1) above, wherein the surfactant is an anionic surfactant or a nonionic surfactant.
　（３）前記界面活性剤が、アニオン性界面活性剤であって、該アニオン性界面活性剤の含有量が、前記成分Ａに対して５０質量％以下である、前記（１）に記載の乳化組成物。 (3) The emulsification according to (1) above, wherein the surfactant is an anionic surfactant, and the content of the anionic surfactant is 50% by mass or less relative to the component A. Composition.
　（４）前記界面活性剤が、非イオン性界面活性剤であって、該非イオン性界面活性剤の含有量が、前記成分Ａに対して６０質量％以下である、前記（１）に記載の乳化組成物。 (4) The above (1), wherein the surfactant is a nonionic surfactant, and the content of the nonionic surfactant is 60% by mass or less relative to the component A. emulsified composition.
　（５）前記界面活性剤が、アニオン性界面活性剤または非イオン性界面活性剤であって、該アニオン性界面活性剤または非イオン性界面活性剤の含有量が、前記成分Ａに対して３０質量％以下である、前記（１）または（２）に記載の乳化組成物。 (5) the surfactant is an anionic surfactant or a nonionic surfactant, and the content of the anionic surfactant or nonionic surfactant is 30% relative to the component A; The emulsion composition according to (1) or (2) above, which is at most % by mass.
　（６）前記乳化組成物が、界面活性剤を実質的に含まないものである、前記（１）に記載の乳化組成物。 (6) The emulsified composition according to (1), wherein the emulsified composition does not substantially contain a surfactant.
　（７）前記乳化組成物が、更に電解質を含むものである、前記（１）～（６）のいずれか１つに記載の乳化組成物。 (7) The emulsified composition according to any one of (1) to (6) above, which further contains an electrolyte.
　（８）前記電解質が、多価電解質である、前記（７）に記載の乳化組成物。 (8) The emulsion composition according to (7) above, wherein the electrolyte is a polyelectrolyte.
　（９）前記アクリル酸エステル（ａ）／化合物（ｂ）共重合体が、更に（ｃ）エチレン性不飽和基を２個以上有する化合物を構成成分として含むものである、前記（１）～（８）のいずれか１つに記載の乳化組成物。 (9) The above (1) to (8), wherein the acrylic acid ester (a)/compound (b) copolymer further contains (c) a compound having two or more ethylenically unsaturated groups as a constituent component. The emulsified composition according to any one of.
　（１０）前記化合物（ｂ）が、一般式［２］～［５］で示される化合物である、前記（１）～（９）のいずれか１つに記載の乳化組成物。
一般式［２］：
Figure JPOXMLDOC01-appb-I000008
（式中、Ｒ２は、水素原子または炭素数１～６のアルキル基を表す。）
一般式［３］：
Figure JPOXMLDOC01-appb-I000009
（式中、Ａは、酸素原子または－ＮＨ－基を表し、Ｔ１は、ヒドロキシル基を有していてもよい炭素数１～６のアルキレン基を表し、Ｒ３は、水素原子または炭素数１～６のアルキル基を表す。）
一般式［４］：
Figure JPOXMLDOC01-appb-I000010
（式中、Ｔ２は、結合手または炭素数１～６のアルキレン基を表し、Ｒ４は、水素原子または炭素数１～６のアルキル基を表す。）
一般式［５］：
Figure JPOXMLDOC01-appb-I000011
（式中、Ｔ３は、炭素数１～６のアルキレン基を表し、Ｒ５は、水素原子または炭素数１～６のアルキル基を表す。） (10) The emulsified composition according to any one of (1) to (9) above, wherein the compound (b) is a compound represented by formulas [2] to [5].
General formula [2]:
Figure JPOXMLDOC01-appb-I000008
(In the formula, R 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
General formula [3]:
Figure JPOXMLDOC01-appb-I000009
(In the formula, A represents an oxygen atom or -NH- group, T 1 represents an alkylene group having 1 to 6 carbon atoms which may have a hydroxyl group, R 3 represents a hydrogen atom or a represents an alkyl group of 1 to 6.)
General formula [4]:
Figure JPOXMLDOC01-appb-I000010
(In the formula, T 2 represents a bond or an alkylene group having 1 to 6 carbon atoms, and R 4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
General formula [5]:
Figure JPOXMLDOC01-appb-I000011
(In the formula, T 3 represents an alkylene group having 1 to 6 carbon atoms, and R 5 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
　（１１）前記化合物（ｂ）が、一般式［２］で示される化合物である、前記（１）～（９）のいずれか１つに記載の乳化組成物。
一般式［２］：
Figure JPOXMLDOC01-appb-I000012
（式中、Ｒ２は、水素原子または炭素数１～６のアルキル基を表す。） (11) The emulsified composition according to any one of (1) to (9) above, wherein the compound (b) is a compound represented by the general formula [2].
General formula [2]:
Figure JPOXMLDOC01-appb-I000012
(In the formula, R 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
　（１２）前記油性成分が、炭化水素類、エステル油類、高級アルコール類、シリコーン油類、ロウ類および動植物油類からなる群から選ばれる少なくとも１種である、前記（１）～（１１）のいずれか１つに記載の乳化組成物。 (12) The above (1) to (11), wherein the oily component is at least one selected from the group consisting of hydrocarbons, ester oils, higher alcohols, silicone oils, waxes and animal and vegetable oils. The emulsified composition according to any one of.
　（１３）前記（１）～（１２）のいずれか１つに記載の乳化組成物を含有する皮膚外用剤。 (13) A skin external preparation containing the emulsified composition according to any one of (1) to (12).
　（１４）前記（１）～（１２）のいずれか１つに記載の乳化組成物を含有する化粧料。 (14) A cosmetic containing the emulsified composition according to any one of (1) to (12) above.
　（１５）成分Ａを含む水相を調製する工程と、油性成分を含む油相を調製する工程と、前記水相と前記油相を混合して乳化させる工程を含む、前記（１）に記載の乳化組成物の製造方法。 (15) The method according to (1) above, comprising a step of preparing an aqueous phase containing component A, a step of preparing an oil phase containing an oily component, and a step of mixing and emulsifying the aqueous phase and the oil phase. A method for producing an emulsified composition.
　本発明の乳化組成物は、均一な乳化状態の経時安定性や外観のツヤに優れ、皮膚へ塗布時の高いみずみずしさと塗布（塗り広げた）後のしっとりとした高いコク感を両立した水中油型（Ｏ／Ｗ）の乳化組成物である。 The emulsified composition of the present invention is an oil-in-water oil that has excellent stability over time in a uniform emulsified state and a glossy appearance, and has both a high freshness when applied to the skin and a moist and rich feeling after application (spreading). It is an emulsion composition of the type (O/W).
　本発明の乳化組成物を含有する皮膚外用剤および化粧料は、乳化状態の経時安定性に優れ、ツヤのある外観を有し、使用感としてみずみずしさとコク感を備える皮膚外用剤および化粧料である。 The external skin preparations and cosmetics containing the emulsified composition of the present invention are excellent in the stability of the emulsified state over time, have a glossy appearance, and have freshness and richness when used. be.
　以下、本発明について詳細に説明する。なお、本明細書等において、「有していてもよい」とは、「有する」または「有さない」ことを意味し、「および／または」は、いずれか一方、あるいは、両方を包含する意味で使用される。数値範囲を表す「～」は、その上限および下限の値を含む範囲を意味する。本明細書中の「発明を実施するための形態」の項で引用されるすべての刊行物および特許は、例えば、本発明で使用できる化合物や材料、あるいは方法等を示すものとして、本明細書の一部を構成する。 The present invention will be described in detail below. In this specification and the like, "may have" means "has" or "does not have", and "and/or" includes either one or both used with meaning. "~" representing a numerical range means the range including the upper and lower limits. All publications and patents cited in this specification section in the Detailed Description section are hereby incorporated by reference, for example, as indicative of compounds, materials, methods, etc. that may be used in the present invention. form part of
－本発明の乳化組成物－
　本発明の乳化組成物は、乳化粒子中に油性成分を含む水中油型（Ｏ／Ｗ）の乳化組成物であって、成分Ａと油性成分とを含み、上記成分Ａの含有量が、上記油性成分に対して０．４～２５０質量％であり、上記乳化組成物は界面活性剤を実質的に含まないか、界面活性剤を含む場合には、該界面活性剤の含有量が、上記成分Ａに対して９０質量％以下、かつ、上記油性成分に対して３質量％以下であり、上記乳化組成物中における上記油性成分の含有量が、１～６５質量％である、乳化組成物である。
成分Ａ：（ａ）一般式［１］で示されるアクリル酸エステル、ならびに（ｂ）重合性不飽和基と、カルボキシル基、スルホ基およびリン酸基からなる群から選ばれるいずれかの官能基とを分子内に有する化合物を構成成分とし、上記アクリル酸エステル（ａ）と上記化合物（ｂ）との割合（質量比）が、（ａ）／（ｂ）＝６．０／９４．０～３０．０／７０．０である、アクリル酸エステル（ａ）／化合物（ｂ）共重合体。
一般式［１］：
Figure JPOXMLDOC01-appb-I000013
（式中、Ｒ１は、水素原子または炭素数１～６のアルキル基を表し、ｍは、２～４の整数を表す。） -Emulsified composition of the present invention-
The emulsified composition of the present invention is an oil-in-water (O/W) emulsified composition containing an oily component in emulsified particles, comprising component A and an oily component, wherein the content of component A is It is 0.4 to 250% by mass with respect to the oily component, and the emulsified composition does not substantially contain a surfactant, or when it contains a surfactant, the content of the surfactant is 90% by mass or less of component A and 3% by mass or less of the oily component, and the content of the oily component in the emulsion composition is 1 to 65% by mass. is.
Component A: (a) an acrylic acid ester represented by the general formula [1], and (b) a polymerizable unsaturated group and any functional group selected from the group consisting of a carboxyl group, a sulfo group and a phosphoric acid group in the molecule, and the ratio (mass ratio) of the acrylic acid ester (a) and the compound (b) is (a)/(b) = 6.0/94.0 to 30 Acrylic acid ester (a)/compound (b) copolymer, which is .0/70.0.
General formula [1]:
Figure JPOXMLDOC01-appb-I000013
(In the formula, R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and m represents an integer of 2 to 4.)
－本発明にかかる成分Ａ：アクリル酸エステル（ａ）／化合物（ｂ）共重合体－
　本発明にかかる成分Ａ、すなわち、本発明にかかる共重合体とは、少なくとも、アクリル酸エステル（ａ）と化合物（ｂ）を構成成分とする、アクリル酸エステル（ａ）由来の構成単位と化合物（ｂ）由来の構成単位を有する共重合体を意味する。より具体的には、アクリル酸エステル（ａ）／化合物（ｂ）共重合体は、上記一般式［１］で示されるアクリル酸エステル、ならびに重合性不飽和基と、カルボキシル基、スルホ基およびリン酸基からなる群から選ばれるいずれかの官能基とを分子内に有する化合物を構成成分とし、上記アクリル酸エステル（ａ）と上記化合物（ｂ）との割合（質量比）が、（ａ）／（ｂ）＝６．０／９４．０～３０．０／７０．０であることを特徴とするものである。 -Component A according to the present invention: acrylic acid ester (a) / compound (b) copolymer-
The component A according to the present invention, that is, the copolymer according to the present invention is at least the acrylic ester (a)-derived structural unit and the compound, which are composed of the acrylic ester (a) and the compound (b). It means a copolymer having structural units derived from (b). More specifically, the acrylic acid ester (a)/compound (b) copolymer comprises an acrylic acid ester represented by the above general formula [1], a polymerizable unsaturated group, a carboxyl group, a sulfo group and a phosphorus A compound having a functional group selected from the group consisting of acid groups in the molecule is a constituent component, and the ratio (mass ratio) of the acrylic acid ester (a) and the compound (b) is (a) /(b)=6.0/94.0 to 30.0/70.0.
　一般式［１］におけるＲ１で示される炭素数１～６のアルキル基としては、炭素数１～３のアルキル基が好ましく、炭素数１のアルキル基がより好ましい。また、該アルキル基としては、直鎖状、分枝状もしくは環状のいずれであってもよく、なかでも、直鎖状もしくは分枝状のものが好ましい。このようなアルキル基の具体例としては、例えば、メチル基、エチル基、ｎ-プロピル基、イソプロピル基、シクロプロピル基、ｎ-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、シクロブチル基、ｎ-ペンチル基、イソペンチル基、sec-ペンチル基、tert-ペンチル基、ネオペンチル基、２-メチルブチル基、１，２-ジメチルプロピル基、１-エチルプロピル基、シクロペンチル基、ｎ-ヘキシル基、イソヘキシル基、sec-ヘキシル基、tert-ヘキシル基、ネオヘキシル基、２-メチルペンチル基、１，２-ジメチルブチル基、２，３-ジメチルブチル基、１-エチルブチル基、シクロヘキシル基等が挙げられる。これらのアルキル基のなかでも、炭素数１～３の直鎖状もしくは分枝状のアルキル基が好ましく、メチル基がより好ましい。 The alkyl group having 1 to 6 carbon atoms represented by R 1 in general formula [1] is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 carbon atom. In addition, the alkyl group may be linear, branched or cyclic, with linear or branched being preferred. Specific examples of such alkyl groups include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, cyclopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, 2-methylpentyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, cyclohexyl group and the like. Among these alkyl groups, linear or branched alkyl groups having 1 to 3 carbon atoms are preferred, and methyl groups are more preferred.
　一般式［１］におけるＲ１としては、水素原子が好ましい。 A hydrogen atom is preferable as R 1 in the general formula [1].
　一般式［１］におけるｍとしては、２～３の整数が好ましく、２がより好ましい。 m in the general formula [1] is preferably an integer of 2 to 3, more preferably 2.
　このような一般式［１］で示されるアクリル酸エステルの具体例としては、例えば、（メタ）アクリル酸パーフルオロへキシルエチル、（メタ）アクリル酸パーフルオロへキシルプロピル、（メタ）アクリル酸パーフルオロへキシルブチル等が挙げられる。これらのアクリル酸エステルは、市販のものを用いてもよいし、自体公知の方法によって適宜合成したものを用いてもよい。 Specific examples of the acrylic acid ester represented by the general formula [1] include perfluorohexylethyl (meth)acrylate, perfluorohexylpropyl (meth)acrylate, and perfluoro(meth)acrylate. Hexyl butyl etc. are mentioned. These acrylic acid esters may be commercially available ones, or may be appropriately synthesized by a method known per se.
　本明細書において、（メタ）アクリル酸とは、アクリル酸および／またはメタクリル酸を意味する。また、（メタ）アクリル酸エステルや（メタ）アクリル酸塩も同様である。 As used herein, (meth)acrylic acid means acrylic acid and/or methacrylic acid. The same applies to (meth)acrylic acid esters and (meth)acrylic acid salts.
　上述した一般式［１］で示されるアクリル酸エステルのなかでも、（メタ）アクリル酸パーフルオロへキシルエチルが好ましく、アクリル酸パーフルオロへキシルエチルがより好ましい。 Among the acrylic esters represented by the general formula [1] described above, perfluorohexylethyl (meth)acrylate is preferred, and perfluorohexylethyl acrylate is more preferred.
　（ｂ）重合性不飽和基と、カルボキシル基、スルホ基およびリン酸基からなる群から選ばれるいずれかの官能基とを分子内に有する化合物とは、例えば、炭素－炭素二重結合、炭素－炭素三重結合等の重合性不飽和基と、カルボキシル基、スルホ基およびリン酸基からなる群から選ばれるいずれかの官能基とを分子内に有する化合物であって、上記重合性不飽和基が、一般式［１］で示されるアクリル酸エステルと反応して、アクリル酸エステル（ａ）／化合物（ｂ）共重合体を形成する化合物である。 (B) a compound having a polymerizable unsaturated group and any functional group selected from the group consisting of a carboxyl group, a sulfo group and a phosphoric acid group in the molecule is, for example, a carbon-carbon double bond, a carbon - A compound having a polymerizable unsaturated group such as a carbon triple bond and any functional group selected from the group consisting of a carboxyl group, a sulfo group and a phosphoric acid group in the molecule, wherein the polymerizable unsaturated group is a compound that reacts with the acrylic acid ester represented by the general formula [1] to form an acrylic acid ester (a)/compound (b) copolymer.
　このような化合物（ｂ）の具体例としては、例えば、一般式［２］～［５］で示される化合物が挙げられる。
一般式［２］：
Figure JPOXMLDOC01-appb-I000014
（式中、Ｒ２は、水素原子または炭素数１～６のアルキル基を表す。）
一般式［３］：
Figure JPOXMLDOC01-appb-I000015
（式中、Ａは、酸素原子または－ＮＨ－基を表し、Ｔ１は、ヒドロキシル基を有していてもよい炭素数１～６のアルキレン基を表し、Ｒ３は、水素原子または炭素数１～６のアルキル基を表す。）
一般式［４］：
Figure JPOXMLDOC01-appb-I000016
（式中、Ｔ２は、結合手または炭素数１～６のアルキレン基を表し、Ｒ４は、水素原子または炭素数１～６のアルキル基を表す。）
一般式［５］：
Figure JPOXMLDOC01-appb-I000017
（式中、Ｔ３は、炭素数１～６のアルキレン基を表し、Ｒ５は、水素原子または炭素数１～６のアルキル基を表す。） Specific examples of such compound (b) include compounds represented by general formulas [2] to [5].
General formula [2]:
Figure JPOXMLDOC01-appb-I000014
(In the formula, R 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
General formula [3]:
Figure JPOXMLDOC01-appb-I000015
(In the formula, A represents an oxygen atom or -NH- group, T 1 represents an alkylene group having 1 to 6 carbon atoms which may have a hydroxyl group, R 3 represents a hydrogen atom or a represents an alkyl group of 1 to 6.)
General formula [4]:
Figure JPOXMLDOC01-appb-I000016
(In the formula, T 2 represents a bond or an alkylene group having 1 to 6 carbon atoms, and R 4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
General formula [5]:
Figure JPOXMLDOC01-appb-I000017
(In the formula, T 3 represents an alkylene group having 1 to 6 carbon atoms, and R 5 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
　一般式［２］～［５］におけるＲ２～Ｒ５で示される炭素数１～６のアルキル基としては、炭素数１～３のアルキル基が好ましく、炭素数１のアルキル基がより好ましい。また、該アルキル基としては、直鎖状、分枝状もしくは環状のいずれであってもよく、なかでも、直鎖状もしくは分枝状のものが好ましい。このようなアルキル基の具体例としては、一般式［１］におけるＲ１で示される炭素数１～６のアルキル基の具体例と同一の基が挙げられ、好ましい具体例やより好ましい具体例も同一である。 The alkyl group having 1 to 6 carbon atoms represented by R 2 to R 5 in general formulas [2] to [5] is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 carbon atom. In addition, the alkyl group may be linear, branched or cyclic, with linear or branched being preferred. Specific examples of such an alkyl group include the same groups as specific examples of the alkyl group having 1 to 6 carbon atoms represented by R 1 in general formula [1], and preferred specific examples and more preferred specific examples are also given. are identical.
　一般式［２］～［５］におけるＲ２～Ｒ５としては、水素原子が好ましい。 Hydrogen atoms are preferred as R 2 to R 5 in general formulas [2] to [5].
　一般式［３］におけるＡとしては、酸素原子が好ましい。 An oxygen atom is preferable as A in the general formula [3].
　一般式［３］におけるＴ１で示される、ヒドロキシル基を有していてもよい炭素数１～６のアルキレン基としては、ヒドロキシル基を有していてもよい炭素数１～４のアルキレン基が好ましく、ヒドロキシル基を有していてもよい炭素数２～４のアルキレン基がより好ましい。該アルキレン基としては、直鎖状、分枝状もしくは環状のいずれであってもよく、なかでも、直鎖状もしくは分枝状のものが好ましい。また、ヒドロキシル基を有する場合のヒドロキシル基の数は、１つないし複数であってもよい。このようなヒドロキシル基を有していてもよいアルキレン基の具体例としては、例えば、メチレン基、ヒドロキシメチレン基、ジメチレン基（エチレン基）、ヒドロキシジメチレン基（ヒドロキシエチレン基）、トリメチレン基、１-ヒドロキシトリメチレン基、２-ヒドロキシトリメチレン基、イソプロピレン基、ヒドロキシイソプロピレン基、テトラメチレン基、ヒドロキシテトラメチレン基、１-メチルトリメチレン基、２-メチルトリメチレン基、１，１-ジメチルジメチレン基、シクロブチレン基、ペンタメチレン基、シクロペンチレン基、ヘキサメチレン基、シクロヘキシレン基等が挙げられる。これらのヒドロキシル基を有していてもよいアルキレン基のなかでも、ジメチレン基（エチレン基）、トリメチレン基、２-ヒドロキシトリメチレン基、１，１-ジメチルジメチレン基が好ましい。 The alkylene group having 1 to 6 carbon atoms which may have a hydroxyl group represented by T 1 in the general formula [3] is an alkylene group having 1 to 4 carbon atoms which may have a hydroxyl group. An alkylene group having 2 to 4 carbon atoms, which may have a hydroxyl group, is more preferred. The alkylene group may be linear, branched or cyclic, with linear or branched being preferred. Moreover, when having a hydroxyl group, the number of hydroxyl groups may be one or more. Specific examples of the alkylene group optionally having a hydroxyl group include, for example, a methylene group, a hydroxymethylene group, a dimethylene group (ethylene group), a hydroxydimethylene group (hydroxyethylene group), a trimethylene group, -hydroxytrimethylene group, 2-hydroxytrimethylene group, isopropylene group, hydroxyisopropylene group, tetramethylene group, hydroxytetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1,1-dimethyl dimethylene group, cyclobutylene group, pentamethylene group, cyclopentylene group, hexamethylene group, cyclohexylene group and the like. Among these alkylene groups which may have a hydroxyl group, a dimethylene group (ethylene group), a trimethylene group, a 2-hydroxytrimethylene group and a 1,1-dimethyldimethylene group are preferred.
　一般式［４］におけるＴ２で示される結合手とは、Ｔ２には原子が存在せず、Ｔ２に結合している「硫黄原子」と、Ｔ２に結合している「Ｒ４に結合している炭素原子」とが、Ｔ２を介さずに直接結合していることを意味する。 The bond represented by T 2 in the general formula [4] is a “sulfur atom” that does not have an atom in T 2 and is bonded to T 2 , and a “R 4 "bonded carbon atom" means directly bonded without going through T2 .
　一般式［４］におけるＴ２で示される炭素数１～６のアルキレン基としては、炭素数１～４のアルキレン基が好ましく、炭素数１のアルキレン基がより好ましい。また、該アルキレン基としては、直鎖状、分枝状もしくは環状のいずれであってもよく、なかでも、直鎖状のものが好ましい。このようなアルキレン基の具体例としては、例えば、メチレン基、ジメチレン基（エチレン基）、トリメチレン基、イソプロピレン基、テトラメチレン基、１-メチルトリメチレン基、２-メチルトリメチレン基、１，１-ジメチルジメチレン基、シクロブチレン基、ペンタメチレン基、シクロペンチレン基、ヘキサメチレン基、シクロヘキシレン基等が挙げられる。これらのアルキレン基のなかでも、炭素数１～４の直鎖状のアルキレン基が好ましく、メチレン基がより好ましい。 The alkylene group having 1 to 6 carbon atoms represented by T 2 in general formula [4] is preferably an alkylene group having 1 to 4 carbon atoms, and more preferably an alkylene group having 1 carbon atom. Further, the alkylene group may be linear, branched or cyclic, with linear ones being preferred. Specific examples of such alkylene groups include, for example, methylene group, dimethylene group (ethylene group), trimethylene group, isopropylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1, 1-dimethyldimethylene group, cyclobutylene group, pentamethylene group, cyclopentylene group, hexamethylene group, cyclohexylene group and the like. Among these alkylene groups, straight-chain alkylene groups having 1 to 4 carbon atoms are preferred, and methylene groups are more preferred.
　一般式［５］におけるＴ３で示される炭素数１～６のアルキレン基としては、炭素数１～４のアルキレン基が好ましく、炭素数２のアルキレン基がより好ましい。また、該アルキレン基としては、直鎖状、分枝状もしくは環状のいずれであってもよく、なかでも、直鎖状のものが好ましい。このようなアルキレン基の具体例としては、一般式［４］におけるＴ２で示される炭素数１～６のアルキレン基の具体例と同一の基が挙げられる。これらのアルキレン基のなかでも、炭素数１～４の直鎖状のアルキレン基が好ましく、ジメチレン基（エチレン基）がより好ましい。 The alkylene group having 1 to 6 carbon atoms represented by T 3 in general formula [5] is preferably an alkylene group having 1 to 4 carbon atoms, and more preferably an alkylene group having 2 carbon atoms. Further, the alkylene group may be linear, branched or cyclic, with linear ones being preferred. Specific examples of such an alkylene group include the same groups as the specific examples of the alkylene group having 1 to 6 carbon atoms represented by T 2 in general formula [4]. Among these alkylene groups, a linear alkylene group having 1 to 4 carbon atoms is preferable, and a dimethylene group (ethylene group) is more preferable.
　一般式［２］で示される化合物の具体例としては、例えば、アクリル酸、メタクリル酸等が挙げられる。 Specific examples of the compound represented by general formula [2] include acrylic acid and methacrylic acid.
　一般式［３］で示される化合物の具体例としては、例えば、２-（アクリロイルオキシ）エタンスルホン酸、２-（メタクリロイルオキシ）エタンスルホン酸、３-（アクリロイルオキシ）プロパンスルホン酸、３-（メタクリロイルオキシ）プロパンスルホン酸、２-アクリロイルオキシ-２-メチルプロパンスルホン酸、２-メタクリロイルオキシ-２-メチルプロパンスルホン酸、３-アクリロイルオキシ-２-ヒドロキシプロパンスルホン酸、３-メタクリロイルオキシ-２-ヒドロキシプロパンスルホン酸、２-アクリルアミド-２-メチルプロパンスルホン酸、２-メタクリルアミド-２-メチルプロパンスルホン酸等が挙げられる。 Specific examples of the compound represented by the general formula [3] include 2-(acryloyloxy)ethanesulfonic acid, 2-(methacryloyloxy)ethanesulfonic acid, 3-(acryloyloxy)propanesulfonic acid, 3-( methacryloyloxy)propanesulfonic acid, 2-acryloyloxy-2-methylpropanesulfonic acid, 2-methacryloyloxy-2-methylpropanesulfonic acid, 3-acryloyloxy-2-hydroxypropanesulfonic acid, 3-methacryloyloxy-2- Hydroxypropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid and the like.
　一般式［４］で示される化合物の具体例としては、例えば、ビニルスルホン酸、アリルスルホン酸等が挙げられる。 Specific examples of the compound represented by general formula [4] include vinylsulfonic acid, allylsulfonic acid, and the like.
　一般式［５］で示される化合物の具体例としては、例えば、リン酸２-（アクリロイルオキシ）エチル、リン酸２-（メタクリロイルオキシ）エチル等が挙げられる。 Specific examples of the compound represented by general formula [5] include 2-(acryloyloxy)ethyl phosphate, 2-(methacryloyloxy)ethyl phosphate, and the like.
　上述した化合物（ｂ）のなかでも、一般式［２］で示される化合物が好ましく、アクリル酸、メタクリル酸がより好ましく、アクリル酸がさらに好ましい。 Among the compounds (b) described above, the compounds represented by the general formula [2] are preferred, acrylic acid and methacrylic acid are more preferred, and acrylic acid is even more preferred.
　これらの化合物（ｂ）は、市販のものを用いてもよいし、自体公知の方法によって適宜合成したものを用いてもよい。 These compounds (b) may be commercially available ones, or may be appropriately synthesized by a method known per se.
　本発明にかかる共重合体におけるアクリル酸エステル（ａ）と化合物（ｂ）との割合（質量比）は、通常（ａ）／（ｂ）＝６．０／９４．０～３０．０～７０．０であり、好ましくは（ａ）／（ｂ）＝９．０／９１．０～２８．５／７１．５であり、より好ましくは（ａ）／（ｂ）＝１４．０／８６．０～２７．３／７２．７であり、さらに好ましくは（ａ）／（ｂ）＝１４．０／８６．０～２５．０／７５．０であり、特に好ましくは１４．５／８５．５～２０．０／８０．０である。アクリル酸エステル（ａ）と化合物（ｂ）との割合（質量比）が６．０／９４．０より小さい場合には、乳化組成物を調製した際に、電解質の存在下で十分な粘度が得られずに使用しづらくなる場合がある。また、アクリル酸エステル（ａ）と化合物（ｂ）との割合（質量比）が３０．０／７０．０を超える場合には、乳化組成物を調製した際に、低濃度（例えば、０．５質量％以下）の電解質存在下の粘度が著しく高くなるばかりでなく、電解質の濃度が高くなるにつれて、急激に粘度が低くなってしまい、電解質濃度による粘度変化が大きくて使用しづらくなる場合がある。 The ratio (mass ratio) of acrylic acid ester (a) and compound (b) in the copolymer according to the present invention is usually (a)/(b) = 6.0/94.0 to 30.0 to 70. .0, preferably (a)/(b) = 9.0/91.0 to 28.5/71.5, more preferably (a)/(b) = 14.0/86. 0 to 27.3/72.7, more preferably (a)/(b)=14.0/86.0 to 25.0/75.0, particularly preferably 14.5/85. 5 to 20.0/80.0. When the ratio (mass ratio) of the acrylic acid ester (a) and the compound (b) is less than 6.0/94.0, sufficient viscosity is obtained in the presence of the electrolyte when the emulsified composition is prepared. It may become difficult to use without obtaining it. Further, when the ratio (mass ratio) of the acrylic acid ester (a) and the compound (b) exceeds 30.0/70.0, when the emulsified composition is prepared, a low concentration (for example, 0.5%) is obtained. Not only does the viscosity increase significantly in the presence of an electrolyte (5% by mass or less), but as the concentration of the electrolyte increases, the viscosity decreases rapidly, and the viscosity changes greatly depending on the concentration of the electrolyte, making it difficult to use. be.
　本発明にかかる共重合体におけるアクリル酸エステル（ａ）と化合物（ｂ）との割合（質量比）が、（ａ）／（ｂ）＝１４．０／８６．０～２５．０／７５．０の範囲内である場合には、乳化組成物を調製した際に、高濃度（例えば、２～５質量％）の電解質存在下で高い粘度が保たれ易いことから、アクリル酸エステル（ａ）と化合物（ｂ）とが上述した割合（質量比）の範囲内にある本発明にかかる共重合体（成分Ａ）を含む乳化組成物は、高濃度（例えば、２～５質量％）の電解質が共存する皮膚外用剤や化粧料に好適に用いることができる。 The ratio (mass ratio) of acrylic acid ester (a) and compound (b) in the copolymer of the present invention is (a)/(b)=14.0/86.0 to 25.0/75. When it is within the range of 0, when preparing an emulsified composition, a high viscosity (for example, 2 to 5% by mass) in the presence of an electrolyte tends to be maintained, so that the acrylic acid ester (a) and the compound (b) in the range of the ratio (mass ratio) described above, the emulsion composition containing the copolymer (component A) according to the present invention contains a high concentration (for example, 2 to 5% by mass) of the electrolyte It can be suitably used for external skin preparations and cosmetics in which
　本発明にかかる共重合体におけるアクリル酸エステル（ａ）と化合物（ｂ）との割合（質量比）が、（ａ）／（ｂ）＝１４．５／８５．５～２０．０／８０．０の範囲内である場合には、乳化組成物を調製した際に、高濃度（例えば、２～５質量％）の電解質存在下でより高い粘度が保たれ易いことから、アクリル酸エステル（ａ）と化合物（ｂ）とが上述した割合（質量比）の範囲内にある本発明にかかる共重合体（成分Ａ）を含む乳化組成物は、高粘性を特長とする皮膚外用剤や化粧料に好適に用いることができる。 The ratio (mass ratio) of acrylic acid ester (a) and compound (b) in the copolymer of the present invention is (a)/(b)=14.5/85.5 to 20.0/80. When it is within the range of 0, when preparing the emulsified composition, a higher viscosity is likely to be maintained in the presence of a high-concentration (for example, 2 to 5% by mass) electrolyte, so the acrylic acid ester (a ) and the compound (b) in the ratio (mass ratio) described above, the emulsified composition containing the copolymer (component A) according to the present invention is characterized by high viscosity and is used as an external skin preparation or cosmetic. It can be suitably used for
　本発明にかかる共重合体におけるアクリル酸エステル（ａ）と化合物（ｂ）との割合（モル比）は、通常（ａ）／（ｂ）＝１．１／９８．９～６．９／９３．１であり、好ましくは（ａ）／（ｂ）＝１．５／９８．５～６．５／９３．５であり、より好ましくは（ａ）／（ｂ）＝２．０／９８．０～６．０／９４．０であり、さらに好ましくは（ａ）／（ｂ）＝２．５／９７．５～５．５／９４．５であり、特に好ましくは（ａ）／（ｂ）＝２．５／９７．５～４．５／９５．５であり、最も好ましくは３．０／９７．０～４．０／９６．０である。アクリル酸エステル（ａ）と化合物（ｂ）との割合（モル比）が１．１／９８．９より小さい場合には、乳化組成物を調製した際に、電解質の存在下で十分な粘度が得られずに使用しづらくなる場合がある。また、アクリル酸エステル（ａ）と化合物（ｂ）との割合（モル比）が６．９／９３．１を超える場合には、乳化組成物を調製した際に、低濃度（例えば、０．５質量％以下）の電解質存在下の粘度が著しく高くなるばかりでなく、電解質の濃度が高くなるにつれて、急激に粘度が低くなってしまい、電解質濃度による粘度変化が大きくて使用しづらくなる場合がある。 The ratio (molar ratio) of acrylic acid ester (a) and compound (b) in the copolymer according to the present invention is usually (a)/(b) = 1.1/98.9 to 6.9/93. .1, preferably (a)/(b) = 1.5/98.5 to 6.5/93.5, more preferably (a)/(b) = 2.0/98. 0 to 6.0/94.0, more preferably (a)/(b) = 2.5/97.5 to 5.5/94.5, particularly preferably (a)/(b )=2.5/97.5 to 4.5/95.5, most preferably 3.0/97.0 to 4.0/96.0. When the ratio (molar ratio) of the acrylic acid ester (a) and the compound (b) is less than 1.1/98.9, when the emulsified composition is prepared, sufficient viscosity is obtained in the presence of the electrolyte. It may become difficult to use without obtaining it. Further, when the ratio (molar ratio) of the acrylic acid ester (a) and the compound (b) exceeds 6.9/93.1, when the emulsified composition is prepared, a low concentration (for example, 0.1 Not only does the viscosity increase significantly in the presence of an electrolyte (5% by mass or less), but as the concentration of the electrolyte increases, the viscosity decreases rapidly, and the viscosity changes greatly depending on the concentration of the electrolyte, making it difficult to use. be.
　本発明にかかる共重合体におけるアクリル酸エステル（ａ）と化合物（ｂ）との割合（モル比）が、（ａ）／（ｂ）＝２．５／９７．５～４．５／９５．５の範囲内である場合には、乳化組成物を調製した際に、高濃度（例えば、２～５質量％）の電解質存在下で高い粘度が保たれ易いことから、アクリル酸エステル（ａ）と化合物（ｂ）とが上述した割合（モル比）の範囲内にある本発明にかかる共重合体（成分Ａ）を含む乳化組成物は、高濃度（例えば、２～５質量％）の電解質が共存する皮膚外用剤や化粧料に好適に用いることができる。 The ratio (molar ratio) of acrylic acid ester (a) and compound (b) in the copolymer of the present invention is (a)/(b)=2.5/97.5 to 4.5/95. If it is within the range of 5, when preparing an emulsified composition, a high viscosity (for example, 2 to 5% by mass) in the presence of an electrolyte tends to be maintained, so the acrylic acid ester (a) The emulsion composition containing the copolymer (component A) according to the present invention in which the ratio (molar ratio) of the compound (b) and the compound (b) is within the range described above, has a high concentration (for example, 2 to 5% by mass) of the electrolyte It can be suitably used for external skin preparations and cosmetics in which
　本発明にかかる共重合体におけるアクリル酸エステル（ａ）と化合物（ｂ）との割合（モル比）が、（ａ）／（ｂ）＝３．０／９７．０～４．０／９６．０の範囲内である場合には、乳化組成物を調製した際に、高濃度（例えば、２～５質量％）の電解質存在下でより高い粘度が保たれ易いことから、アクリル酸エステル（ａ）と化合物（ｂ）とが上述した割合（モル比）の範囲内にある本発明にかかる共重合体（成分Ａ）を含む乳化組成物は、高粘性を特長とする皮膚外用剤や化粧料に好適に用いることができる。 The ratio (molar ratio) of acrylic acid ester (a) and compound (b) in the copolymer of the present invention is (a)/(b)=3.0/97.0 to 4.0/96. When it is within the range of 0, when preparing the emulsified composition, a higher viscosity is likely to be maintained in the presence of a high-concentration (for example, 2 to 5% by mass) electrolyte, so the acrylic acid ester (a ) and the compound (b) in the ratio (molar ratio) of the present invention is within the range described above (component A). It can be suitably used for
　本発明にかかる共重合体は、アクリル酸エステル（ａ）、化合物（ｂ）のほかに、更に（ｃ）エチレン性不飽和基を２個以上有する化合物を構成成分として含んでいてもよい。すなわち、化合物（ｃ）をさらに含む本発明にかかる共重合体とは、少なくとも、アクリル酸エステル（ａ）と化合物（ｂ）と化合物（ｃ）を構成成分とする、アクリル酸エステル（ａ）由来の構成単位と化合物（ｂ）由来の構成単位と化合物（ｃ）由来の構成単位を有する共重合体である。 The copolymer according to the present invention may further contain (c) a compound having two or more ethylenically unsaturated groups as a constituent component, in addition to the acrylic acid ester (a) and the compound (b). That is, the copolymer according to the present invention further containing the compound (c) is at least the acrylic ester (a)-derived copolymer having the acrylic ester (a), the compound (b), and the compound (c) as constituent components. and a structural unit derived from the compound (b) and a structural unit derived from the compound (c).
　本発明にかかる共重合体としては、更に（ｃ）エチレン性不飽和基を２個以上有する化合物を構成成分として含む、アクリル酸エステル（ａ）／化合物（ｂ）／化合物（ｃ）共重合体が好ましい。 As the copolymer according to the present invention, an acrylic ester (a)/compound (b)/compound (c) copolymer further containing (c) a compound having two or more ethylenically unsaturated groups as a constituent component is preferred.
　（ｃ）エチレン性不飽和基を２個以上有する化合物とは、アクリル酸エステル（ａ）および化合物（ｂ）と反応し得るエチレン性不飽和基を分子内に２個以上有する化合物であって、いわゆる架橋剤の役割を担う化合物である。 (c) The compound having two or more ethylenically unsaturated groups is a compound having two or more ethylenically unsaturated groups in the molecule that can react with the acrylic acid ester (a) and the compound (b), It is a compound that plays the role of a so-called cross-linking agent.
　このような化合物（ｃ）の具体例としては、例えば、一般式［６］～［１６］で示される化合物が挙げられる。
一般式［６］：
Figure JPOXMLDOC01-appb-I000018
（式中、ｋは、１～６の整数を表す。）
一般式［７］：
Figure JPOXMLDOC01-appb-I000019
（式中、Ｔ４は、炭素数１～２０のアルキレン基、一般式［７-１］で示される基または一般式［７-２］で示される基を表し、Ｒ６およびＲ６'はそれぞれ独立して、水素原子またはメチル基を表す。）
一般式［７-１］：
Figure JPOXMLDOC01-appb-I000020
（式中、ｐ個のＴ４'はそれぞれ独立して、炭素数１～６のアルキレン基を表し、ｐは、１～６の整数を表す。）
一般式［７-２］：
Figure JPOXMLDOC01-appb-I000021
（式中、ｐ'個のＴ４''およびＴ４'''はそれぞれ独立して、炭素数１～６のアルキレン基を表し、ｐ'は、１～１２の整数を表す。）
一般式［８］：
Figure JPOXMLDOC01-appb-I000022
（式中、Ｔ５、Ｔ５'、Ｔ５''、Ｔ６、Ｔ６'、Ｔ６''およびＴ７はそれぞれ独立して、炭素数１～３のアルキレン基を表す。）
一般式［９］：
Figure JPOXMLDOC01-appb-I000023
（式中、ｑ個のＴ８、ｑ'個のＴ８'、ｒ個のＴ９およびｒ'個のＴ９'はそれぞれ独立して、炭素数１～６のアルキレン基を表し、ｑおよびｑ'は、０または１を表し、ｒは、１～６の整数を表し、ｒ'は、０～６の整数を表す。）
一般式［１０］：
Figure JPOXMLDOC01-appb-I000024
（式中、Ｒ７～Ｒ１４はそれぞれ独立して、水素原子、ビニル基またはビニルカルボニル基を表す。ただし、Ｒ７～Ｒ１４のうちの少なくとも２つのＲは、ビニル基またはビニルカルボニル基を表す。）
一般式［１１］：
Figure JPOXMLDOC01-appb-I000025
（式中、Ｔ１０、Ｔ１１およびＴ１１'はそれぞれ独立して、炭素数１～６のアルキレン基を表す。）
一般式［１２］：
Figure JPOXMLDOC01-appb-I000026
（式中、ｔ個のＴ１２はそれぞれ独立して、炭素数１～６のアルキレン基を表し、Ｒ１５は、炭素数６～１０の２～４価の芳香族炭化水素基を表し、ｔは、２～４の整数を表す。）
一般式［１３］：
Figure JPOXMLDOC01-appb-I000027
（式中、Ｔ１３は、炭素数１～６のアルキレン基を表し、Ｔ１４およびＴ１４'はそれぞれ独立して、炭素数６～１０のアリーレン基を表す。）
一般式［１４］：
Figure JPOXMLDOC01-appb-I000028
（式中、Ｔ１５は、炭素数６～１０のアリーレン基を表す。）
一般式［１５］：
Figure JPOXMLDOC01-appb-I000029
（式中、ｖは、０～６の整数を表す。）
一般式［１６］：
Figure JPOXMLDOC01-appb-I000030
（式中、Ｔ１６は、炭素数１～６のアルキレン基を表す。） Specific examples of such compound (c) include compounds represented by general formulas [6] to [16].
General formula [6]:
Figure JPOXMLDOC01-appb-I000018
(Wherein, k represents an integer of 1 to 6.)
General formula [7]:
Figure JPOXMLDOC01-appb-I000019
(Wherein, T 4 represents an alkylene group having 1 to 20 carbon atoms, a group represented by general formula [7-1] or a group represented by general formula [7-2], and R 6 and R 6′ are Each independently represents a hydrogen atom or a methyl group.)
General formula [7-1]:
Figure JPOXMLDOC01-appb-I000020
(Wherein, p T 4 's each independently represent an alkylene group having 1 to 6 carbon atoms, and p represents an integer of 1 to 6.)
General formula [7-2]:
Figure JPOXMLDOC01-appb-I000021
(In the formula, p' pieces of T 4 '' and T 4 ''' each independently represent an alkylene group having 1 to 6 carbon atoms, and p' represents an integer of 1 to 12.)
General formula [8]:
Figure JPOXMLDOC01-appb-I000022
(Wherein, T 5 , T 5 ', T 5 '', T 6 , T 6 ', T 6 '' and T 7 each independently represent an alkylene group having 1 to 3 carbon atoms.)
General formula [9]:
Figure JPOXMLDOC01-appb-I000023
(Wherein, q T 8 , q' T 8 ', r T 9 and r' T 9 ' each independently represent an alkylene group having 1 to 6 carbon atoms, and q and q' represents 0 or 1, r represents an integer of 1 to 6, and r' represents an integer of 0 to 6.)
General formula [10]:
Figure JPOXMLDOC01-appb-I000024
(wherein R 7 to R 14 each independently represent a hydrogen atom, a vinyl group or a vinylcarbonyl group, provided that at least two Rs among R 7 to R 14 each represent a vinyl group or a vinylcarbonyl group; show.)
General formula [11]:
Figure JPOXMLDOC01-appb-I000025
(In the formula, T 10 , T 11 and T 11 ' each independently represent an alkylene group having 1 to 6 carbon atoms.)
General formula [12]:
Figure JPOXMLDOC01-appb-I000026
(Wherein, t T 12 each independently represent an alkylene group having 1 to 6 carbon atoms, R 15 represents a divalent to tetravalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and t represents an integer from 2 to 4.)
General formula [13]:
Figure JPOXMLDOC01-appb-I000027
(In the formula, T 13 represents an alkylene group having 1 to 6 carbon atoms, and T 14 and T 14 ' each independently represent an arylene group having 6 to 10 carbon atoms.)
General formula [14]:
Figure JPOXMLDOC01-appb-I000028
(In the formula, T 15 represents an arylene group having 6 to 10 carbon atoms.)
General formula [15]:
Figure JPOXMLDOC01-appb-I000029
(Wherein, v represents an integer from 0 to 6.)
General formula [16]:
Figure JPOXMLDOC01-appb-I000030
(In the formula, T 16 represents an alkylene group having 1 to 6 carbon atoms.)
　一般式［６］におけるｋとしては、１～４の整数が好ましく、１がより好ましい。 k in the general formula [6] is preferably an integer of 1 to 4, more preferably 1.
　一般式［７］におけるＲ６およびＲ６'としては、水素原子が好ましい。 A hydrogen atom is preferable as R 6 and R 6′ in general formula [7].
　一般式［７］におけるＴ４で示される炭素数１～２０のアルキレン基としては、炭素数１～１０のアルキレン基が好ましい。また、該アルキレン基としては、直鎖状、分枝状もしくは環状のいずれであってもよく、なかでも、直鎖状のものが好ましい。このようなアルキレン基の具体例としては、例えば、メチレン基、ジメチレン基（エチレン基）、トリメチレン基、イソプロピレン基、テトラメチレン基、１-メチルトリメチレン基、２-メチルトリメチレン基、１，１-ジメチルジメチレン基、シクロブチレン基、ペンタメチレン基、シクロペンチレン基、ヘキサメチレン基、シクロヘキシレン基、ヘプタメチレン基、シクロヘプチレン基、オクタメチレン基、シクロオクチレン基、ノナメチレン基、シクロノニレン基、デカメチレン基、シクロデシレン基、ウンデカメチレン基、シクロウンデシレン基、ドデカメチレン基、シクロドデシレン基、トリデカメチレン基、シクロトリデシレン基、テトラデカメチレン基、シクロテトラデシレン基、ペンタデカメチレン基、シクロペンタデシレン基、ヘキサデカメチレン基、シクロヘキサデシレン基、ヘプタデカメチレン基、シクロヘプタデシレン基、オクタデカメチレン基、シクロオクタデシレン基、ノナデカメチレン基、シクロノナデシレン基、イコシレン基、シクロイコシレン基等が挙げられる。これらのアルキレン基のなかでも、炭素数１～１０の直鎖状のアルキレン基が好ましい。 The alkylene group having 1 to 20 carbon atoms represented by T 4 in general formula [7] is preferably an alkylene group having 1 to 10 carbon atoms. Further, the alkylene group may be linear, branched or cyclic, with linear ones being preferred. Specific examples of such alkylene groups include, for example, methylene group, dimethylene group (ethylene group), trimethylene group, isopropylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1, 1-dimethyldimethylene group, cyclobutylene group, pentamethylene group, cyclopentylene group, hexamethylene group, cyclohexylene group, heptamethylene group, cycloheptylene group, octamethylene group, cyclooctylene group, nonamethylene group, cyclononylene group, decamethylene group, cyclodecylene group, undecamethylene group, cycloundecylene group, dodecamethylene group, cyclododecylene group, tridecamethylene group, cyclotridecylene group, tetradecamethylene group, cyclotetradecylene group, pentadecamethylene group, cyclopenta decylene group, hexadecamethylene group, cyclohexadecylene group, heptadecamethylene group, cycloheptadecylene group, octadecamethylene group, cyclooctadecylene group, nonadecamethylene group, cyclononadecylene group, icosilene group, A cycloicosylene group and the like can be mentioned. Among these alkylene groups, straight-chain alkylene groups having 1 to 10 carbon atoms are preferred.
　一般式［７-１］におけるＴ４'ならびに一般式［７-２］におけるＴ４''およびＴ４'''で示される炭素数１～６のアルキレン基としては、炭素数１～３のアルキレン基が好ましい。また、該アルキレン基としては、直鎖状、分枝状もしくは環状のいずれであってもよく、なかでも、直鎖状のものが好ましい。このようなアルキレン基の具体例としては、一般式［４］におけるＴ２で示される炭素数１～６のアルキレン基の具体例と同一の基が挙げられる。これらのアルキレン基のなかでも、炭素数１～３の直鎖状のアルキレン基が好ましい。 The alkylene group having 1 to 6 carbon atoms represented by T 4 ' in general formula [7-1] and T 4 '' and T 4 '' in general formula [7-2] includes Alkylene groups are preferred. Further, the alkylene group may be linear, branched or cyclic, with linear ones being preferred. Specific examples of such an alkylene group include the same groups as the specific examples of the alkylene group having 1 to 6 carbon atoms represented by T 2 in general formula [4]. Among these alkylene groups, straight-chain alkylene groups having 1 to 3 carbon atoms are preferred.
　一般式［７-１］におけるｐとしては、２～６の整数が好ましく、４～６の整数がより好ましい。 p in the general formula [7-1] is preferably an integer of 2 to 6, more preferably an integer of 4 to 6.
　一般式［７-２］におけるｐ'としては、１～７の整数が好ましく、１～５の整数がより好ましく、１～３の整数がさらに好ましい。 p' in general formula [7-2] is preferably an integer of 1 to 7, more preferably an integer of 1 to 5, and even more preferably an integer of 1 to 3.
　一般式［８］におけるＴ５、Ｔ５'、Ｔ５''、Ｔ６、Ｔ６'、Ｔ６''およびＴ７で示される炭素数１～３のアルキレン基としては、炭素数１のアルキレン基が好ましい。また、該アルキレン基としては、直鎖状もしくは分枝状のいずれであってもよく、なかでも、直鎖状のものが好ましい。このようなアルキレン基の具体例としては、例えば、メチレン基、ジメチレン基（エチレン基）、トリメチレン基、イソプロピレン基等が挙げられる。これらのアルキレン基のなかでも、メチレン基が好ましい。 The alkylene groups having 1 to 3 carbon atoms represented by T 5 , T 5 ', T 5 '', T 6 , T 6 ', T 6 '' and T 7 in the general formula [8] include Alkylene groups are preferred. In addition, the alkylene group may be linear or branched, with linear ones being preferred. Specific examples of such an alkylene group include, for example, a methylene group, a dimethylene group (ethylene group), a trimethylene group, an isopropylene group and the like. Among these alkylene groups, a methylene group is preferred.
　一般式［９］におけるＴ８、Ｔ８'、Ｔ９およびＴ９'で示される炭素数１～６のアルキレン基としては、炭素数１～３のアルキレン基が好ましく、炭素数１のアルキレン基がより好ましい。また、該アルキレン基としては、直鎖状、分枝状もしくは環状のいずれであってもよく、なかでも、直鎖状のものが好ましい。このようなアルキレン基の具体例としては、一般式［４］におけるＴ２で示される炭素数１～６のアルキレン基の具体例と同一の基が挙げられる。これらのアルキレン基のなかでも、Ｔ８およびＴ８'にあっては、メチレン基が好ましく、Ｔ９およびＴ９'にあっては、炭素数１～３の直鎖状のアルキレン基が好ましい。 The alkylene group having 1 to 6 carbon atoms represented by T 8 , T 8 ', T 9 and T 9 ' in the general formula [9] is preferably an alkylene group having 1 to 3 carbon atoms, and an alkylene group having 1 carbon atom. is more preferred. Further, the alkylene group may be linear, branched or cyclic, with linear ones being preferred. Specific examples of such an alkylene group include the same groups as the specific examples of the alkylene group having 1 to 6 carbon atoms represented by T 2 in general formula [4]. Among these alkylene groups, T 8 and T 8 ' are preferably methylene groups, and T 9 and T 9 ' are preferably linear alkylene groups having 1 to 3 carbon atoms.
　一般式［９］におけるｑおよびｑ'としては、１が好ましい。 1 is preferable as q and q' in general formula [9].
　一般式［９］におけるｒとしては、１～２の整数が好ましい。 An integer of 1 to 2 is preferable as r in general formula [9].
　一般式［９］におけるｒ'としては、０～２の整数が好ましい。 An integer of 0 to 2 is preferable as r' in general formula [9].
　一般式［１０］におけるＲ７～Ｒ１４は、少なくとも２つがビニル基またはビニルカルボニル基であればよく、５～８つがビニル基またはビニルカルボニル基であることが好ましく、５～７つがビニル基またはビニルカルボニル基であることがより好ましい。 At least two of R 7 to R 14 in general formula [10] may be vinyl groups or vinylcarbonyl groups, preferably 5 to 8 are vinyl groups or vinylcarbonyl groups, and 5 to 7 are vinyl groups or A vinyl carbonyl group is more preferred.
　一般式［１１］におけるＴ１０、Ｔ１１およびＴ１１'で示される炭素数１～６のアルキレン基としては、直鎖状、分枝状もしくは環状のいずれであってもよい。このようなアルキレン基の具体例としては、一般式［４］におけるＴ２で示される炭素数１～６のアルキレン基の具体例と同一の基が挙げられる。これらのアルキレン基のなかでも、Ｔ１０にあっては、シクロペンチレン基およびシクロヘキシレン基が好ましく、シクロヘキシレン基がより好ましく、Ｔ１１およびＴ１１'にあっては、メチレン基およびジメチレン基（エチレン基）が好ましく、メチレン基がより好ましい。 The alkylene group having 1 to 6 carbon atoms represented by T 10 , T 11 and T 11 ′ in general formula [11] may be linear, branched or cyclic. Specific examples of such an alkylene group include the same groups as the specific examples of the alkylene group having 1 to 6 carbon atoms represented by T 2 in general formula [4]. Among these alkylene groups, T 10 is preferably a cyclopentylene group and a cyclohexylene group, more preferably a cyclohexylene group, and T 11 and T 11 ' are a methylene group and a dimethylene group ( ethylene group) is preferred, and a methylene group is more preferred.
　一般式［１２］におけるＲ１５で示される炭素数６～１０の２～４価の芳香族炭化水素基としては、炭素数６の３～４価の芳香族炭化水素基が好ましい。このような芳香族炭化水素基の具体例としては、例えば、フェニレン基、ナフチレン基等の炭素数６～１０の２価の芳香族炭化水素基（アリーレン基）；ベンゼン、ナフタレンに由来する３価の芳香族炭化水素基；ベンゼン、ナフタレンに由来する４価の芳香族炭化水素基等が挙げられる。 As the divalent to tetravalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R 15 in general formula [12], a trivalent to tetravalent aromatic hydrocarbon group having 6 carbon atoms is preferable. Specific examples of such aromatic hydrocarbon groups include, for example, a divalent aromatic hydrocarbon group (arylene group) having 6 to 10 carbon atoms such as a phenylene group and a naphthylene group; aromatic hydrocarbon group; benzene, tetravalent aromatic hydrocarbon group derived from naphthalene, and the like.
　一般式［１２］におけるＴ１２で示される炭素数１～６のアルキレン基としては、炭素数１～３のアルキレン基が好ましい。また、該アルキレン基としては、直鎖状、分枝状もしくは環状のいずれであってもよく、直鎖状のものが好ましい。このようなアルキレン基の具体例としては、一般式［４］におけるＴ２で示される炭素数１～６のアルキレン基の具体例と同一の基が挙げられる。これらのアルキレン基のなかでも、炭素数１～３の直鎖状のアルキレン基が好ましい。 The alkylene group having 1 to 6 carbon atoms represented by T 12 in general formula [12] is preferably an alkylene group having 1 to 3 carbon atoms. The alkylene group may be linear, branched or cyclic, and preferably linear. Specific examples of such an alkylene group include the same groups as the specific examples of the alkylene group having 1 to 6 carbon atoms represented by T 2 in general formula [4]. Among these alkylene groups, straight-chain alkylene groups having 1 to 3 carbon atoms are preferred.
　一般式［１２］におけるｔとしては、３～４の整数が好ましい。 An integer of 3 to 4 is preferable as t in general formula [12].
　一般式［１３］におけるＴ１３で示される炭素数１～６のアルキレン基としては、炭素数１～３のアルキレン基が好ましい。また、該アルキレン基としては、直鎖状、分枝状もしくは環状のいずれであってもよく、直鎖状のものが好ましい。このようなアルキレン基の具体例としては、一般式［４］におけるＴ２で示される炭素数１～６のアルキレン基の具体例と同一の基が挙げられる。これらのアルキレン基のなかでも、炭素数１～３の直鎖状のアルキレン基が好ましい。 The alkylene group having 1 to 6 carbon atoms represented by T 13 in the general formula [13] is preferably an alkylene group having 1 to 3 carbon atoms. The alkylene group may be linear, branched or cyclic, and preferably linear. Specific examples of such an alkylene group include the same groups as the specific examples of the alkylene group having 1 to 6 carbon atoms represented by T 2 in general formula [4]. Among these alkylene groups, straight-chain alkylene groups having 1 to 3 carbon atoms are preferred.
　一般式［１３］におけるＴ１４およびＴ１４'ならびに一般式［１４］におけるＴ１５で示される炭素数６～１０のアリーレン基としては、炭素数６のアリーレン基が好ましい。このようなアリーレン基の具体例としては、例えば、フェニレン基、ナフチレン基等が挙げられる。これらのアリーレン基のなかでも、フェニレン基が好ましい。 As the arylene group having 6 to 10 carbon atoms represented by T 14 and T 14 ′ in general formula [13] and T 15 in general formula [14], an arylene group having 6 carbon atoms is preferred. Specific examples of such arylene groups include, for example, a phenylene group and a naphthylene group. Among these arylene groups, a phenylene group is preferred.
　一般式［１５］におけるｖとしては、０～２の整数が好ましく、０がより好ましい。 v in general formula [15] is preferably an integer of 0 to 2, more preferably 0.
　一般式［１６］におけるＴ１６で示される炭素数１～６のアルキレン基としては、炭素数１～３のアルキレン基が好ましく、炭素数１のアルキレン基がより好ましい。また、該アルキレン基としては、直鎖状、分枝状もしくは環状のいずれであってもよく、直鎖状のものが好ましい。このようなアルキレン基の具体例としては、一般式［４］におけるＴ２で示される炭素数１～６のアルキレン基の具体例と同一の基が挙げられる。これらのアルキレン基のなかでも、炭素数１～３の直鎖状のアルキレン基が好ましく、メチレン基がより好ましい。 The alkylene group having 1 to 6 carbon atoms represented by T 16 in general formula [16] is preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an alkylene group having 1 carbon atom. The alkylene group may be linear, branched or cyclic, and preferably linear. Specific examples of such an alkylene group include the same groups as the specific examples of the alkylene group having 1 to 6 carbon atoms represented by T 2 in general formula [4]. Among these alkylene groups, straight-chain alkylene groups having 1 to 3 carbon atoms are preferred, and methylene groups are more preferred.
　上述した化合物（ｃ）のなかでも、一般式［７］～［９］で示される化合物および一般式［１６］で示される化合物が好ましい。 Among the compounds (c) described above, compounds represented by general formulas [7] to [9] and compounds represented by general formula [16] are preferable.
　一般式［７］で示される化合物の具体例としては、例えば、１，１０-デカンジオールジアクリレート等が挙げられる。 Specific examples of the compound represented by general formula [7] include 1,10-decanediol diacrylate.
　一般式［８］で示される化合物の具体例としては、例えば、ペンタエリスリトールトリアリルエーテル等が挙げられる。 Specific examples of the compound represented by general formula [8] include pentaerythritol triallyl ether.
　一般式［９］で示される化合物の具体例としては、例えば、ジエチレングリコールジアリルエーテル、ジプロピレングリコールジアリルエーテル、ジブチレングリコールジアリルエーテル等のジアルキレングリコールジアリルエーテル；トリエチレングリコールジアリルエーテル、トリプロピレングリコールジアリルエーテル、トリブチレングリコールジアリルエーテル等のトリアルキレングリコールジアリルエーテル；ポリエチレングリコールジアリルエーテル、ポリプロピレングリコールジアリルエーテル、ポリブチレングリコールジアリルエーテル等のポリアルキレングリコールジアリルエーテル等が挙げられる。 Specific examples of the compound represented by the general formula [9] include dialkylene glycol diallyl ether such as diethylene glycol diallyl ether, dipropylene glycol diallyl ether, and dibutylene glycol diallyl ether; triethylene glycol diallyl ether, tripropylene glycol diallyl. ether, trialkylene glycol diallyl ether such as tributylene glycol diallyl ether; polyalkylene glycol diallyl ether such as polyethylene glycol diallyl ether, polypropylene glycol diallyl ether, polybutylene glycol diallyl ether;
　一般式［１６］で示される化合物の具体例としては、例えば、Ｎ，Ｎ'-メチレンビスアクリルアミド等が挙げられる。 Specific examples of the compound represented by general formula [16] include N,N'-methylenebisacrylamide and the like.
　上述した一般式［７］～［９］で示される化合物および一般式［１６］で示される化合物のなかでも、１，１０-デカンジオールジアクリレート、ペンタエリスリトールトリアリルエーテル、ジエチレングリコールジアリルエーテルおよびＮ，Ｎ'-メチレンビスアクリルアミドが好ましく、ジエチレングリコールジアリルエーテルがより好ましい。 Among the compounds represented by the general formulas [7] to [9] and the compounds represented by the general formula [16], 1,10-decanediol diacrylate, pentaerythritol triallyl ether, diethylene glycol diallyl ether and N, N'-methylenebisacrylamide is preferred, and diethylene glycol diallyl ether is more preferred.
　これらの化合物（ｃ）は、市販のものを用いてもよいし、自体公知の方法によって適宜合成したものを用いてもよい。 These compounds (c) may be commercially available ones, or may be appropriately synthesized by a method known per se.
　本発明にかかる共重合体における化合物（ｃ）の割合は、アクリル酸エステル（ａ）および化合物（ｂ）の合計１００質量部に対して、通常０．０００１～１．５質量部であり、好ましくは０．０２～１．５質量部であり、より好ましくは０．０４～１．２５質量部であり、さらに好ましくは０．０５～１．０１質量部であり、最も好ましくは０．２０～０．７０質量部である。アクリル酸エステル（ａ）および化合物（ｂ）の合計を１００質量部とした場合に、化合物（ｃ）の使用量が該１００質量部に対して１．５質量部を越える場合には、乳化組成物を調製した際に、電解質の存在下で十分な粘度が得られず使用しづらくなる場合がある。 The ratio of the compound (c) in the copolymer according to the present invention is usually 0.0001 to 1.5 parts by mass, preferably 100 parts by mass in total of the acrylic acid ester (a) and the compound (b). is 0.02 to 1.5 parts by mass, more preferably 0.04 to 1.25 parts by mass, still more preferably 0.05 to 1.01 parts by mass, most preferably 0.20 to It is 0.70 parts by mass. When the total amount of acrylic acid ester (a) and compound (b) is 100 parts by mass, and the amount of compound (c) used exceeds 1.5 parts by mass with respect to 100 parts by mass, the emulsified composition When preparing a product, it may not be possible to obtain sufficient viscosity in the presence of an electrolyte, making it difficult to use.
　本発明にかかる共重合体における化合物（ｃ）の割合が、アクリル酸エステル（ａ）および化合物（ｂ）の合計１００質量部に対して、０．０５～１．０１質量部の範囲内である場合には、乳化組成物を調製した際に、高濃度（例えば、２～５質量％）の電解質存在下で高い粘度が保たれ易いことから、化合物（ｃ）の割合が上述した質量部の範囲内にある本発明にかかる共重合体（成分Ａ）を含む乳化組成物は、高濃度（例えば、２～５質量％）の電解質が共存する皮膚外用剤や化粧料に好適に用いることができる。 The ratio of the compound (c) in the copolymer according to the present invention is within the range of 0.05 to 1.01 parts by mass with respect to a total of 100 parts by mass of the acrylic acid ester (a) and the compound (b). In some cases, when the emulsified composition is prepared, the high viscosity (for example, 2 to 5% by mass) of the electrolyte is likely to be maintained in the presence of a high concentration, so the proportion of the compound (c) is the above-mentioned parts by mass. Emulsified compositions containing the copolymer (component A) according to the present invention within the range can be suitably used for external skin preparations and cosmetics in which high concentration (for example, 2 to 5% by mass) electrolytes coexist. can.
　本発明にかかる共重合体における化合物（ｃ）の割合が、アクリル酸エステル（ａ）および化合物（ｂ）の合計１００質量部に対して、０．２０～０．７０質量部の範囲内である場合には、乳化組成物を調製した際に、高濃度（例えば、２～５質量％）の電解質存在下でより高い粘度が保たれ易いことから、化合物（ｃ）の割合が上述した質量部の範囲内にある本発明にかかる共重合体（成分Ａ）を含む乳化組成物は、高粘性を特長とする皮膚外用剤や化粧料に好適に用いることができる。 The ratio of the compound (c) in the copolymer according to the present invention is within the range of 0.20 to 0.70 parts by mass with respect to the total 100 parts by mass of the acrylic acid ester (a) and the compound (b). In some cases, when the emulsified composition is prepared, a higher viscosity is likely to be maintained in the presence of a high-concentration (for example, 2 to 5% by mass) electrolyte, so the proportion of the compound (c) is the above parts by mass. The emulsion composition containing the copolymer (component A) according to the present invention within the range of can be suitably used for external skin preparations and cosmetics characterized by high viscosity.
　本発明にかかる共重合体における化合物（ｃ）の割合は、アクリル酸エステル（ａ）および化合物（ｂ）の合計１００モルに対して、通常０．００００５～１．０モルであり、好ましくは０．０００５～０．７０モルであり、より好ましくは０．０００５～０．６０モルであり、さらに好ましくは０．０００５～０．５０モルであり、最も好ましくは０．０５～０．３０モルである。アクリル酸エステル（ａ）および化合物（ｂ）の合計を１００モルとした場合に、化合物（ｃ）の使用量が該１００モルに対して１．０モルを越える場合には、乳化組成物を調製した際に、電解質の存在下で十分な粘度が得られず使用しづらくなる場合がある。 The ratio of the compound (c) in the copolymer according to the present invention is usually 0.00005 to 1.0 mol, preferably 0, per 100 mol in total of the acrylic acid ester (a) and the compound (b). 0.0005 to 0.70 mol, more preferably 0.0005 to 0.60 mol, still more preferably 0.0005 to 0.50 mol, most preferably 0.05 to 0.30 mol. be. When the total amount of acrylic acid ester (a) and compound (b) is 100 mol, and the amount of compound (c) used exceeds 1.0 mol per 100 mol, an emulsified composition is prepared. However, in the presence of electrolyte, sufficient viscosity may not be obtained, making it difficult to use.
　本発明にかかる共重合体において、アクリル酸エステル（ａ）と化合物（ｂ）との割合（モル比）が、（ａ）／（ｂ）＝２．５／９７．５～３．５／９６．５である場合には、化合物（ｃ）の割合は、アクリル酸エステル（ａ）および化合物（ｂ）の合計１００モルに対して、好ましくは０．０１～１．０モルであり、より好ましくは０．０３～０．７０モルであり、さらに好ましくは０．０５～０．６０モルであり、特に好ましくは０．０５～０．５０モルであり、最も好ましくは０．０５～０．３０モルである。 In the copolymer according to the present invention, the ratio (molar ratio) of acrylic acid ester (a) and compound (b) is (a)/(b) = 2.5/97.5 to 3.5/96 .5, the ratio of compound (c) is preferably 0.01 to 1.0 mol, more preferably 100 mol in total of acrylic acid ester (a) and compound (b). is 0.03 to 0.70 mol, more preferably 0.05 to 0.60 mol, particularly preferably 0.05 to 0.50 mol, most preferably 0.05 to 0.30 Mole.
　本発明にかかる共重合体において、特に、アクリル酸エステル（ａ）と化合物（ｂ）との割合（モル比）が、（ａ）／（ｂ）＝３．０／９７．０である場合には、化合物（ｃ）の割合は、アクリル酸エステル（ａ）および化合物（ｂ）の合計１００モルに対して、好ましくは０．０１～１．０モルであり、より好ましくは０．０３～０．７０モルであり、さらに好ましくは０．０５～０．６０モルであり、特に好ましくは０．０５～０．５０モルであり、最も好ましくは０．０５～０．３０モルである。 In the copolymer according to the present invention, especially when the ratio (molar ratio) of acrylic acid ester (a) and compound (b) is (a)/(b) = 3.0/97.0 is preferably 0.01 to 1.0 mol, more preferably 0.03 to 0 0.70 mol, more preferably 0.05 to 0.60 mol, particularly preferably 0.05 to 0.50 mol, most preferably 0.05 to 0.30 mol.
　本発明にかかる共重合体において、アクリル酸エステル（ａ）と化合物（ｂ）との割合（モル比）が、（ａ）／（ｂ）＝４．５／９５．５～５．５／９４．５である場合には、化合物（ｃ）の割合は、アクリル酸エステル（ａ）および化合物（ｂ）の合計１００モルに対して、好ましくは０．００００５～０．７０モルであり、より好ましくは０．０００５～０．７０モルであり、さらに好ましくは０．０００５～０．５０モルであり、特に好ましくは０．０００５～０．４０モルであり、最も好ましくは０．０００５～０．３０モルである。 In the copolymer according to the present invention, the ratio (molar ratio) of acrylic acid ester (a) and compound (b) is (a)/(b) = 4.5/95.5 to 5.5/94 .5, the ratio of compound (c) is preferably 0.00005 to 0.70 mol, more preferably 100 mol in total of acrylic acid ester (a) and compound (b). is 0.0005 to 0.70 mol, more preferably 0.0005 to 0.50 mol, particularly preferably 0.0005 to 0.40 mol, most preferably 0.0005 to 0.30 Mole.
　本発明にかかる共重合体において、特に、アクリル酸エステル（ａ）と化合物（ｂ）との割合（モル比）が、（ａ）／（ｂ）＝５．０／９５．０である場合には、化合物（ｃ）の割合は、アクリル酸エステル（ａ）および化合物（ｂ）の合計１００モルに対して、好ましくは０．００００５～０．７０モルであり、より好ましくは０．０００５～０．７０モルであり、さらに好ましくは０．０００５～０．５０モルであり、特に好ましくは０．０００５～０．４０モルであり、最も好ましくは０．０００５～０．３０モルである。 In the copolymer according to the present invention, especially when the ratio (molar ratio) between the acrylic acid ester (a) and the compound (b) is (a)/(b) = 5.0/95.0 The ratio of compound (c) is preferably 0.00005 to 0.70 mol, more preferably 0.0005 to 0 0.70 mol, more preferably 0.0005 to 0.50 mol, particularly preferably 0.0005 to 0.40 mol, most preferably 0.0005 to 0.30 mol.
　本発明にかかる共重合体において、アクリル酸エステル（ａ）と化合物（ｂ）との割合（モル比）が、（ａ）／（ｂ）＝４．５／９５．５～５．５／９４．５である場合には、化合物（ｃ）を含まない共重合体が望ましい場合もある。 In the copolymer according to the present invention, the ratio (molar ratio) of acrylic acid ester (a) and compound (b) is (a)/(b) = 4.5/95.5 to 5.5/94 .5, a copolymer that does not contain compound (c) may be desirable.
　本発明にかかる共重合体において、特に、アクリル酸エステル（ａ）と化合物（ｂ）との割合（モル比）が、（Ａ）／（Ｂ）＝５．０／９５．０である場合には、化合物（ｃ）を含まない共重合体が望ましい場合もある。 In the copolymer according to the present invention, especially when the ratio (molar ratio) between the acrylic acid ester (a) and the compound (b) is (A)/(B) = 5.0/95.0 may be desired to be a copolymer that does not contain compound (c).
　本発明にかかる共重合体には、上述したアクリル酸エステル（ａ）、化合物（ｂ）および化合物（ｃ）以外の構成成分として、化合物（ｄ）を含んでいてもよい。すなわち、本発明にかかる共重合体としては、アクリル酸エステル（ａ）／化合物（ｂ）／化合物（ｃ）／化合物（ｄ）共重合体でもよい。 The copolymer according to the present invention may contain compound (d) as a constituent component other than acrylic acid ester (a), compound (b) and compound (c) described above. That is, the copolymer according to the present invention may be an acrylic acid ester (a)/compound (b)/compound (c)/compound (d) copolymer.
　このような化合物（ｄ）としては、アクリル酸エステル（ａ）、化合物（ｂ）および化合物（ｃ）以外のものであり、例えば、炭素－炭素二重結合、炭素－炭素三重結合等の重合性不飽和基を分子内に有する化合物であって、上記重合性不飽和基が、アクリル酸エステル（ａ）、化合物（ｂ）または化合物（ｃ）中の重合性不飽和基と反応することができる化合物である。このような化合物（ｄ）の具体例としては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル等の（メタ）アクリル酸エステル等が挙げられる。これらの化合物（ｄ）は、市販のものを用いてもよいし、自体公知の方法によって適宜合成したものを用いてもよい。 Examples of such compound (d) include those other than acrylate (a), compound (b) and compound (c), and include, for example, carbon-carbon double bonds, carbon-carbon triple bonds, and other polymerizable A compound having an unsaturated group in the molecule, wherein the polymerizable unsaturated group can react with the polymerizable unsaturated group in the acrylic acid ester (a), the compound (b), or the compound (c) is a compound. Specific examples of such compound (d) include (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate. These compounds (d) may be commercially available ones, or may be appropriately synthesized by a method known per se.
　本発明にかかる共重合体は、化合物（ｂ）由来の構成単位中のカルボキシル基、スルホ基またはリン酸基がアルカリ性化合物によって中和されていてもよい。すなわち、化合物（ｂ）由来の構成単位中のカルボキシル基、スルホ基またはリン酸基が塩の形態となっている共重合体も、本発明にかかる共重合体に含まれる。 In the copolymer according to the present invention, the carboxyl group, sulfo group or phosphoric acid group in the structural unit derived from compound (b) may be neutralized with an alkaline compound. That is, copolymers in which the carboxyl group, sulfo group or phosphoric acid group in the constituent units derived from compound (b) are in the form of salts are also included in the copolymers of the present invention.
　本発明にかかる共重合体の中和度は、通常０～１００％、好ましくは３０～１００％、より好ましくは６０～１００％である。なお、本明細書でいう「中和度」とは、共重合体中の酸基（カルボキシル基、スルホ基またはリン酸基）が、アルカリ性化合物によって中和されている度合いを指す。共重合体中のすべての酸基がアルカリ性化合物によって中和され、塩の形態となっている場合を１００％と定義する。 The degree of neutralization of the copolymer of the present invention is usually 0-100%, preferably 30-100%, more preferably 60-100%. As used herein, the term "neutralization degree" refers to the degree to which acid groups (carboxyl groups, sulfo groups or phosphoric acid groups) in the copolymer are neutralized by an alkaline compound. 100% is defined as the case where all the acid groups in the copolymer are neutralized with an alkaline compound to form a salt.
　上述したアルカリ性化合物としては、酸基を中和できるものであれば特に限定されず、例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物；水酸化マグネシウム、水酸化カルシウム等のアルカリ土類金属水酸化物；トリメチルアミン、トリエチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、２-アミノ-２-メチルプロパノール、２-アミノ-２-メチル-１，３-プロパンジオール、ジイソプロパノールアミン、トロメタミン、コカミドメチルモノエタノールアミン等のアミン類；アンモニア等が挙げられる。これらのアルカリ性化合物のなかでも、アルカリ金属水酸化物が好ましく、水酸化ナトリウムがより好ましい。 The above-mentioned alkaline compound is not particularly limited as long as it can neutralize an acid group, and examples thereof include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; magnesium hydroxide and calcium hydroxide. alkaline earth metal hydroxides such as; amines such as amine, tromethamine, cocamidemethylmonoethanolamine; and ammonia. Among these alkaline compounds, alkali metal hydroxides are preferred, and sodium hydroxide is more preferred.
　本発明にかかる共重合体は、成分Ａとして、乳化組成物中に１種類の共重合体を単独で用いてもよいし、２種以上の共重合体を組み合わせて用いてもよい。 As for the copolymer according to the present invention, as component A, one type of copolymer may be used alone in the emulsion composition, or two or more types of copolymers may be used in combination.
　本発明にかかる共重合体は、以下に示す特性を有するものが有用である。
　１質量％のアクリル酸エステル（ａ）／化合物（ｂ）共重合体と、２質量％のリン酸-Ｌ-アスコルビルマグネシウム・ｎ水和物（水分含有量１６～２０質量％）を含み、ｐＨが７．５である水溶液の２０℃における粘度が、９，０００ｍＰａ・ｓ以上である。 Copolymers according to the present invention that have the following properties are useful.
1% by mass of acrylic ester (a) / compound (b) copolymer and 2% by mass of magnesium phosphate-L-ascorbyl n-hydrate (moisture content: 16 to 20% by mass), pH is 7.5, the viscosity at 20° C. is 9,000 mPa·s or more.
　すなわち、本発明にかかる共重合体は、（ａ）一般式［１］で示されるアクリル酸エステル、ならびに（ｂ）重合性不飽和基と、カルボキシル基、スルホ基およびリン酸基からなる群から選ばれるいずれかの官能基とを分子内に有する化合物、要すれば、（ｃ）エチレン性不飽和基を２個以上有する化合物のそれぞれを単量体とし、それぞれの単量体を、アクリル酸エステル（ａ）と化合物（ｂ）との割合（質量比）が、（ａ）／（ｂ）＝６．０／９４．０～３０．０／７０．０であり、化合物（ｃ）を含む場合には、化合物（ｃ）の割合が、アクリル酸エステル（ａ）および化合物（ｂ）の合計１００質量部に対して、０．０００１～１．５質量部となるように重合して得られる、アクリル酸エステル（ａ）／化合物（ｂ）共重合体であって、上述した特性を有する共重合体が好ましい。 That is, the copolymer according to the present invention is composed of (a) an acrylic acid ester represented by the general formula [1], and (b) a polymerizable unsaturated group, a carboxyl group, a sulfo group, and a phosphoric acid group. A compound having any selected functional group in the molecule, if necessary, (c) a compound having two or more ethylenically unsaturated groups as monomers, each monomer being acrylic acid The ratio (mass ratio) between the ester (a) and the compound (b) is (a)/(b) = 6.0/94.0 to 30.0/70.0, and the compound (c) is included In some cases, the proportion of the compound (c) is obtained by polymerizing so that it is 0.0001 to 1.5 parts by mass with respect to a total of 100 parts by mass of the acrylic acid ester (a) and the compound (b). , acrylic acid ester (a)/compound (b) copolymers having the properties described above are preferred.
　なお、粘度は、Ｂ型回転粘度計とローターＮｏ．４を使用し、２０℃の温度で、回転数３ｒｐｍのときに測定した値である。 The viscosity was measured using a B-type rotational viscometer and rotor No. 4 at a temperature of 20° C. and a rotation speed of 3 rpm.
　本発明にかかる共重合体１質量％、かつ、リン酸-Ｌ-アスコルビルマグネシウム・ｎ水和物（水分含有量１６～２０質量％）２質量％を含むｐＨ７．５の水溶液の２０℃における粘度は、９，０００ｍＰａ・ｓ以上であることが好ましく、１１，０００ｍＰａ・ｓ以上であることがより好ましく、１３，０００ｍＰａ・ｓ以上であることがさらに好ましく、１５，０００ｍＰａ・ｓ以上であることが特に好ましく、１７，０００ｍＰａ・ｓ以上であることが最も好ましい。また、粘度の上限としては、本発明にかかる共重合体（成分Ａ）を含む乳化組成物の用途によって異なる場合があるが、例えば、２００，０００ｍＰａ・ｓ以下である。本発明にかかる共重合体はこのような特性を有するため、本発明にかかる共重合体（成分Ａ）を含む乳化組成物を化粧料に配合すると、少ない添加量で増粘でき、使用感および塗布性に優れ、独特の触感を有する化粧料が得られる。 Viscosity at 20° C. of pH 7.5 aqueous solution containing 1% by mass of the copolymer of the present invention and 2% by mass of L-ascorbylmagnesium phosphate n-hydrate (moisture content: 16 to 20% by mass) is preferably 9,000 mPa s or more, more preferably 11,000 mPa s or more, even more preferably 13,000 mPa s or more, and 15,000 mPa s or more. It is particularly preferred, and most preferably 17,000 mPa·s or more. The upper limit of the viscosity may vary depending on the application of the emulsion composition containing the copolymer (component A) of the present invention, but is, for example, 200,000 mPa·s or less. Since the copolymer according to the present invention has such properties, when an emulsified composition containing the copolymer according to the present invention (component A) is blended into a cosmetic, the viscosity can be increased with a small addition amount, and the feeling of use is improved. A cosmetic having excellent applicability and a unique feel can be obtained.
　本発明にかかる共重合体１質量％、かつ、リン酸-Ｌ-アスコルビルマグネシウム・ｎ水和物（水分含有量１６～２０質量％）２質量％を含むｐＨ７．５の水溶液の２０℃における粘度が、１５，０００ｍＰａ・ｓ以上である場合には、高濃度（例えば、２～５質量％）の電解質存在下で高い粘度が保たれ易いことから、本発明にかかる共重合体（成分Ａ）を含む乳化組成物は、高濃度（例えば、２～５質量％）の電解質を配合した種々の化粧料に用いることができる。 Viscosity at 20° C. of pH 7.5 aqueous solution containing 1% by mass of the copolymer of the present invention and 2% by mass of L-ascorbylmagnesium phosphate n-hydrate (moisture content: 16 to 20% by mass) However, when it is 15,000 mPa s or more, the high viscosity is easily maintained in the presence of a high concentration (for example, 2 to 5% by mass) of electrolyte, so the copolymer according to the present invention (component A) The emulsified composition containing can be used in various cosmetics formulated with a high concentration (eg, 2 to 5% by mass) of electrolyte.
　本発明にかかる共重合体１質量％、かつ、リン酸-Ｌ-アスコルビルマグネシウム・ｎ水和物（水分含有量１６～２０質量％）２質量％を含むｐＨ７．５の水溶液の２０℃における粘度が、１７，０００ｍＰａ・ｓ以上である場合には、高濃度（例えば、２～５質量％）の電解質存在下でより高い粘度が保たれ易いことから、本発明にかかる共重合体（成分Ａ）を含む乳化組成物は、高粘性を特長とする化粧料に好適に用いることができる。 Viscosity at 20° C. of pH 7.5 aqueous solution containing 1% by mass of the copolymer of the present invention and 2% by mass of L-ascorbylmagnesium phosphate n-hydrate (moisture content: 16 to 20% by mass) However, when it is 17,000 mPa s or more, the copolymer of the present invention (component A ) can be suitably used for cosmetics characterized by high viscosity.
　本発明にかかる共重合体（成分Ａ）が、このような特性を有する理由は定かではないが、特定量の（ａ）一般式［１］で示されるアクリル酸エステルを使用することに起因していると推察される。本発明にかかる共重合体におけるアクリル酸エステル（ａ）中のフッ素原子が、水溶液中で電解質と静電的相互作用によりポリマー鎖間で会合体を形成することで、増粘性が増すとともに、電解質による減粘の影響を低減させているものと推察される。 The reason why the copolymer (component A) according to the present invention has such properties is not clear, but it is due to the use of a specific amount of (a) acrylic acid ester represented by general formula [1]. It is presumed that The fluorine atoms in the acrylic acid ester (a) in the copolymer according to the present invention form associations between polymer chains due to electrostatic interaction with the electrolyte in an aqueous solution, thereby increasing the viscosity and increasing the electrolyte It is presumed that the effect of viscosity reduction due to is reduced.
　本発明にかかる化合物（ｃ）は、架橋剤として作用することで、粘度に影響を与えているものと推察される。 It is presumed that the compound (c) according to the present invention affects the viscosity by acting as a cross-linking agent.
　上述した本発明にかかる共重合体を製造する方法としては、特に限定されず、例えば、（ａ）一般式［１］で示されるアクリル酸エステルと、（ｂ）重合性不飽和基と、カルボキシル基、スルホ基およびリン酸基からなる群から選ばれるいずれかの官能基とを分子内に有する化合物と、（ｃ）エチレン性不飽和基を２個以上有する化合物と、要すれば化合物（ｄ）とを不活性ガス雰囲気下、溶媒中で攪拌し、重合開始剤を用いて重合させることにより、本発明にかかる共重合体を製造することができる。具体的には、例えば、国際公開第ＷＯ２０１７／１７０９６１号公報等に記載の方法により、本発明にかかる共重合体を製造することができる。 The method for producing the above-described copolymer according to the present invention is not particularly limited. For example, (a) an acrylic ester represented by the general formula [1], (b) a polymerizable unsaturated group, (c) a compound having two or more ethylenically unsaturated groups, and optionally a compound (d ) are stirred in a solvent under an inert gas atmosphere and polymerized using a polymerization initiator to produce the copolymer of the present invention. Specifically, for example, the copolymer according to the present invention can be produced by the method described in International Publication No. WO2017/170961.
　本発明にかかる共重合体の中和方法としては、上述したアルカリ性化合物を用いて、この分野で通常行われる方法等が挙げられる。 Examples of the method for neutralizing the copolymer according to the present invention include methods commonly performed in this field using the above-described alkaline compound.
－本発明にかかる油性成分－
　本発明にかかる油性成分とは、水中油型（Ｏ／Ｗ）の乳化組成物を形成し得る油性の物質であれば特に限定されず、動物油、植物油、合成油等の起源や、固形油、半固形油、液体油、揮発性油等の性状を問わず使用することができる。これらのなかでも、皮膚外用剤や化粧料に配合され得る油性の物質が好ましい。このような油性成分の具体例としては、例えば、炭化水素類、エステル油類、高級アルコール類、脂肪酸類、シリコーン油類、ロウ類、動植物油類等が挙げられる。 -Oil-based component according to the present invention-
The oily component according to the present invention is not particularly limited as long as it is an oily substance capable of forming an oil-in-water (O/W) emulsified composition. Semi-solid oil, liquid oil, volatile oil, etc. can be used regardless of properties. Among these, oily substances that can be blended in external skin preparations and cosmetics are preferred. Specific examples of such oily components include hydrocarbons, ester oils, higher alcohols, fatty acids, silicone oils, waxes, and animal and vegetable oils.
　炭化水素類の具体例としては、例えば、流動パラフィン、流動イソパラフィン、オレフィンオリゴマー、スクワラン、オリーブスクワラン、ライススクワラン、ジオクチルシクロヘキサン、ポリブテン、水添ポリイソブテン、イソドデカン、イソヘキサデカン、オゾケライト、プリスタン、パラフィンワックス、セレシンワックス、マイクロクリスタリンワックス、ワセリン、ポリエチレンワックス、フィッシャートロプッシュワックス等が挙げられる。 Specific examples of hydrocarbons include liquid paraffin, liquid isoparaffin, olefin oligomer, squalane, olive squalane, rice squalane, dioctylcyclohexane, polybutene, hydrogenated polyisobutene, isododecane, isohexadecane, ozokerite, pristane, paraffin wax, and ceresin. wax, microcrystalline wax, petrolatum, polyethylene wax, Fischer-Tropsch wax and the like.
　エステル油類の具体例としては、例えば、炭酸ジアルキル、安息香酸アルキル、パラメトキシ桂皮酸オクチル、酢酸ラノリン、オクタン酸セチル、イソオクタン酸セチル、２-エチルヘキサン酸セチル、イソノナン酸-２-エチルヘキシル、イソノナン酸ノニル、イソノナン酸イソノニル、イソノナン酸イソデシル、イソノナン酸イソトリデシル、イソノナン酸セトステアリル、ジメチルオクタン酸ヘキシルデシル、ジメチルオクタン酸オクチルドデシル、ラウリン酸エチル、ラウリン酸イソプロピル、ラウリン酸ヘキシル、ラウリン酸ヘキシルデシル、ミリスチン酸イソプロピル、ミリスチン酸ブチル、ミリスチン酸ミリスチル、ミリスチン酸イソセチル（ミリスチン酸-２-ヘキシルデシル）、ミリスチン酸イソステアリル、ミリスチン酸-２-オクチルドデシル、パルミチン酸イソプロピル、パルミチン酸オクチル、パルミチン酸-２-エチルヘキシル、パルミチン酸セチル、パルミチン酸-２-ヘキシルデシル、パルミチン酸イソステアリル、パルミチン酸-２-ヘプチルウンデシル、ステアリン酸ブチル、ステアリン酸イソセチル、ステアリン酸コレステリル、１２-ヒドロキシステアリン酸コレステリル、イソステアリン酸イソプロピル、イソステアリン酸イソセチル（イソステアリン酸-２-ヘキシルデシル）、イソステアリン酸イソステアリル、イソステアリン酸-２-オクチルドデシル、イソステアリン酸コレステリル、リノール酸エチル、リノール酸イソプロピル、オレイン酸エチル、オレイン酸デシル、オレイン酸オレイル、乳酸ミリスチル、乳酸セチル、乳酸イソステアリル、コハク酸-２-エチルヘキシル、コハク酸ジ-２-エチルヘキシル、リンゴ酸ジイソステアリル、アジピン酸ジイソブチル、アジピン酸-２-ヘキシルデシル、アジピン酸ジ-２-ヘプチルウンデシル、セバシン酸ジイソプロピル、セバシン酸ジ-２-エチルヘキシル、ダイマー酸ジイソプロピル、ダイマー酸ジイソステアリル、クエン酸トリエチル、クエン酸トリイソオクチル、クエン酸トリイソセチル、クエン酸アセチルトリエチル、クエン酸アセチルトリブチル、テトラ-２-エチルヘキサン酸ペンタエリスリット、テトラ-２-イソステアリン酸ペンタエリスリット、ジ-２-エチルヘキサン酸エチレングリコール、ジカプリル酸プロピレングリコール、ジカプリン酸プロピレングリコール、ジ-２-エチルヘキサン酸ネオペンチルグリコール、ジカプリル酸ネオペンチルグリコール、ジカプリン酸ネオペンチルグリコール、イソステアリン酸-Ｎ-アルキルグリコール、Ｎ-ラウロイル-Ｌ-グルタミン酸-２-オクチルドデシルエステル、Ｎ-ラウロイル-Ｌ-グルタミン酸ジ（コレステリル、オクチルドデシル）、ジ-２-ヘプチルウンデカン酸グリセリル、トリカプリル酸グリセリル、トリ-２-エチルヘキサン酸グリセリル、トリミリスチン酸グリセリル、トリパルミチン酸グリセリル、トリイソパルミチン酸グリセリル、トリイソステアリン酸グリセリル、トリ-２-ヘプチルウンデカン酸グリセリル、トリ（カプリル・カプリン酸）グリセリル、トリ（カプリル・カプリン・ミリスチン・ステアリン酸）グリセリル、トリアシルグリセロール（トリグリセリド）、トリ-２-エチルヘキサン酸トリメチロールプロパン、トリイソステアリン酸トリメチロールプロパン、テトラ-２-エチルヘキサン酸ペンタエリスリトール、ジペンタエリスリトール脂肪酸エステル、デカステアリン酸デカグリセリル、デカイソステアリン酸デカグリセリル、デカオレイン酸デカグリセリル、アセトグリセリド、ヒマシ油脂肪酸メチルエステル等が挙げられる。 Specific examples of ester oils include dialkyl carbonate, alkyl benzoate, octyl paramethoxycinnamate, lanolin acetate, cetyl octanoate, cetyl isooctanoate, cetyl 2-ethylhexanoate, 2-ethylhexyl isononanoate, and isononanoic acid. nonyl, isononyl isononanoate, isodecyl isononanoate, isotridecyl isononanoate, cetostearyl isononanoate, hexyldecyl dimethyloctanoate, octyldodecyl dimethyloctanoate, ethyl laurate, isopropyl laurate, hexyl laurate, hexyldecyl laurate, myristic acid Isopropyl, butyl myristate, myristyl myristate, isocetyl myristate (2-hexyldecyl myristate), isostearyl myristate, 2-octyldodecyl myristate, isopropyl palmitate, octyl palmitate, 2-ethylhexyl palmitate , cetyl palmitate, 2-hexyldecyl palmitate, isostearyl palmitate, 2-heptylundecyl palmitate, butyl stearate, isocetyl stearate, cholesteryl stearate, cholesteryl 12-hydroxystearate, isopropyl isostearate, isocetyl isostearate (2-hexyldecyl isostearate), isostearyl isostearate, 2-octyldodecyl isostearate, cholesteryl isostearate, ethyl linoleate, isopropyl linoleate, ethyl oleate, decyl oleate, oleyl oleate, Myristyl lactate, cetyl lactate, isostearyl lactate, 2-ethylhexyl succinate, di-2-ethylhexyl succinate, diisostearyl malate, diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptyl adipate Undecyl, diisopropyl sebacate, di-2-ethylhexyl sebacate, diisopropyl dimate, diisostearyl dimate, triethyl citrate, triisooctyl citrate, triisocetyl citrate, acetyltriethyl citrate, acetyltributyl citrate, tetra pentaerythrityl-2-ethylhexanoate, pentaerythrityl tetra-2-isostearate, ethylene glycol di-2-ethylhexanoate, propylene glycol dicaprylate, propylene glycol dicaprate, di-2-ethylhexanoate Neopentyl glycol xanoate, neopentyl glycol dicaprylate, neopentyl glycol dicaprate, N-alkyl glycol isostearate, N-lauroyl-L-glutamic acid 2-octyldodecyl ester, N-lauroyl-L-glutamic acid di(cholesteryl) , Octyldodecyl), glyceryl di-2-heptylundecanoate, glyceryl tricaprylate, glyceryl tri-2-ethylhexanoate, glyceryl trimyristate, glyceryl tripalmitate, glyceryl triisopalmitate, glyceryl triisostearate, tri- Glyceryl 2-heptylundecanoate, caprylic-capric triglyceride, caprylic-capric myristic stearic triglyceryl, triacylglycerol (triglyceride), trimethylolpropane tri-2-ethylhexanoate, triisostearic acid Trimethylolpropane, pentaerythritol tetra-2-ethylhexanoate, dipentaerythritol fatty acid ester, decaglyceryl destearate, decaglyceryl decaisostearate, decaglyceryl decaoleate, acetoglyceride, castor oil fatty acid methyl ester and the like.
　高級アルコール類の具体例としては、例えば、セチルアルコール、ステアリルアルコール、イソステアリルアルコール、オレイルアルコール等が挙げられる。 Specific examples of higher alcohols include cetyl alcohol, stearyl alcohol, isostearyl alcohol, and oleyl alcohol.
　脂肪酸類の具体例としては、例えば、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、イソステアリン酸、ベヘン酸、ウンデシレン酸、オレイン酸、リノール酸、リノレン酸、アラキドン酸、ヤシ油脂肪酸等が挙げられる。 Specific examples of fatty acids include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, behenic acid, undecylenic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, coconut oil fatty acids and the like.
　シリコーン油類の具体例としては、例えば、ジメチルポリシロキサン、メチルフェニルポリシロキサン、メチルセチルポリシロキサン、ジフェニルポリシロキサン、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン（シクロメチコン）、ドデカメチルシクロヘキサシロキサン、高重合メチルポリシロキサン、ジメチコン、高重合メチルフェニルポリシロキサン、アルキル変性ポリシロキサン、フッ素変性ポリシロキサン、アミノ変性ポリシロキサン、オレイル変性メチルポリシロキサン、トリメチルシロキシケイ酸、アルキル変性シリコーン、アルコキシ変性シリコーン、フッ素変性シリコーン、アクリル変性シリコーン等が挙げられる。 Specific examples of silicone oils include dimethylpolysiloxane, methylphenylpolysiloxane, methylcetylpolysiloxane, diphenylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane (cyclomethicone), and dodecamethylcyclohexasiloxane. , highly polymerized methylpolysiloxane, dimethicone, highly polymerized methylphenylpolysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane, amino-modified polysiloxane, oleyl-modified methylpolysiloxane, trimethylsiloxysilicate, alkyl-modified silicone, alkoxy-modified silicone, Examples include fluorine-modified silicone and acrylic-modified silicone.
　ロウ類の具体例としては、例えば、ミツロウ、高酸価ミツロウ、カルナウバロウ、キャンデリラロウ、ゲイロウ、セラック、ミンクロウ、ラノリン、液状ラノリン、コメヌカロウ、モクロウ、綿ロウ、ベイベリーロウ、イボタロウ、モンタンロウ、カボックロウ、ジョジョバロウ、サトウキビロウ、ラノリン脂肪酸イソプロピル、還元ラノリン、硬質ラノリン等が挙げられる。 Specific examples of waxes include, for example, beeswax, high acid value beeswax, carnauba wax, candelilla wax, gay wax, shellac, mink wax, lanolin, liquid lanolin, rice bran wax, Japanese wax, cotton wax, bayberry wax, wart wax, montan wax, kabok wax, and jojo wax. Barlow, sugarcane wax, lanolin fatty acid isopropyl, reduced lanolin, hard lanolin and the like.
　動植物油類の具体例としては、例えば、アボガド油、アマニ油、アーモンド油、オリーブ油、キョウニン油、ゴマ油、コメ胚芽油、小麦胚芽油、胚芽油、コメヌカ油、サフラワー油、大豆油、トウモロコシ油、ホホバ油、マカダミアナッツ油、綿実油、ヤシ油、硬化ヤシ油、ヒマシ油、ヒマワリ油、菜種油、メドウフォーム油、月見草油、シア油、トール油、ミンク油、ツバキ油、パーシック油、サザンカ油、エノ油、落花生油、茶実油、カヤ油、シナギリ油、日本キリ油、パーム油、パーム核油、ココナッツ油、ピーナッツ油、ヘーゼルナッツ油、ウォルナッツ油、グレープシード油、タートル油、魚油等の精製油または硬化（水添）油等が挙げられる。 Specific examples of animal and vegetable oils include avocado oil, linseed oil, almond oil, olive oil, Chinese ginseng oil, sesame oil, rice germ oil, wheat germ oil, germ oil, rice bran oil, safflower oil, soybean oil, and corn oil. , jojoba oil, macadamia nut oil, cottonseed oil, coconut oil, hydrogenated coconut oil, castor oil, sunflower oil, rapeseed oil, meadowfoam oil, evening primrose oil, shea oil, tall oil, mink oil, camellia oil, persic oil, sasanqua oil, Eno oil, peanut oil, tea seed oil, kaya oil, sinagiri oil, Japanese paulownia oil, palm oil, palm kernel oil, coconut oil, peanut oil, hazelnut oil, walnut oil, grape seed oil, turtle oil, fish oil, etc. Refined oil, hardened (hydrogenated) oil, and the like can be mentioned.
　これらの油性成分は、１種類の油性成分を単独で用いてもよいし、２種以上の油性成分を組み合わせて用いてもよい。また、これらの油性成分は、市販のものを用いればよい。 As for these oily components, one type of oily component may be used alone, or two or more types of oily components may be used in combination. In addition, commercially available products may be used as these oily components.
　上述した油性成分のなかでも、常温で液体状の、炭化水素類、エステル油類、高級アルコール類、シリコーン油類、ロウ類、動植物油類が好ましい。これらの好ましい油性成分を用いると、ツヤのある外観を有し、塗布後のコク感に優れる乳化組成物を得ることができる。 Among the oily components mentioned above, hydrocarbons, ester oils, higher alcohols, silicone oils, waxes, and animal and vegetable oils that are liquid at room temperature are preferred. By using these preferred oily components, it is possible to obtain an emulsified composition that has a glossy appearance and an excellent rich feeling after application.
－水－
　本発明の水中油型（Ｏ／Ｗ）の乳化組成物は、水を含む。このような水としては、皮膚外用剤や化粧料に用いられるものであれば特に限定されず、例えば、水道水、精製水、蒸留水、イオン交換水（脱イオン水）、純水、超純水等が挙げられる。 -water-
The oil-in-water (O/W) emulsion composition of the present invention comprises water. Such water is not particularly limited as long as it is used for external skin preparations and cosmetics. Water etc. are mentioned.
－成分Ａと油性成分と水の含有量－
　乳化組成物中における本発明にかかる成分Ａの含有量、すなわち、乳化組成物中における本発明にかかる共重合体の含有量としては、所望の効果が発揮される限り特に限定されないが、乳化組成物中、本発明にかかる成分Ａを０．１～５質量％含有することが好ましく、０．３～５質量％含有することがより好ましく、０．５～２質量％含有することがさらに好ましい。油性成分の乳化効果の観点から、成分Ａの含有量は０．１質量％以上であることが好ましく、良好な使用感が得られるという観点から、成分Ａの含有量は５質量％以下であることが好ましい。 - Content of component A, oily component and water -
The content of the component A according to the present invention in the emulsion composition, that is, the content of the copolymer according to the present invention in the emulsion composition is not particularly limited as long as the desired effect is exhibited. In the product, it is preferable to contain 0.1 to 5% by mass, more preferably 0.3 to 5% by mass, and even more preferably 0.5 to 2% by mass of Component A according to the present invention. . The content of component A is preferably 0.1% by mass or more from the viewpoint of the emulsifying effect of the oily component, and the content of component A is 5% by mass or less from the viewpoint of obtaining a good feeling during use. is preferred.
　乳化組成物中における本発明にかかる油性成分の含有量としては、通常１～６５質量％、好ましくは４～６５質量％、より好ましくは６～５０質量％である。乳化組成物のツヤやコク感の観点から、油性成分の含有量は１質量％以上であることが好ましく、乳化組成物が分離せずに均一な状態を保持できるという観点から、油性成分の含有量は６５質量％以下であることが好ましい。 The content of the oily component according to the present invention in the emulsified composition is usually 1-65% by mass, preferably 4-65% by mass, more preferably 6-50% by mass. From the viewpoint of the luster and richness of the emulsified composition, the content of the oily component is preferably 1% by mass or more. The amount is preferably 65 mass % or less.
　乳化組成物中における油性成分に対する成分Ａの含有量としては、通常０．４～２５０質量％、好ましくは０．６～１２０質量％、より好ましくは１～９０質量％、さらに好ましくは１～１０質量％である。乳化組成物が分離せずに均一な状態を保持できるという観点から、油性成分に対する成分Ａの含有量は０．４質量％以上であることが好ましく、乳化組成物のツヤやコク感の観点から、油性成分に対する成分Ａの含有量は２５０質量％以下であることが好ましい。 The content of Component A relative to the oily component in the emulsified composition is usually 0.4-250% by mass, preferably 0.6-120% by mass, more preferably 1-90% by mass, still more preferably 1-10% by mass. % by mass. From the viewpoint that the emulsion composition can maintain a uniform state without separation, the content of component A relative to the oily component is preferably 0.4% by mass or more, and from the viewpoint of gloss and richness of the emulsion composition. , the content of component A with respect to the oil component is preferably 250% by mass or less.
　乳化組成物中における水の含有量としては、成分Ａおよび油性成分の含有量が上述した範囲となるような量であればよく、通常１～９９．９質量％、好ましくは１０～９５．９質量％、より好ましくは３０～９５．９質量％である。 The content of water in the emulsified composition may be such that the content of component A and the oily component is in the range described above, usually 1 to 99.9% by mass, preferably 10 to 95.9%. % by mass, more preferably 30 to 95.9% by mass.
　成分Ａや油性成分の含有量を上述した範囲に調整することにより、ツヤのある外観を有し、使用感としてみずみずしさとコク感を備える、均一な水中油型（Ｏ／Ｗ）の乳化組成物を得ることができる。 A uniform oil-in-water (O/W) emulsified composition that has a glossy appearance and a fresh and rich feeling when used by adjusting the contents of the component A and the oil component within the ranges described above. can be obtained.
－界面活性剤－
　本発明の乳化組成物は、界面活性剤を実質的に含まないか、界面活性剤を含む場合には、該界面活性剤の含有量が、成分Ａに対して９０質量％以下、かつ、油性成分に対して３質量％以下であることが好ましい。 -Surfactant-
The emulsified composition of the present invention does not substantially contain a surfactant, or if it contains a surfactant, the content of the surfactant is 90% by mass or less with respect to component A, and an oily It is preferably 3% by mass or less with respect to the component.
　本明細書において、「実質的に含まない」とは、全く含まないか、含むとしても本発明の効果に悪影響を及ぼさない程度の極微量しか含まないことを意味し、本発明の乳化組成物中の含有量として、０．００１質量％未満を意味する。 As used herein, the term "substantially free" means that the emulsified composition of the present invention contains no As the content in the medium, it means less than 0.001% by mass.
　本発明にかかる界面活性剤とは、例えば、皮膚外用剤や化粧料に配合され得る物質（カチオン性・アニオン性・両性・非イオン性界面活性剤）であれば特に限定されず、なかでも、アニオン性界面活性剤、非イオン性界面活性剤が好ましく挙げられる。 The surfactant according to the present invention is not particularly limited as long as it is a substance (cationic, anionic, amphoteric, nonionic surfactant) that can be blended in, for example, external skin preparations and cosmetics. Anionic surfactants and nonionic surfactants are preferred.
　アニオン性界面活性剤の具体例としては、例えば、ポリオキシエチレンラウリルエーテル硫酸ナトリウム、ポリオキシエチレンラウリルエーテル硫酸アンモニム、ポリオキシエチレンラウリルエーテル硫酸トリエタノールアミン、ポリオキシエチレンアルキル（Ｃ１２～１３）エーテル硫酸ナトリウム、ポリオキシエチレンアルキル（Ｃ１２～１３）エーテル硫酸アンモニウム、ポリオキシエチレンアルキル（Ｃ１２～１３）エーテル硫酸トリエタノールアミン等のポリオキシエチレンアルキルエーテル硫酸塩類；ラウリル硫酸ナトリウム、ラウリル硫酸アンモニム、ラウリル硫酸トリエタノールアミン等のアルキル硫酸塩類；ポリオキシエチレンラウリルエーテル酢酸ナトリウム、ポリオキシエチレントリデシルエーテル酢酸ナトリウム、ポリオキシエチレンヤシ油脂肪酸酢酸ナトリウム等のポリオキシエチレンアルキルエーテル酢酸ナトリウム類；スルホコハク酸ジオクチルナトリウム、スルホコハク酸ラウリル二ナトリウム、ジアルキルスルホコハク酸、ポリオキシエチレンスルホコハク酸ラウリル二ナトリウム、ポリオキシエチレンアルキル（Ｃ１２～１３）スルホコハク酸二ナトリウム、ポリオキシエチレンアルキル（Ｃ１２～１４）スルホコハク酸二ナトリウム、ポリオキシアルキレンアルキルスルホコハク酸塩、スルホコハク酸ポリオキシエチレンラウロイルエタノールアミド二ナトリウム等のアルキルスルホコハク酸塩類；ポリオキシエチレンヤシ油脂肪酸モノエタノールアミド硫酸ナトリウム等のポリオキシエチレン脂肪酸アミドエーテル硫酸塩類；ラウリン酸タウリンナトリウム、ラウロイルメチルタウリンナトリウム、ミリストイルメチルタウリンナトリウム、パルミトイルメチルタウリンナトリウム、ステアロイルメチルタウリンナトリウム、ヤシ油脂肪酸タウリンナトリウム、ヤシ油脂肪酸メチルタウリンナトリウム、Ｎ-アシルメチルタウリンナトリウム等のタウリン塩類；ラウロイルサルコシンナトリウム、ラウロイルサルコシンカリウム、ラウロイルサルコシントリエタノールアミン、ヤシ油脂肪酸サルコシンナトリウム、ヤシ油脂肪酸サルコシンカリウム、ヤシ油脂肪酸サルコシントリエタノールアミン等のサルコシン塩類；ラウリルリン酸、オレイルリン酸、ポリオキシエチレンラウリルエーテルリン酸、ポリオキシエチレンアルキル（Ｃ１２～１５）エーテルリン酸、ポリオキシエチレンセチルエーテルリン酸、ポリオキシエチレンステアリルエーテルリン酸、ジポリオキシエチレンアルキルエーテルリン酸、トリポリオキシエチレンアルキルエーテルリン酸、ポリオキシエチレンオレイルエーテルリン酸、ポリオキシエチレンヤシ油脂肪酸モノエタノールアミドリン酸塩等のナトリウム、カリウム、アンモニウム、トリエタノールアミン等の塩であるリン酸塩類；トルエンスルホン酸ナトリウム、ドデシルベンゼンスルホン酸ナトリウム等のアルキルベンゼンスルホン酸塩類；アルカンスルホン酸ナトリウム、アルキルエタンスルホン酸ナトリウム、オレフィンスルホン酸ナトリウム、ヤシ油脂肪酸エチルエステルスルホン酸ナトリウム等のスルホン酸塩類；ポリオキシエチレンアルキルエーテルカルボン酸ナトリウム等のカルボン酸塩類等が挙げられる。 Specific examples of anionic surfactants include sodium polyoxyethylene lauryl ether sulfate, ammonium polyoxyethylene lauryl ether sulfate, triethanolamine polyoxyethylene lauryl ether sulfate, and polyoxyethylene alkyl (C12-13) ether sulfate. Polyoxyethylene alkyl ether sulfates such as sodium, polyoxyethylene alkyl (C12-13) ammonium ether sulfate, polyoxyethylene alkyl (C12-13) ether sulfate triethanolamine; sodium lauryl sulfate, ammonium lauryl sulfate, triethanol lauryl sulfate Alkyl sulfates such as amines; Sodium polyoxyethylene lauryl ether acetate, sodium polyoxyethylene tridecyl ether acetate, sodium polyoxyethylene coconut oil fatty acid acetate and other sodium polyoxyethylene alkyl ether acetates; dioctyl sodium sulfosuccinate, sulfosuccinic acid Disodium Lauryl, Dialkyl Sulfosuccinate, Disodium Lauryl Polyoxyethylene Sulfosuccinate, Disodium Polyoxyethylene Alkyl (C12-13) Sulfosuccinate, Disodium Polyoxyethylene Alkyl (C12-14) Sulfosuccinate, Polyoxyalkylene Alkyl Sulfosuccinate Alkyl sulfosuccinates such as polyoxyethylene lauroyl ethanolamide disodium sulfosuccinate; Polyoxyethylene fatty acid amide ether sulfates such as sodium polyoxyethylene coconut oil fatty acid monoethanolamide sulfate; Sodium laurate taurine, lauroyl methyl taurine Taurine salts such as sodium, sodium myristoyl methyl taurate, sodium palmitoyl methyl taurate, sodium stearoyl methyl taurate, sodium coco fatty acid taurate, sodium coco fatty acid methyl taurate, sodium N-acyl methyl taurate; sodium lauroyl sarcosinate, potassium lauroyl sarcosinate, lauroyl Sarcosine salts such as sarcosine triethanolamine, sodium coconut sarcosine, potassium coconut sarcosine, and sarcosine triethanolamine; lauryl phosphate, oleyl phosphate, polyoxyethylene lauryl ether phosphate, polyoxyethylene alkyl (C12 ~15) ether phosphate, polyoxy Ethylene cetyl ether phosphate, polyoxyethylene stearyl ether phosphate, dipolyoxyethylene alkyl ether phosphate, tripolyoxyethylene alkyl ether phosphate, polyoxyethylene oleyl ether phosphate, polyoxyethylene coconut oil fatty acid monoethanolamide phosphate Phosphates, which are salts such as sodium, potassium, ammonium, and triethanolamine salts; Alkylbenzenesulfonates such as sodium toluenesulfonate and sodium dodecylbenzenesulfonate; sulfonates such as sodium sulfonate and coconut oil fatty acid ethyl ester sodium sulfonate; and carboxylates such as sodium polyoxyethylene alkyl ether carboxylate.
　非イオン性界面活性剤の具体例としては、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンベヘニルエーテル、ポリオキシエチレンオクチルドデシルエーテル、ポリオキシエチレンデシルテトラデシルエーテル等のポリオキシエチレンアルキルエーテル類；ポリオキシエチレンポリオキシプロピレンデシルエーテル、ポリオキシエチレンポリオキシプロピレンセチルエーテル、ポリオキシエチレンポリオキシプロピレンデシルテトラデシルエーテル等のポリオキシエチレンポリオキシプロピレンアルキルエーテル類；ラウリン酸モノエタノールアミド、ミリスチン酸モノエタノールアミド、パルミチン酸モノエタノールアミド、ステアリン酸モノエタノールアミド、イソステアリン酸モノエタノールアミド、オレイン酸モノエタノールアミド、ヤシ油脂肪酸モノエタノールアミド等のモノエタノールアミド類；ラウリン酸ジエタノールアミド、ミリスチン酸ジエタノールアミド、パルミチン酸ジエタノールアミド、ステアリン酸ジエタノールアミド、イソステアリン酸ジエタノールアミド、オレイン酸ジエタノールアミド、ヤシ油脂肪酸ジエタノールアミド、パーム核油脂肪酸ジエタノールアミド等のジエタノールアミド類；ラウリン酸イソプロパノールアミド、ミリスチン酸イソプロパノールアミド、パルミチン酸イソプロパノールアミド、ステアリン酸イソプロパノールアミド、イソステアリン酸イソプロパノールアミド、オレイン酸イソプロパノールアミド、ヤシ油脂肪酸イソプロパノールアミド等のイソプロパノールアミド類；ポリオキシエチレンラウリン酸モノエタノールアミド、ポリオキシエチレンミリスチン酸モノエタノールアミド、ポリオキシエチレンパルミチン酸モノエタノールアミド、ポリオキシエチレンステアリン酸モノエタノールアミド、ポリオキシエチレンイソステアリン酸モノエタノールアミド、ポリオキシエチレンオレイン酸モノエタノールアミド、ポリオキシエチレンヤシ油脂肪酸モノエタノールアミド等のポリオキシエチレンモノエタノールアミド類；ＰＰＧ-２-ヒドロキシエチルココイソステアラミド等のステアリルアミド類；カプリルグルコシド、デシルグルコシド、ラウリルグルコシド等のアルキルグルコシド類；ラウリルジメチルアミンオキシド、ステアリルジメチルアミンオキシド等のアルキルジメチルアミンオキシド類；モノラウリン酸ソルビタン、モノパルミチン酸ソルビタン、モノステアリン酸ソルビタン、トリステアリン酸ソルビタン、セスキステアリン酸ソルビタン、モノイソステアリン酸ソルビタン、セスキイソステアリン酸ソルビタン、モノオレイン酸ソルビタン、トリオレイン酸ソルビタン、セスキオレイン酸ソルビタン等のソルビタン脂肪酸エステル類；モノラウリン酸ポリオキシエチレンソルビタン、モノパルミチン酸ポリオキシエチレンソルビタン、モノステアリン酸ポリオキシエチレンソルビタン、トリステアリン酸ポリオキシエチレンソルビタン、モノイソステアリン酸ポリオキシエチレンスルビタン、トリイソステアリン酸ポリオキシエチレンソルビタン、モノオレイン酸ポリオキシエチレンソルビタン、トリオレイン酸ポリオキシエチレンソルビタン、ヤシ油脂肪酸ポリオキシエチレンソルビタン等のポリオキシエチレンソルビタン脂肪酸エステル類；モノラウリン酸ポリオキシエチレンソルビット、テトラステアリン酸ポリオキシエチレンソルビット、ヘキサステアリン酸ポリオキシエチレンソルビット、テトラオレイン酸ポリオキシエチレンソルビット等のポリオキシエチレンソルビット脂肪酸エステル類；モノラウリン酸ポリエチレングリコール、ジラウリン酸ポリエチレングリコール、モノステアリン酸ポリエチレングリコール、ジステアリン酸ポリエチレングリコール、ジイソステアリン酸ポリエチレングリコール、モノオレイン酸ポリエチレングリコール、ジオレイン酸ポリエチレングリコール、ラノリン脂肪酸ポリエチレングリコール等のポリエチレングリコール脂肪酸エステル類；モノカプリン酸プロピレングリコール等のモノ脂肪酸プロピレングリコール類；モノミリスチン酸グリセリル、モノステアリン酸グリセリル、ジステアリン酸グリセリル、モノイソステアリン酸グリセリル、モノオレイン酸グリセリル、ジオレイン酸グリセリル等のグリセリン脂肪酸エステル類；モノステアリン酸ジグリセリル、モノイソステアリン酸ジグリセリル、モノオレイン酸ジグリセリル、ジオレイン酸ジグリセリル、モノステアリン酸テトラグリセリル、トリステアリン酸テトラグリセリル、ペンタステアリン酸テトラグリセリル、モノオレイン酸テトラグリセリル、ペンタオレイン酸テトラグリセリル、モノラウリン酸ヘキサグリセリル、モノミリスチン酸ヘキサグリセリル、モノステアリン酸ヘキサグリセリル、トリステアリン酸ヘキサグリセリル、ペンタステアリン酸ヘキサグリセリル、モノオレイン酸ヘキサグリセリル、ペンタオレイン酸ヘキサグリセリル、ポリリシノール酸ヘキサグリセリル、モノラウリン酸デカグリセリル、モノミリスチン酸デカグリセリル、モノステアリン酸デカグリセリル、ジステアリン酸デカグリセリル、トリステアリン酸デカグリセリル、ペンタステアリン酸デカグリセリル、ヘプタステアリン酸デカグリセリル、デカステアリン酸デカグリセリル、モノイソステアリン酸デカグリセリル、ジイソステアリン酸デカグリセリル、ペンタイソステアリン酸デカグリセリル、モノリノール酸デカグリセリル、モノオレイン酸デカグリセリル、トリオレイン酸デカグリセリル、ペンタオレイン酸デカグリセリル、ヘプタオレイン酸デカグリセリル、デカオレイン酸デカグリセリル等のポリグリセリン脂肪酸エステル類；ポリオキシエチレンモノステアリン酸グリセリル、ポリオキシエチレンジステアリン酸グリセリル、ポリオキシエチレントリステアリン酸グリセリル、ポリオキシエチレンモノイソステアリン酸グリセリル、ポリオキシエチレントリイソステアリン酸グリセリル、ポリオキシエチレントリオレイン酸グリセリル等のポリオキシエチレングリセリン脂肪酸エステル類；ポリオキシエチレンヒマシ油、ポリオキシエチレン硬化ヒマシ油等のポリオキシエチレンヒマシ油類；ステアリン酸ジエチルアミノエチルアミド、ステアリン酸ジメチルアミノプロピルアミド等のアルキルアミドアミン類；ポリオキシエチレンフィトステロール等のポリオキシエチレンコレステリルエーテル類；ポリオキシエチレンラノリンアルコールエーテル、ポリオキシエチレンラノリンアルコールアセテート、ポリオキシエチレン水素添加ラノリンアルコールエーテル、ポリオキシエチレンコレステロールエーテル等のポリオキシエチレンラノリンアルコール類；ポリエーテル変性ポリシロキサン、ポリビニルピロリドン変性メチルポリシロキサン等の変性ポリシロキサン類；マルチトールヒドロキシ脂肪酸アルキルエーテル、アルキル化多糖、ショ糖脂肪酸エステル等の糖誘導体類等が挙げられる。 Specific examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene behenyl ether, and polyoxyethylene octyldodecyl ether. , polyoxyethylene alkyl ethers such as polyoxyethylene decyltetradecyl ether; polyoxyethylenes such as polyoxyethylene polyoxypropylene decyl ether, polyoxyethylene polyoxypropylene cetyl ether, polyoxyethylene polyoxypropylene decyltetradecyl ether Polyoxypropylene alkyl ethers; lauric acid monoethanolamide, myristic acid monoethanolamide, palmitic acid monoethanolamide, stearic acid monoethanolamide, isostearic acid monoethanolamide, oleic acid monoethanolamide, coconut oil fatty acid monoethanolamide, etc. monoethanolamides; lauric acid diethanolamide, myristic acid diethanolamide, palmitic acid diethanolamide, stearic acid diethanolamide, isostearic acid diethanolamide, oleic acid diethanolamide, coconut oil fatty acid diethanolamide, palm kernel oil fatty acid diethanolamide, etc. Diethanolamides; Isopropanolamides such as lauric acid isopropanolamide, myristate isopropanolamide, palmitic acid isopropanolamide, stearic acid isopropanolamide, isostearic acid isopropanolamide, oleic acid isopropanolamide, coconut oil fatty acid isopropanolamide; polyoxyethylene lauric acid monoethanolamide, polyoxyethylene myristic monoethanolamide, polyoxyethylene palmitic monoethanolamide, polyoxyethylene stearic monoethanolamide, polyoxyethylene isostearic monoethanolamide, polyoxyethylene oleic monoethanolamide, poly Polyoxyethylene monoethanolamides such as oxyethylene coconut oil fatty acid monoethanolamide; Stearylamides such as PPG-2-hydroxyethyl cocoisostearamide; Alkyl glucosides such as capryl glucoside, decyl glucoside and lauryl glucoside; Lauryl dimethyl ah amine oxide, alkyldimethylamine oxides such as stearyldimethylamine oxide; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan sesquistearate, sorbitan monoisostearate, sorbitan sesquiisostearate, monoolein Sorbitan fatty acid esters such as sorbitan acid, sorbitan trioleate, and sorbitan sesquioleate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, Polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sulbitan monoisostearate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, coconut oil fatty acid polyoxyethylene sorbitan; Polyoxyethylene sorbitol fatty acid esters such as polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol tetrastearate, polyoxyethylene sorbitol hexastearate, and polyoxyethylene sorbitol tetraoleate; polyethylene glycol monolaurate, polyethylene glycol dilaurate, Polyethylene glycol fatty acid esters such as polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol diisostearate, polyethylene glycol monooleate, polyethylene glycol dioleate, lanolin fatty acid polyethylene glycol; mono fatty acid propylene glycol such as propylene glycol monocaprate Glyceryl fatty acid esters such as glyceryl monomyristate, glyceryl monostearate, glyceryl distearate, glyceryl monoisostearate, glyceryl monooleate, glyceryl dioleate; diglyceryl monostearate, diglyceryl monoisostearate, monoolein Diglyceryl acid, diglyceryl dioleate, tetraglyceryl monostearate, tetraglyceryl tristearate, tetraglyceryl pentastearate, tetraglyceryl monooleate, tetraglyceryl pentaoleate, mono Hexaglyceryl laurate, hexaglyceryl monomyristate, hexaglyceryl monostearate, hexaglyceryl tristearate, hexaglyceryl pentastearate, hexaglyceryl monooleate, hexaglyceryl pentaoleate, hexaglyceryl polyricinoleate, deca monolaurate Glyceryl, Decaglyceryl Monomyristate, Decaglyceryl Monostearate, Decaglyceryl Distearate, Decaglyceryl Tristearate, Decaglyceryl Pentastearate, Decaglyceryl Heptastearate, Decaglyceryl Decastearate, Decaglyceryl Monoisostearate, Diisostearin Polyglycerin fatty acid esters such as decaglyceryl acid, decaglyceryl pentaisostearate, decaglyceryl monolinoleate, decaglyceryl monooleate, decaglyceryl trioleate, decaglyceryl pentaoleate, decaglyceryl heptoleate, and decaglyceryl decoleate Glyceryl polyoxyethylene monostearate, glyceryl polyoxyethylene distearate, glyceryl polyoxyethylene tristearate, glyceryl polyoxyethylene monoisostearate, glyceryl polyoxyethylene triisostearate, glyceryl polyoxyethylene trioleate, etc. Polyoxyethylene glycerin fatty acid esters; Polyoxyethylene castor oils such as polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil; Alkylamidoamines such as diethylaminoethylamide stearate and dimethylaminopropylamide stearate; Polyoxyethylene Polyoxyethylene cholesteryl ethers such as phytosterol; polyoxyethylene lanolin alcohols such as polyoxyethylene lanolin alcohol ether, polyoxyethylene lanolin alcohol acetate, polyoxyethylene hydrogenated lanolin alcohol ether, polyoxyethylene cholesterol ether; polyether modification modified polysiloxanes such as polysiloxane and polyvinylpyrrolidone-modified methylpolysiloxane; sugar derivatives such as maltitol hydroxy fatty acid alkyl ethers, alkylated polysaccharides and sucrose fatty acid esters;
　これらの界面活性剤は、１種類の界面活性剤を単独で用いてもよいし、２種以上の界面活性剤を組み合わせて用いてもよい。また、これらの界面活性剤は、市販のものを用いればよい。 As for these surfactants, one type of surfactant may be used alone, or two or more types of surfactants may be used in combination. In addition, commercial products may be used as these surfactants.
　本発明の乳化組成物中に界面活性剤を含む場合において、該界面活性剤がアニオン性界面活性剤にあっては、その含有量は、成分Ａに対して５０質量％以下であることが好ましく、３０質量％以下であることがより好ましい。 When the emulsified composition of the present invention contains a surfactant, if the surfactant is an anionic surfactant, the content thereof is preferably 50% by mass or less relative to component A. , 30% by mass or less.
　本発明の乳化組成物中に界面活性剤を含む場合において、該界面活性剤が非イオン性界面活性剤にあっては、その含有量は、成分Ａに対して６０質量％以下であることが好ましく、３０質量％以下であることがより好ましい。 When the emulsified composition of the present invention contains a surfactant, if the surfactant is a nonionic surfactant, the content thereof should be 60% by mass or less with respect to component A. It is preferably 30% by mass or less, and more preferably 30% by mass or less.
　本発明の乳化組成物中に界面活性剤を含む場合において、該界面活性剤の含有量は、油性成分に対して２質量％以下であることがより好ましく、１質量％以下であることがさらに好ましく、０．１質量％以下であることが特に好ましい。 When the emulsified composition of the present invention contains a surfactant, the content of the surfactant is more preferably 2% by mass or less, more preferably 1% by mass or less, relative to the oily component. It is preferably 0.1% by mass or less, and particularly preferably 0.1% by mass or less.
　本発明の乳化組成物中に界面活性剤を含む場合において、界面活性剤の含有量の下限値は、乳化組成物中の界面活性剤の含有量として、０．００１質量％である。 When the emulsified composition of the present invention contains a surfactant, the lower limit of the surfactant content is 0.001% by mass as the content of the surfactant in the emulsified composition.
　本発明の乳化組成物は、界面活性剤を実質的に含まないことが最も好ましい。 Most preferably, the emulsified composition of the present invention is substantially free of surfactants.
　本発明の乳化組成物は乳化のための界面活性剤の含有量を少なくすることで、肌への刺激を少なくできる等の安全面で有用なだけでなく、ツヤのある外観とみずみずしさとコク感を備える乳化組成物とすることができる。このような特性は、本発明にかかる成分Ａ、すなわち、アクリル酸エステル（ａ）／化合物（ｂ）共重合体を乳化剤として用いることに起因していると推察される。アクリル酸エステル（ａ）／化合物（ｂ）共重合体は、一般的な界面活性剤を用いて油性成分を乳化させた場合と比較して、乳化粒子径の大きい乳化組成物を得ることができ、これにより、ツヤやコク感といった特性を備える乳化組成物とすることができる。 By reducing the content of the surfactant for emulsification, the emulsified composition of the present invention is not only useful in terms of safety such as less irritation to the skin, but also has a glossy appearance, freshness and richness. It can be an emulsion composition comprising It is speculated that such properties are due to the use of the component A of the present invention, that is, the acrylic acid ester (a)/compound (b) copolymer as an emulsifier. The acrylic acid ester (a)/compound (b) copolymer can provide an emulsified composition with a larger emulsified particle size than when an oily component is emulsified using a general surfactant. As a result, an emulsified composition having properties such as luster and richness can be obtained.
－添加剤－
　本発明の乳化組成物は、上述した成分Ａ、油性成分、界面活性剤および水のほかに、添加剤が含まれていてもよい。このような添加剤としては、乳化組成物に一般的に用いられるものであれば特に限定されず、例えば、ｐＨ調整剤、電解質、増粘剤等が挙げられる。 -Additive-
The emulsified composition of the present invention may contain additives in addition to the component A, oil component, surfactant and water described above. Such additives are not particularly limited as long as they are commonly used in emulsified compositions, and examples thereof include pH adjusters, electrolytes, thickeners, and the like.
　ｐＨ調整剤の具体例としては、例えば、炭酸、酢酸、乳酸、グルコン酸、コハク酸、グルタル酸、アジピン酸、リンゴ酸、酒石酸、マレイン酸、フマル酸、イタコン酸、クエン酸、安息香酸、サリチル酸、没食子酸、フタル酸、ジエチルバルビツル酸、ヒアルロン酸、ＤＬ-ピロリドンカルボン酸、アスコルビン酸、パントテン酸、チオグリコール酸等のカルボン酸類；グリシン、アラニン、バリン、ロイシン、セリン、グルタミン酸、アスパラギン酸等のアミノ酸類；エタンスルホン酸、フェノールスルホン酸、ｐ-トルエンスルホン酸、ｍ-キシレンスルホン酸等の有機スルホン酸類；タウリン等のアミノスルホン酸類；塩酸、硫酸、硝酸、リン酸等の無機酸類等の酸剤；トリメチルアミン、トリエチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、２-アミノ-２-メチルプロパノール、２-アミノ-２-メチル-１，３-プロパンジオール、ジイソプロパノールアミン、トロメタミン、コカミドメチルモノエタノールアミン等のアミン類；アンモニア、炭酸アンモニウム、リン酸二水素一アンモニウム、塩化ステアリルトリメチルアンモニウム等のアンモニアおよびアンモニウム類；水酸化リチウム、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物；水酸化マグネシウム、水酸化カルシウム等のアルカリ土類金属水酸化物の無機塩基類等のアルカリ剤等が挙げられる。 Specific examples of pH adjusters include carbonic acid, acetic acid, lactic acid, gluconic acid, succinic acid, glutaric acid, adipic acid, malic acid, tartaric acid, maleic acid, fumaric acid, itaconic acid, citric acid, benzoic acid, and salicylic acid. , gallic acid, phthalic acid, diethylbarbituric acid, hyaluronic acid, DL-pyrrolidone carboxylic acid, ascorbic acid, pantothenic acid, thioglycolic acid; glycine, alanine, valine, leucine, serine, glutamic acid, aspartic acid, etc. Amino acids; organic sulfonic acids such as ethanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, m-xylenesulfonic acid; aminosulfonic acids such as taurine; inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc. Acid agents; trimethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methylpropanol, 2-amino-2-methyl-1,3-propanediol, diisopropanolamine, tromethamine, cocamidomethyl Amines such as monoethanolamine; ammonia and ammoniums such as ammonia, ammonium carbonate, monoammonium dihydrogen phosphate, and stearyltrimethylammonium chloride; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; Examples include alkali agents such as inorganic bases of alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide.
　これらのｐＨ調整剤は、１種類のｐＨ調整剤を単独で用いてもよいし、２種以上のｐＨ調整剤を組み合わせて用いてもよい。また、これらのｐＨ調整剤は、市販のものを用いればよい。 As for these pH adjusters, one type of pH adjuster may be used alone, or two or more types of pH adjusters may be used in combination. Moreover, these pH adjusters should just use a commercial thing.
　上述したｐＨ調整剤は、本発明の乳化組成物が所望のｐＨとなるように、任意の量を添加すればよい。本発明の乳化組成物は、ｐＨが４～１２の弱酸性～アルカリ性であることが好ましく、ｐＨが５～１０であることがより好ましく、ｐＨが６～９であることがさらに好ましい。乳化組成物のｐＨは、乳化組成物を含有する皮膚外用剤や化粧料の用途によって適宜調節してもよい。 Any amount of the above-described pH adjuster may be added so that the emulsified composition of the present invention has a desired pH. The emulsified composition of the present invention preferably has a weakly acidic to alkaline pH of 4-12, more preferably a pH of 5-10, and even more preferably a pH of 6-9. The pH of the emulsified composition may be appropriately adjusted depending on the use of the external skin preparation or cosmetic containing the emulsified composition.
　電解質の具体例としては、例えば、炭酸、酢酸、乳酸、グルコン酸、コハク酸、グルタル酸、アジピン酸、リンゴ酸、酒石酸、マレイン酸、フマル酸、イタコン酸、クエン酸、安息香酸、サリチル酸、没食子酸、フタル酸、ジエチルバルビツル酸、ヒアルロン酸、ＤＬ-ピロリドンカルボン酸、アスコルビン酸、パントテン酸、チオグリコール酸等のカルボン酸類；グリシン、アラニン、バリン、ロイシン、セリン、グルタミン酸、アスパラギン酸等のアミノ酸類；エタンスルホン酸、フェノールスルホン酸、ｐ-トルエンスルホン酸、ｍ-キシレンスルホン酸等の有機スルホン酸類；タウリン等のアミノスルホン酸類；塩酸、硫酸、硝酸、リン酸等の無機酸類等の酸剤；トリメチルアミン、トリエチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、２-アミノ-２-メチルプロパノール、２-アミノ-２-メチル-１，３-プロパンジオール、ジイソプロパノールアミン、トロメタミン、コカミドメチルモノエタノールアミン等のアミン類と上述したカルボン酸類、有機スルホン酸類、無機酸類等の酸剤との中和生成塩；例えば、リジン、アルギニン等の塩基性アミノ酸類と上述したカルボン酸類、有機スルホン酸類、無機酸類等の酸剤との中和生成塩；例えば、アンモニア、水酸化ナトリウム、水酸化カリウム、水酸化マグネシウム、水酸化カルシウム等の無機塩基類等のアルカリ剤と上述したカルボン酸類、有機スルホン酸類、無機酸類等の酸剤との中和生成塩；エデト酸二ナトリウム、ココイルメチルタウリンナトリウム、ラウロイルメチルアラニンナトリウム、ラウロイルサルコシンナトリウム、ラウレス-４-カルボン酸ナトリウム、ココイルグルタミン酸ナトリウム、エチレンジアミン四酢酸二ナトリウム、ラウレス硫酸ナトリウム、フェニルベンズイミダゾールスルホン酸ナトリウム、亜硫酸ナトリウム（無水）、エチレンジアミンジコハク酸三ナトリウム、臭素酸ナトリウム、リン酸-Ｌ-アスコルビルナトリウム、リン酸-Ｌ-アスコルビルマグネシウム、塩化ステアリルトリメチルアンモニウム等のこの分野で通常用いられる酸剤とアルカリ剤との中和生成塩；グリチルリチン酸ジカリウム等の有効成分等が挙げられる。なお、ここで挙げた電解質は、上述したｐＨ調整剤の機能を兼ねるものも含まれる。 Specific examples of electrolytes include carbonic acid, acetic acid, lactic acid, gluconic acid, succinic acid, glutaric acid, adipic acid, malic acid, tartaric acid, maleic acid, fumaric acid, itaconic acid, citric acid, benzoic acid, salicylic acid, and gallic acid. Acids, phthalic acid, diethylbarbituric acid, hyaluronic acid, DL-pyrrolidonecarboxylic acid, ascorbic acid, pantothenic acid, carboxylic acids such as thioglycolic acid; amino acids such as glycine, alanine, valine, leucine, serine, glutamic acid, aspartic acid organic sulfonic acids such as ethanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid and m-xylenesulfonic acid; aminosulfonic acids such as taurine; acid agents such as inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid ; trimethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methylpropanol, 2-amino-2-methyl-1,3-propanediol, diisopropanolamine, tromethamine, cocamide methyl monoethanol Salts produced by neutralization of amines such as amines and acid agents such as the above-mentioned carboxylic acids, organic sulfonic acids, and inorganic acids; Salts produced by neutralization with an acid agent such as acids; Salts produced by neutralization with acid agents such as inorganic acids; disodium edetate, sodium cocoyl taurate, sodium lauroyl methyl alanine, sodium lauroyl sarcosinate, sodium laureth-4-carboxylate, sodium cocoyl glutamate, disodium ethylenediaminetetraacetate, Sodium laureth sulfate, sodium phenylbenzimidazole sulfonate, sodium sulfite (anhydrous), trisodium ethylenediaminedisuccinate, sodium bromate, sodium L-ascorbyl phosphate, magnesium L-ascorbyl phosphate, stearyltrimethylammonium chloride, etc. Neutralization salts of acid agents and alkali agents commonly used in this field; active ingredients such as dipotassium glycyrrhizinate; The electrolytes mentioned here include those that also function as the above-described pH adjuster.
　これらの電解質は、１種類の電解質を単独で用いてもよいし、２種以上の電解質を組み合わせて用いてもよい。また、これらの電解質は、市販のものを用いればよい。 As for these electrolytes, one type of electrolyte may be used alone, or two or more types of electrolytes may be used in combination. Moreover, these electrolytes should just use a commercial thing.
　これらの電解質のなかでも、本発明の乳化組成物を含有する皮膚外用剤や化粧料への安定配合および肌塗布時の保水性、保湿性等の観点から、炭酸水素ナトリウム、炭酸ナトリウム、炭酸マグネシウム、炭酸カルシウム、乳酸ナトリウム、乳酸マグネシウム、乳酸カルシウム、コハク酸二ナトリウム、リンゴ酸ナトリウム、クエン酸ナトリウム、クエン酸カリウム、クエン酸マグネシウム、クエン酸カルシウム、ＤＬ-ピロリドンカルボン酸ナトリウム、ＤＬ-ピロリドンカルボン酸マグネシウム、パントテン酸カルシウム、アスパラギン酸ナトリウム、アスパラギン酸マグネシウム、ココイルアルギニンエチルＰＣＡ、水酸化マグネシウム、塩化ナトリウム、塩化カリウム、塩化マグネシウム、塩化カルシウム、アスコルビン酸、リン酸-Ｌ-アスコルビルナトリウム、リン酸-Ｌ-アスコルビルマグネシウム、グリチルリチン酸ジカリウムが好ましい。 Among these electrolytes, sodium bicarbonate, sodium carbonate, and magnesium carbonate are preferred from the standpoint of stably blending in external skin preparations and cosmetics containing the emulsified composition of the present invention, and from the viewpoint of water retention and moisturizing properties when applied to the skin. , calcium carbonate, sodium lactate, magnesium lactate, calcium lactate, disodium succinate, sodium malate, sodium citrate, potassium citrate, magnesium citrate, calcium citrate, sodium DL-pyrrolidonecarboxylate, DL-pyrrolidone carboxylic acid Magnesium, Calcium Pantothenate, Sodium Aspartate, Magnesium Aspartate, Ethyl Cocoyl Arginine PCA, Magnesium Hydroxide, Sodium Chloride, Potassium Chloride, Magnesium Chloride, Calcium Chloride, Ascorbic Acid, L-Sodium Ascorbyl Phosphate, L-Phosphate - magnesium ascorbyl, dipotassium glycyrrhizinate are preferred.
　上述した電解質のなかでも、本発明の乳化組成物を含有する皮膚外用剤や化粧料の種類によっては、水酸化マグネシウム、水酸化カルシウム、塩化マグネシウム、塩化カルシウム、クエン酸マグネシウム、クエン酸カルシウム、安息香酸マグネシウム、安息香酸カルシウム、炭酸マグネシウム、炭酸カルシウム、リン酸マグネシウム、リン酸カルシウム、リン酸-Ｌ-アスコルビルマグネシウム等の多価電解質が好ましい場合がある。本発明の乳化組成は、このような多価電解質の存在下において、所望の使用感を有する乳化組成物を形成できる。 Among the electrolytes described above, magnesium hydroxide, calcium hydroxide, magnesium chloride, calcium chloride, magnesium citrate, calcium citrate, and benzoin may be used depending on the type of external skin preparation or cosmetic containing the emulsified composition of the present invention. Polyelectrolytes such as magnesium acid, calcium benzoate, magnesium carbonate, calcium carbonate, magnesium phosphate, calcium phosphate, magnesium-L-ascorbyl phosphate may be preferred. In the presence of such a polyelectrolyte, the emulsified composition of the present invention can form an emulsified composition with a desired feel.
　本発明の乳化組成物中に電解質を含む場合において、該電解質の含有量は、乳化組成物に対して０．００１～１５質量％であることが好ましく、０．０１～１０質量％であることがより好ましく、０．１～５質量％であることがさらに好ましい。 When the emulsion composition of the present invention contains an electrolyte, the content of the electrolyte is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, relative to the emulsion composition. is more preferable, and 0.1 to 5% by mass is even more preferable.
　また、本発明の乳化組成物中に電解質を含む場合において、該電解質の含有量は、成分Ａに対して１０～５００質量％であることが好ましく、１００～４００質量％であることがより好ましく、２００～３００質量％であることがさらに好ましい。電解質の含有量を成分Ａに対して２００～３００質量％の範囲に調整することにより、成分Ａが増粘して、タレ落ちしにくい性質を有する化粧料（例えば、乳液等）を調製することができる。 In addition, when the emulsion composition of the present invention contains an electrolyte, the content of the electrolyte is preferably 10 to 500% by mass, more preferably 100 to 400% by mass, relative to component A. , 200 to 300% by mass. To prepare a cosmetic composition (e.g., milky lotion, etc.) having a property of preventing dripping by increasing the viscosity of component A by adjusting the content of the electrolyte in the range of 200 to 300% by mass with respect to component A. can be done.
　本発明の乳化組成物は、高濃度（例えば、２～５質量％）の電解質の存在下において高い粘性を有し、使用感および塗布性に優れ、独特の触感を有する。 The emulsified composition of the present invention has a high viscosity in the presence of a high-concentration (for example, 2 to 5% by mass) electrolyte, is excellent in usability and spreadability, and has a unique tactile sensation.
　増粘剤の具体例としては、例えば、カルボキシメチルセルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、カチオン化セルロース、アラビアガム、カラギーナン、寒天、マンナン、グアーガム、クインスシード（マルメロ）、タマリンドガム、ローカストビーンガム、カラヤガム、トラガカントガム、ペクチン、キサンタンガム、ジェランガム、アルギン酸またはその塩、ヒアルロン酸またはその塩、コラーゲン、カゼイン、アルブミン、ゼラチン、キトサン、サクシノグリカン、デキストラン、カルボキシビニルポリマー、アルキル変性カルボキシビニルポリマー、ポリアクリルアミド、ポリビニルアルコール、ポリビニルピロリドン、高重合度ポリエチレングリコール、疎水変性ポリウレタン、セルロースナノファイバー、ベントナイト、ケイ酸アルミニウムマグネシウム、ラボナイト、ヘクトライト等が挙げられる。また、特開２０２１－１２３５９２号公報に記載の水溶性化合物を増粘剤として使用することもできる。なお、ここで挙げた増粘剤は、上述したｐＨ調整剤や電解質の機能を兼ねるものも含まれる。 Specific examples of thickeners include carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, cationized cellulose, gum arabic, carrageenan, agar, mannan, guar gum, quince seed (quince), tamarind gum, and locust bean. gum, karaya gum, tragacanth gum, pectin, xanthan gum, gellan gum, alginic acid or its salts, hyaluronic acid or its salts, collagen, casein, albumin, gelatin, chitosan, succinoglycan, dextran, carboxyvinyl polymer, alkyl-modified carboxyvinyl polymer, poly Acrylamide, polyvinyl alcohol, polyvinylpyrrolidone, highly polymerized polyethylene glycol, hydrophobically modified polyurethane, cellulose nanofiber, bentonite, aluminum magnesium silicate, labonite, hectorite and the like. Also, a water-soluble compound described in JP-A-2021-123592 can be used as a thickening agent. In addition, the thickening agent mentioned here also includes the pH adjusting agent and the electrolyte having the functions described above.
　上述した増粘剤のなかでも、使用用途や所望される粘度によっては、ヒドロキシエチルセルロース、寒天、キサンタンガム、カルボキシビニルポリマー、アルキル変性カルボキシビニルポリマーが好ましい場合がある。 Among the thickeners mentioned above, hydroxyethyl cellulose, agar, xanthan gum, carboxyvinyl polymer, and alkyl-modified carboxyvinyl polymer may be preferred depending on the intended use and desired viscosity.
　これらの増粘剤は、１種類の増粘剤を単独で用いてもよいし、２種以上の増粘剤を組み合わせて用いてもよい。また、これらの増粘剤は、市販のものを用いればよい。 As for these thickeners, one type of thickener may be used alone, or two or more types of thickeners may be used in combination. Moreover, these thickeners should just use a commercial thing.
　本発明の乳化組成物中に増粘剤を含む場合において、該増粘剤の含有量は、乳化組成物に対して０．００１～１０質量％であることが好ましく、０．０１～５質量％であることがより好ましく、０．０１～３質量％であることがさらに好ましい。 When the emulsion composition of the present invention contains a thickener, the content of the thickener is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, relative to the emulsion composition. %, more preferably 0.01 to 3% by mass.
　本発明の乳化組成物は、増粘剤の存在下において高粘度の組成物とすることができ、高い粘性が望まれる皮膚外用剤や化粧料に好適に用いることができる。 The emulsified composition of the present invention can be made into a highly viscous composition in the presence of a thickener, and can be suitably used for external skin preparations and cosmetics that require high viscosity.
－本発明の乳化組成物の製造方法－
　本発明の乳化組成物の製造方法（以下、本発明の製造方法と略記する場合がある。）は、上記成分Ａを含む水相を調製する工程と、上記油性成分を含む油相を調製する工程と、該水相と該油相を混合して乳化させる工程を含む。 -Method for producing emulsion composition of the present invention-
The method for producing an emulsified composition of the present invention (hereinafter sometimes abbreviated as the production method of the present invention) includes the steps of preparing an aqueous phase containing the component A, and preparing an oil phase containing the oily component. and mixing and emulsifying the water phase and the oil phase.
　本発明の製造方法の具体例としては、イオン交換水等の水中に成分Ａを添加した後、溶液をｐＨが中性付近になるように水酸化ナトリウム水溶液を添加して適宜攪拌して溶液１を得る。次いで、別の容器に電解質を含む水溶液を用意し、この溶液を上記溶液１に添加し水相を得る（水相調製工程）。水相とは別に、油性成分を含む油相を調製する（油相調製工程）。なお、乳化組成物中に界面活性剤を含む場合には、その特性に応じて、水溶性の界面活性剤は水相に添加し、油溶性の界面活性剤は油相に添加すればよい。その後、上記水相と上記油相を混合し、ホモミキサーもしくはディスパーまたは自公転式ミキサー等を用い、目的の乳化粒子の大きさになるまで水相と油相を攪拌して乳化することにより（乳化工程）、本発明の乳化組成物を調製できる。 As a specific example of the production method of the present invention, after adding component A to water such as ion-exchanged water, a sodium hydroxide aqueous solution is added so that the pH of the solution becomes near neutral, and the solution is stirred as appropriate to obtain solution 1. get Next, an aqueous solution containing an electrolyte is prepared in another container, and this solution is added to the solution 1 to obtain an aqueous phase (aqueous phase preparation step). Separately from the water phase, an oil phase containing an oily component is prepared (oil phase preparation step). When the emulsified composition contains a surfactant, a water-soluble surfactant may be added to the water phase, and an oil-soluble surfactant may be added to the oil phase, depending on the properties of the emulsion composition. After that, the aqueous phase and the oil phase are mixed, and the aqueous phase and the oil phase are stirred and emulsified using a homomixer, a disper, a rotation-revolution mixer, or the like until the desired emulsified particle size is achieved ( emulsification step), the emulsified composition of the present invention can be prepared.
　乳化工程における水相と油相の混合方法は特に限定されず、水相に油相を添加して混合してもよいし、油相に水相を添加して混合してもよい。 The method of mixing the water phase and the oil phase in the emulsification step is not particularly limited, and the oil phase may be added to the water phase and mixed, or the water phase may be added to the oil phase and mixed.
　水相調製工程、油相調製工程および乳化工程時の温度は特に限定されないが、一般的には、本発明の製造方法に用いられる油性成分の融点以上、１００℃以下に設定することが望ましい。 The temperature during the aqueous phase preparation step, the oil phase preparation step and the emulsification step is not particularly limited, but it is generally desirable to set the temperature above the melting point of the oily component used in the production method of the present invention and below 100°C.
　乳化工程時の攪拌速度としては、水相と油相が乳化できる攪拌速度であれば特に限定されないが、通常１００～１０，０００ｒｐｍ、好ましくは５００～５，０００ｒｐｍである。なお、水相調製工程時および油相調製工程時における攪拌速度は、水相あるいは油相に含まれる各成分が混合・溶解・分散できる速度であれば特に限定されない。 The stirring speed during the emulsification process is not particularly limited as long as it is a stirring speed at which the water phase and the oil phase can be emulsified. The stirring speed during the water phase preparation step and the oil phase preparation step is not particularly limited as long as it is a speed at which each component contained in the water phase or the oil phase can be mixed, dissolved, and dispersed.
　乳化工程時の乳化時間は特に限定されないが、バッチ式の乳化機で製造する場合は１～６０分、連続式の乳化機で製造する場合は１分以下が好ましい。 The emulsification time during the emulsification process is not particularly limited, but it is preferably 1 to 60 minutes when manufacturing with a batch emulsifier, and 1 minute or less when manufacturing with a continuous emulsifier.
　乳化工程時の圧力は、常圧のみならず減圧もしくは加圧でもよい。減圧もしくは加圧下で撹拌すると、泡が混入しにくくなり効果的に乳化できる場合がある。 The pressure during the emulsification process may be not only normal pressure but also reduced pressure or increased pressure. Stirring under reduced pressure or increased pressure may result in effective emulsification because bubbles are less likely to mix.
　本発明の製造方法にかかる乳化工程は、上述した方法に限定されるわけではなく、種々の手法を採用することができる。例えば、機械乳化法、Ｄ相乳化法、転相乳化法、液晶乳化法、アミノ酸ゲル乳化法が挙げられる。機械乳化法には、例えば、高圧ホモジナイザー、コロイドミル、ナノマイザー、マイクロフルイタイザー、プロペラ付攪拌機、ホモミキサー、ホモディスパー、自公転式ミキサー、マグネチックスターラー等を使用することができる。また、プロペラ付攪拌機、ホモミキサー、ホモディスパー等を用いる場合の回転数は、通常５００ｒｐｍ以上、好ましくは８００ｒｐｍ以上、より好ましくは１，２００ｒｐｍ以上であり、通常２０，０００ｒｐｍ以下である。 The emulsification process according to the production method of the present invention is not limited to the method described above, and various methods can be adopted. For example, a mechanical emulsification method, a D phase emulsification method, a phase inversion emulsification method, a liquid crystal emulsification method, and an amino acid gel emulsification method can be mentioned. For the mechanical emulsification method, for example, a high-pressure homogenizer, colloid mill, nanomizer, microfluidizer, stirrer with propeller, homomixer, homodisper, rotation-revolution mixer, magnetic stirrer and the like can be used. When using a propeller-equipped stirrer, homomixer, homodisper, or the like, the rotation speed is usually 500 rpm or more, preferably 800 rpm or more, more preferably 1,200 rpm or more, and usually 20,000 rpm or less.
－本発明の皮膚外用剤および化粧料－
　本発明の皮膚外用剤および化粧料は、本発明の乳化組成物を含有するものであり、該乳化組成物に、皮膚外用剤や化粧料として一般的に用いられる他の任意成分を配合してもよいし、皮膚外用剤にあっては、本発明の乳化組成物をそのまま皮膚外用剤とすることも可能である。 -External preparation for skin and cosmetics of the present invention-
The external skin preparation and cosmetic of the present invention contain the emulsified composition of the present invention, and the emulsified composition is blended with other optional ingredients generally used as external skin preparations and cosmetics. Alternatively, the emulsified composition of the present invention can be directly used as an external skin preparation.
　本発明の皮膚外用剤および化粧料中における本発明の乳化組成物の含有量としては、通常１～１００質量％、好ましくは３０～１００質量％である。 The content of the emulsified composition of the present invention in the external skin preparation and cosmetic of the present invention is usually 1-100% by mass, preferably 30-100% by mass.
－任意成分－
　本発明の皮膚外用剤および化粧料に配合される他の任意成分としては、この分野で通常用いられる添加剤であれば特に制限なく用いることができる。このような成分の具体例としては、例えば、増粘剤、染毛剤、整髪剤、紫外線防止剤、美白剤、抗老化（アンチエイジング）剤、保湿剤、柔軟剤、酸化防止剤、防腐剤、抗菌剤、抗炎症剤、細胞賦活剤、ｐＨ調整剤、緩衝剤、界面活性剤、制酸剤、増泡剤、泡質改善剤、油剤、乳化剤、分散剤、粘度調整剤、帯電防止剤、色材、香料、植物抽出物、ビタミン類、清涼剤等の医薬部外品原料規格２００６に収録されている種々の成分や、粉体、本発明にかかる共重合体以外のポリマー成分等が挙げられる。 -Optional Ingredients-
Other optional ingredients to be blended in the external preparation for skin and cosmetics of the present invention can be used without particular limitation as long as they are additives commonly used in this field. Specific examples of such ingredients include thickeners, hair dyes, hair styling agents, UV inhibitors, whitening agents, anti-aging agents, moisturizers, softeners, antioxidants, and preservatives. , antibacterial agents, anti-inflammatory agents, cell activators, pH adjusters, buffers, surfactants, antacids, foam boosters, foam improvers, oils, emulsifiers, dispersants, viscosity adjusters, antistatic agents , Coloring materials, fragrances, plant extracts, vitamins, various ingredients listed in the Standards for Quasi-drug Ingredients 2006 such as cooling agents, powders, polymer ingredients other than the copolymer according to the present invention, etc. mentioned.
　本発明の皮膚外用剤および化粧料の調製方法としては、この分野で通常行われる方法（配合方法）であれば特に限定されず、本発明の乳化組成物と必要に応じて他の任意成分を一般的な手法で配合し、本発明の皮膚外用剤および化粧料とすればよい。 The method for preparing the external preparation for skin and the cosmetic of the present invention is not particularly limited as long as it is a method (compounding method) commonly practiced in this field, and the emulsified composition of the present invention and, if necessary, other optional ingredients are combined. The external preparation for skin and the cosmetic of the present invention may be prepared by blending by a general method.
　このようにして得られる本発明の皮膚外用剤および化粧料は、使用用途に適したｐＨを有することが望ましい。本発明の皮膚外用剤および化粧料のｐＨとしては、ｐＨ４～１２の弱酸性～アルカリ性であることが好ましく、ｐＨ５～１０であることがより好ましい。本発明の皮膚外用剤および化粧料のｐＨを調整するには、上述したｐＨ調整剤を用いて行えばよい。 It is desirable that the external preparation for skin and the cosmetic of the present invention thus obtained have a pH suitable for the intended use. The pH of the external preparation for skin and the cosmetic of the present invention is preferably weakly acidic to alkaline of pH 4-12, more preferably pH 5-10. In order to adjust the pH of the external preparation for skin and the cosmetic of the present invention, the above-described pH adjuster may be used.
　本発明の皮膚外用剤の用途としては、例えば、外用液剤、外用ゲル剤、クリーム剤、軟膏剤、リニメント剤、ローション剤、ハップ剤、硬膏剤、スプレー剤、エアゾール剤、フォーム剤等が挙げられる。 Examples of applications of the external preparation for skin of the present invention include liquids for external use, gels for external use, creams, ointments, liniments, lotions, poultices, plasters, sprays, aerosols, foams, and the like. .
　本発明の化粧料の用途としては、例えば、化粧水、乳液、美容液、美容ジェル、クリーム、アイクリーム、クリームパック、マッサージクリーム、クレンジングクリーム、クレンジングジェル、洗顔フォーム、ボディーシャンプー、ボディーローション、スタイリングジェル、育毛剤、発毛剤、抗フケ剤、アイライナー、コンシーラー、アイシャドウ、マスカラ、ファンデーション、リップグロス、口紅、日焼け止め、保湿剤、制汗剤、美白剤、抗加齢剤、抗しわ剤等が挙げられる。これらの用途のなかでも、本発明の乳化組成物は、界面活性剤の配合量を少なくできることから、化粧水、乳液、美容液、クリーム、アイクリーム等の、洗い流す必要のない化粧料（製剤）に使用することが好ましい。 Applications of the cosmetic of the present invention include, for example, lotions, milky lotions, serums, beauty gels, creams, eye creams, cream packs, massage creams, cleansing creams, cleansing gels, facial cleansing foams, body shampoos, body lotions, and styling. Gel, hair restorer, hair growth agent, anti-dandruff agent, eyeliner, concealer, eyeshadow, mascara, foundation, lip gloss, lipstick, sunscreen, moisturizer, antiperspirant, whitening agent, anti-aging agent, anti-wrinkle agents and the like. Among these uses, the emulsified composition of the present invention can reduce the amount of surfactant blended. is preferably used for
　本発明の乳化組成物は、皮膚外用剤や化粧料用途以外にも、種々の用途に供することができる。例えば、医薬品（抗菌剤、抗真菌剤、う蝕予防剤、抗歯石剤、抗プラーク剤、ハップ剤、軟膏等）用途、土壌保水剤用途、帯電防止剤用途、医療廃棄物固化剤用途、石油掘削用流体、石油随伴水の処理用途、塗料（油性ペンキ、防腐用塗料、船底塗料、エマルション塗料、外壁塗料、放熱塗料、遮熱塗料、防汚コート剤、艶消し剤等）用途、インキ（油性ペイント、エマルションペイント、スプレーインク、インクジェットインク、ＵＶ硬化インク）用途、筆記用具（油性ボールペン、ゲルインクボールペン、エマルションボールペン、フリクションボールペン、フェルトペン、筆ペン、ラインマーカー、蛍光ペン、油性絵具、アクリル絵具）用途、高分子アクチュエーター用途、イオン交換膜用途、レジスト材（カラーレジスト、ブラックマトリクス）用途、透明導電膜用途、カラムスペーサー用途、オーバーコート剤用途、反射防止膜用途、スクリーン製版用乳剤用途、抄紙用粘剤用途、パルプ分散剤用途、コンクリート混和剤用途、インク受容層用途、セラミックス成形剤用途、有機染料・有機顔料・無機顔料・体質顔料等の染料や顔料を含む着色樹脂組成物（樹脂粒子）用の分散剤用途等にも、本発明の乳化組成物を供することができる。また、これらの用途に用いられる添加剤は、これらの分野で通常用いられている添加剤を使用すればよく、添加量についても、通常添加され得る添加量から適宜設定すればよい。 The emulsified composition of the present invention can be used for various purposes other than external skin preparations and cosmetics. For example, pharmaceuticals (antibacterial agents, antifungal agents, caries preventatives, anticalculus agents, antiplaque agents, poultices, ointments, etc.), soil water retention agents, antistatic agents, medical waste solidifying agents, petroleum Drilling fluids, oil-related water treatment applications, paints (oil-based paints, antiseptic paints, ship bottom paints, emulsion paints, exterior wall paints, heat-radiating paints, heat-shielding paints, antifouling coating agents, matting agents, etc.), inks ( Oil-based paint, emulsion paint, spray ink, inkjet ink, UV curing ink), writing utensils (oil-based ballpoint pen, gel ink ballpoint pen, emulsion ballpoint pen, friction ballpoint pen, felt-tip pen, brush pen, line marker, highlighter, oil-based paint, acrylic paint ) applications, polymer actuator applications, ion-exchange membrane applications, resist materials (color resist, black matrix) applications, transparent conductive film applications, column spacer applications, overcoat agent applications, anti-reflection film applications, screen-making emulsion applications, paper making Viscosity, pulp dispersant, concrete admixture, ink-receiving layer, ceramic molding agent, organic dye, organic pigment, inorganic pigment, extender pigment, etc. Colored resin composition (resin particles ), the emulsified composition of the present invention can also be used as a dispersant. Additives that are commonly used in these fields may be used as additives for these applications, and the amount to be added may be appropriately set based on the amount that can be normally added.
　以下、実施例および比較例に基づいて本発明を具体的に説明するが、実施例は本発明の単なる例示を示すものにすぎず、本発明の範囲をなんら限定するものではない。 The present invention will be specifically described below based on examples and comparative examples, but the examples are merely illustrative of the present invention and do not limit the scope of the present invention.
　合成例に記載したものを除き、各実施例および比較例に記載のポリマー、油性成分、界面活性剤、電解質およびｐＨ調整剤は、以下に示すものを使用した。
－ポリマー－
（アクリル酸パーフルオロへキシルエチル／アクリル酸）クロスポリマー；ソルトレラ：富士フイルム和光純薬株式会社製
アクリレーツ／アクリル酸アルキル（Ｃ１０－３０クロスポリマー）；ＡＱＵＰＥＣ ＨＶ８０３ＥＲＫ：住友精化株式会社製
－油性成分－
流動パラフィン：富士フイルム和光純薬株式会社製
スクワラン：富士フイルム和光純薬株式会社製
ホホバ油：富士フイルム和光純薬株式会社製
オリーブ油：富士フイルム和光純薬株式会社製
オレイルアルコール：富士フイルム和光純薬株式会社製
オレイン酸：富士フイルム和光純薬株式会社製
－界面活性剤－
ポリオキシエチレンラウリルエーテル；エマルゲン１０５：花王株式会社製
ラウリル硫酸ナトリウム：富士フイルム和光純薬株式会社製
－電解質－
リン酸-Ｌ-アスコルビルマグネシウム・ｎ水和物（水分含有量１６～２０質量％）：富士フイルム和光純薬株式会社製
－ｐＨ調整剤－
２ｍｏｌ／Ｌ水酸化ナトリウム水溶液：富士フイルム和光純薬株式会社製 Except for those described in Synthesis Examples, the following polymers, oily components, surfactants, electrolytes and pH adjusters described in Examples and Comparative Examples were used.
-polymer-
(Perfluorohexylethyl acrylate/acrylic acid) crosspolymer; Saltella: Acrylates/alkyl acrylate (C10-30 crosspolymer) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.;
Liquid paraffin: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. Squalane: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. Jojoba oil: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. Olive oil: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. Oleyl alcohol: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. Co., Ltd. Oleic acid: FUJIFILM Wako Pure Chemical Co., Ltd. -Surfactant-
Polyoxyethylene lauryl ether; Emulgen 105: manufactured by Kao Corporation Sodium lauryl sulfate: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. -Electrolyte-
Phosphate-L-ascorbyl magnesium n-hydrate (moisture content: 16-20% by mass): manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. -pH adjuster-
2 mol / L sodium hydroxide aqueous solution: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.
－合成例１－
本発明にかかる成分Ａ：アクリル酸エステル（ａ）／化合物（ｂ）共重合体の合成（１）
　アクリル酸３８．１５ｇ（０．５３ｍｏｌ；富士フイルム和光純薬株式会社製）、アクリル酸パーフルオロへキシルエチル６．８５ｇ（０．０１６ｍｏｌ；ユニマテック株式会社製）、ジエチレングリコールジアリルエーテル０．１４ｇ（０．７６ｍｍｏｌ；富士フイルム和光純薬株式会社製）およびジ（４-tert-ブチルシクロヘキシル）パーオキシジカーボネート０．０７８ｇ（０．２０ｍｍｏｌ；製品名：パーカドックス１６；化薬アクゾ株式会社製）をシクロヘキサン４０５ｍＬおよび酢酸エチル４５ｍＬの混合溶媒中に投入し、溶液を均一に混合した。混合した溶液を窒素ガス雰囲気下で３０分間バブリングし、溶液中に含まれる酸素を脱気した。その後、溶液を回転数２００ｒｐｍで攪拌しながら、３０分かけて５５℃まで加熱し、同温度を維持しながら溶液をさらに１時間攪拌した。次いで、溶液を１時間３０分かけて７５℃まで加熱し、同温度を維持しながら溶液を回転数２００ｒｐｍでさらに２時間攪拌した。攪拌後、溶液を室温まで冷却し、冷却することによって析出した共重合体（ポリマー）を濾取した後、濾取した共重合体を９０～１１０℃で８時間減圧乾燥することにより、本発明にかかる成分（Ａ）４１．８５ｇを得た（収率：９３％）。合成例１で得た成分（Ａ）（アクリル酸パーフルオロへキシルエチル／アクリル酸／ジエチレングリコールジアリルエーテル＝３：９７：０．１４（※））を本発明にかかる共重合体（１）と称する。なお、※０．１４は、アクリル酸パーフルオロへキシルエチルとアクリル酸の合計を１００ｍｏｌとした場合のジエチレングリコールジアリルエーテルのｍｏｌ量を表す。 -Synthesis Example 1-
Component A according to the present invention: Synthesis of acrylic acid ester (a) / compound (b) copolymer (1)
Acrylic acid 38.15 g (0.53 mol; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), perfluorohexylethyl acrylate 6.85 g (0.016 mol; manufactured by Unimatec Co., Ltd.), diethylene glycol diallyl ether 0.14 g (0.76 mmol) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and di(4-tert-butylcyclohexyl)peroxydicarbonate 0.078 g (0.20 mmol; product name: Perkadox 16; manufactured by Kayaku Akzo Co., Ltd.) were added to 405 mL of cyclohexane and The mixture was poured into a mixed solvent of 45 mL of ethyl acetate, and the solution was uniformly mixed. The mixed solution was bubbled for 30 minutes in a nitrogen gas atmosphere to deaerate oxygen contained in the solution. The solution was then heated to 55° C. over 30 minutes while being stirred at a rotation speed of 200 rpm, and the solution was further stirred for 1 hour while maintaining the same temperature. The solution was then heated to 75° C. over 1 hour and 30 minutes, and the solution was stirred at 200 rpm for an additional 2 hours while maintaining the same temperature. After stirring, the solution is cooled to room temperature, the copolymer (polymer) precipitated by cooling is collected by filtration, and the filtered copolymer is dried under reduced pressure at 90 to 110° C. for 8 hours to obtain the present invention. 41.85 g of component (A) was obtained (yield: 93%). Component (A) (perfluorohexylethyl acrylate/acrylic acid/diethylene glycol diallyl ether=3:97:0.14 (*)) obtained in Synthesis Example 1 is referred to as copolymer (1) of the present invention. *0.14 represents the molar amount of diethylene glycol diallyl ether when the total of perfluorohexylethyl acrylate and acrylic acid is 100 mol.
－合成例２－
本発明にかかる成分Ａ：アクリル酸エステル（ａ）／化合物（ｂ）共重合体の合成（２）
　アクリル酸３８．１５ｇ（０．５３ｍｏｌ）、アクリル酸パーフルオロへキシルエチル６．８５ｇ（０．０１６ｍｏｌ）、ジエチレングリコールジアリルエーテル０．２３ｇ（１．２６ｍｍｏｌ）および２，２’-アゾビス（イソ酪酸）ジメチル０．０７５ｇ（０．３３ｍｍｏｌ；製品名：Ｖ－６０１；富士フイルム和光純薬株式会社製）をｎ-へプタン４５０ｍＬの混合溶媒中に投入し、溶液を均一に混合した。混合した溶液を窒素ガス雰囲気下で３０分間バブリングし、溶液中に含まれる酸素を脱気した。その後、溶液を回転数２００ｒｐｍで攪拌しながら、３０分かけて７５℃まで加熱し、同温度を維持しながら溶液をさら３時間攪拌した。次いで、溶液を３０分かけて９５℃まで加熱し、同温度を維持しながら溶液を回転数２００ｒｐｍでさらに１時間攪拌した。攪拌後、溶液を室温まで冷却し、冷却することによって析出した共重合体（ポリマー）を濾取した後、濾取した共重合体を９０～１１０℃で８時間減圧乾燥することにより、本発明にかかる成分（Ａ）４２．３９ｇを得た（収率：９４％）。合成例１で得た成分（Ａ）（アクリル酸パーフルオロへキシルエチル／アクリル酸／ジエチレングリコールジアリルエーテル＝３：９７：０．２３（※））を本発明にかかる共重合体（２）と称する。なお、※０．２３は、アクリル酸パーフルオロへキシルエチルとアクリル酸の合計を１００ｍｏｌとした場合のジエチレングリコールジアリルエーテルのｍｏｌ量を表す。 -Synthesis Example 2-
Component A according to the present invention: Synthesis of acrylic acid ester (a)/compound (b) copolymer (2)
38.15 g (0.53 mol) of acrylic acid, 6.85 g (0.016 mol) of perfluorohexylethyl acrylate, 0.23 g (1.26 mmol) of diethylene glycol diallyl ether and 2,2′-azobis(isobutyrate)dimethyl 0 0.075 g (0.33 mmol; product name: V-601; manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was put into a mixed solvent of 450 mL of n-heptane, and the solution was uniformly mixed. The mixed solution was bubbled for 30 minutes in a nitrogen gas atmosphere to deaerate oxygen contained in the solution. The solution was then heated to 75° C. over 30 minutes while being stirred at a rotation speed of 200 rpm, and the solution was further stirred for 3 hours while maintaining the same temperature. The solution was then heated to 95° C. over 30 minutes, and the solution was stirred at 200 rpm for an additional hour while maintaining the same temperature. After stirring, the solution is cooled to room temperature, the copolymer (polymer) precipitated by cooling is collected by filtration, and the filtered copolymer is dried under reduced pressure at 90 to 110° C. for 8 hours to obtain the present invention. 42.39 g of component (A) was obtained (yield: 94%). Component (A) (perfluorohexylethyl acrylate/acrylic acid/diethylene glycol diallyl ether=3:97:0.23 (*)) obtained in Synthesis Example 1 is referred to as copolymer (2) of the present invention. *0.23 represents the molar amount of diethylene glycol diallyl ether when the total of perfluorohexylethyl acrylate and acrylic acid is 100 mol.
－合成例３－
本発明にかかる成分Ａ：アクリル酸エステル（ａ）／化合物（ｂ）共重合体の合成（３）
　合成例３では、合成例２のアクリル酸の使用量を３４．４７ｇ（０．４８ｍｏｌ）に変更し、アクリル酸パーフルオロへキシルエチルの使用量を１０．５３ｇ（０．０２５ｍｏｌ）に変更し、ジエチレングリコールジアリルエーテルの使用量を０．２２ｇ（１．１６ｍｍｏｌ）に変更し、２，２’-アゾビス（イソ酪酸）ジメチルの使用量を０．０７０ｇ（０．３０ｍｍｏｌ）変更した以外は、合成例２と同様の方法に準じて、本発明にかかる成分（Ａ）を得た。合成例３で得た成分（Ａ）（アクリル酸パーフルオロへキシルエチル／アクリル酸／ジエチレングリコールジアリルエーテル＝５：９５：０．２３（※））を本発明にかかる共重合体（３）と称する。なお、※０．２３は、アクリル酸パーフルオロへキシルエチルとアクリル酸の合計を１００ｍｏｌとした場合のジエチレングリコールジアリルエーテルのｍｏｌ量を表す。 -Synthesis Example 3-
Component A according to the present invention: Synthesis of acrylic acid ester (a) / compound (b) copolymer (3)
In Synthesis Example 3, the amount of acrylic acid used in Synthesis Example 2 was changed to 34.47 g (0.48 mol), the amount of perfluorohexylethyl acrylate used was changed to 10.53 g (0.025 mol), and diethylene glycol was added. Synthesis Example 2 and A component (A) according to the present invention was obtained according to a similar method. Component (A) obtained in Synthesis Example 3 (perfluorohexylethyl acrylate/acrylic acid/diethylene glycol diallyl ether=5:95:0.23 (*)) is referred to as copolymer (3) of the present invention. *0.23 represents the molar amount of diethylene glycol diallyl ether when the total of perfluorohexylethyl acrylate and acrylic acid is 100 mol.
－合成例４－
本発明にかかる成分Ａ：アクリル酸エステル（ａ）／化合物（ｂ）共重合体の合成（４）
　合成例４では、合成例１のアクリル酸の使用量を４０．２４ｇ（０．５６ｍｏｌ）に変更し、アクリル酸パーフルオロへキシルエチルの使用量を４．７６ｇ（０．０１１ｍｏｌ）に変更し、ジエチレングリコールジアリルエーテルをペンタエリスリトールトリアリルエーテルに変更して、その使用量を０．１５ｇ（０．５７ｍｍｏｌ）とし、ジ（４-tert-ブチルシクロヘキシル）パーオキシジカーボネートの使用量を０．０８２ｇ（０．２１ｍｍｏｌ）に変更した以外は、合成例１と同様の方法に準じて、本発明にかかる成分（Ａ）を得た。合成例４で得た成分（Ａ）（アクリル酸パーフルオロへキシルエチル／アクリル酸／ペンタエリスリトールトリアリルエーテル＝２：９８：０．１０）を本発明にかかる共重合体（４）と称する。なお、※０．１０は、アクリル酸パーフルオロへキシルエチルとアクリル酸の合計を１００ｍｏｌとした場合のペンタエリスリトールトリアリルエーテルのｍｏｌ量を表す。 -Synthesis Example 4-
Component A according to the present invention: Synthesis of acrylic acid ester (a) / compound (b) copolymer (4)
In Synthesis Example 4, the amount of acrylic acid used in Synthesis Example 1 was changed to 40.24 g (0.56 mol), the amount of perfluorohexylethyl acrylate used was changed to 4.76 g (0.011 mol), and diethylene glycol was added. Diallyl ether was changed to pentaerythritol triallyl ether, the amount used was changed to 0.15 g (0.57 mmol), and the amount of di(4-tert-butylcyclohexyl)peroxydicarbonate used was changed to 0.082 g (0.57 mmol). 21 mmol), the component (A) according to the present invention was obtained in the same manner as in Synthesis Example 1. Component (A) obtained in Synthesis Example 4 (perfluorohexylethyl acrylate/acrylic acid/pentaerythritol triallyl ether=2:98:0.10) is referred to as copolymer (4) of the present invention. *0.10 represents the molar amount of pentaerythritol triallyl ether when the total of perfluorohexylethyl acrylate and acrylic acid is 100 mol.
－実施例１－
本発明の乳化組成物の調製（１）
　常温条件下、イオン交換水２０．５ｇに（アクリル酸パーフルオロへキシルエチル／アクリル酸）クロスポリマー０．５ｇを加え、回転数５５０ｒｐｍで攪拌し、均一な分散液を得た。次いで、得られた分散液に、分散液のｐＨが７．５となるように２ｍｏｌ／Ｌの水酸化ナトリウム水溶液を添加して中和した後、自公転式ミキサー（あわとり練太郎ＡＲＥ－３１０：株式会社シンキー製）を用い、回転数２，０００～２，２００ｒｐｍで２０分間攪拌して、溶液１を得た。次いで、別の容器にリン酸-Ｌ-アスコルビルマグネシウム・ｎ水和物１．０ｇをイオン交換水に溶解させた溶液１０．０ｇを用意し、この溶液を、先の溶液１に添加し、イオン交換水１．０ｇを加え、自公転式ミキサー（あわとり練太郎ＡＲＥ－３１０：株式会社シンキー製）を用い、回転数２，０００～２，２００ｒｐｍで２０分間攪拌することで水相Ａを得た（水相調製工程）。水相Ａとは別に、流動パラフィン１５ｇを含む油相Ｂを用意した（油相調製工程）。該水相Ａに油相Ｂを添加し、自公転式ミキサー（あわとり練太郎ＡＲＥ－３１０：株式会社シンキー製）を用い、回転数２，０００～２，２００ｒｐｍで２０分間混錬することにより、水中油型（Ｏ／Ｗ）の乳化組成物を得た。 -Example 1-
Preparation of emulsified composition of the present invention (1)
Under normal temperature conditions, 0.5 g of (perfluorohexylethyl acrylate/acrylic acid) crosspolymer was added to 20.5 g of ion-exchanged water, and the mixture was stirred at a rotation speed of 550 rpm to obtain a uniform dispersion. Next, the obtained dispersion was neutralized by adding a 2 mol/L sodium hydroxide aqueous solution so that the pH of the dispersion became 7.5, and then a rotation-revolution mixer (Awatori Mixer ARE-310 : manufactured by Thinky Co., Ltd.) and stirred at a rotation speed of 2,000 to 2,200 rpm for 20 minutes to obtain a solution 1. Next, prepare 10.0 g of a solution in which 1.0 g of magnesium L-ascorbyl phosphate n-hydrate is dissolved in ion-exchanged water in another container, add this solution to the previous solution 1, and ion 1.0 g of exchanged water is added, and the water phase A is obtained by stirring for 20 minutes at a rotation speed of 2,000 to 2,200 rpm using a rotation-revolution mixer (Awatori Mixer ARE-310: manufactured by Thinky Co., Ltd.). (aqueous phase preparation step). Separately from the water phase A, an oil phase B containing 15 g of liquid paraffin was prepared (oil phase preparation step). The oil phase B is added to the water phase A, and kneaded for 20 minutes at a rotation speed of 2,000 to 2,200 rpm using a rotation-revolution mixer (Awatori Mixer ARE-310: manufactured by Thinky Co., Ltd.). , to obtain an oil-in-water (O/W) emulsified composition.
－実施例２～１７－
本発明の乳化組成物の調製（２）～（１７）
　実施例２～１７では、表１に記載の成分を、各成分の割合（質量％）が表１となるように使用した以外は、実施例１と同様の方法に準じて、本発明の乳化組成物（２）～（１７）を得た。なお、表中の界面活性剤は、水相調製工程において、リン酸-Ｌ-アスコルビルマグネシウム・ｎ水和物を含む溶液を溶液１に加えた後の溶液に添加して、水相Ａを調製した。実施例２～１７における各成分の名称と各成分の割合（組成物の全量を１００とした場合における各成分の質量％）を表１に示す。 - Examples 2 to 17 -
Preparation of emulsified composition of the present invention (2) to (17)
In Examples 2 to 17, the emulsification of the present invention was performed in the same manner as in Example 1, except that the components shown in Table 1 were used so that the proportions (mass%) of each component were as shown in Table 1. Compositions (2) to (17) were obtained. The surfactants in the table were added to the solution after adding the solution containing magnesium L-ascorbyl phosphate n-hydrate to the solution 1 in the aqueous phase preparation step to prepare the aqueous phase A. bottom. Table 1 shows the name of each component and the ratio of each component (mass% of each component when the total amount of the composition is 100) in Examples 2 to 17.
－比較例１～７－
比較用の乳化組成物の調製（１）～（７）
　比較例１～７では、表１に記載の成分を、各成分の割合（質量％）が表１となるように使用した以外は、実施例１と同様の方法に準じて、比較用の乳化組成物（１）～（７）を得た。なお、表中の界面活性剤は、水相調製工程において、リン酸-Ｌ-アスコルビルマグネシウム・ｎ水和物を含む溶液を溶液１に加えた後の溶液に添加して、水相Ａを調製した。比較例１～７における各成分の名称と各成分の割合（組成物の全量を１００とした場合における各成分の質量％）を表１に示す。 -Comparative Examples 1 to 7-
Preparation of emulsified composition for comparison (1) to (7)
In Comparative Examples 1 to 7, emulsification for comparison was performed in the same manner as in Example 1, except that the components shown in Table 1 were used so that the proportions (% by mass) of each component were as shown in Table 1. Compositions (1) to (7) were obtained. The surfactants in the table were added to the solution after adding the solution containing magnesium L-ascorbyl phosphate n-hydrate to the solution 1 in the aqueous phase preparation step to prepare the aqueous phase A. bottom. Table 1 shows the name of each component and the ratio of each component (mass% of each component when the total amount of the composition is 100) in Comparative Examples 1 to 7.
－実施例１８～３４－
本発明の乳化組成物の調製（１８）～（３４）
　実施例１８～３４では、表２に記載の成分を、各成分の割合（質量％）が表２となるように使用した以外は、実施例１と同様の方法に準じて、本発明の乳化組成物（１８）～（３４）を得た。なお、表中の界面活性剤は、水相調製工程において、リン酸-Ｌ-アスコルビルマグネシウム・ｎ水和物を含む溶液を溶液１に加えた後の溶液に添加して、水相Ａを調製した。実施例１８～３４における各成分の名称と各成分の割合（組成物の全量を１００とした場合における各成分の質量％）を表２に示す。 - Examples 18 to 34 -
Preparation of emulsified composition of the present invention (18) to (34)
In Examples 18 to 34, the emulsification of the present invention was prepared in the same manner as in Example 1, except that the components shown in Table 2 were used so that the proportions (mass%) of each component were as shown in Table 2. Compositions (18) to (34) were obtained. The surfactants in the table were added to the solution after adding the solution containing magnesium L-ascorbyl phosphate n-hydrate to the solution 1 in the aqueous phase preparation step to prepare the aqueous phase A. bottom. Table 2 shows the name of each component and the ratio of each component (mass% of each component when the total amount of the composition is 100) in Examples 18 to 34.
－実施例３５～４１－
本発明の乳化組成物の調製（３５）～（４１）
　実施例３５～４１では、表３に記載の成分を、各成分の割合（質量％）が表３となるように使用した以外は、実施例１と同様の方法に準じて、本発明の乳化組成物（３５）～（４１）を得た。なお、表中の界面活性剤は、水相調製工程において、リン酸-Ｌ-アスコルビルマグネシウム・ｎ水和物を含む溶液を溶液１に加えた後の溶液に添加して、水相Ａを調製した。実施例３５～４１における各成分の名称と各成分の割合（組成物の全量を１００とした場合における各成分の質量％）を表３に示す。 - Examples 35 to 41 -
Preparation of emulsified composition of the present invention (35) to (41)
In Examples 35 to 41, the emulsification of the present invention was prepared in the same manner as in Example 1, except that the components shown in Table 3 were used so that the proportions (mass%) of each component were as shown in Table 3. Compositions (35) to (41) were obtained. The surfactants in the table were added to the solution after adding the solution containing magnesium L-ascorbyl phosphate n-hydrate to the solution 1 in the aqueous phase preparation step to prepare the aqueous phase A. bottom. Table 3 shows the name of each component and the ratio of each component (mass% of each component when the total amount of the composition is 100) in Examples 35 to 41.
－実施例４２～４３－
本発明の乳化組成物の調製（４２）～（４３）
　実施例４２～４３では、表４に記載の成分を、各成分の割合（質量％）が表４となるように使用した以外は、実施例１と同様の方法に準じて、本発明の乳化組成物（４２）～（４３）を得た。実施例４２～４３における各成分の名称と各成分の割合（組成物の全量を１００とした場合における各成分の質量％）を、実施例１８および実施例３５の結果とあわせて表４に示す。 - Examples 42 to 43 -
Preparation of emulsified composition of the present invention (42) to (43)
In Examples 42 and 43, the emulsification of the present invention was prepared according to the same method as in Example 1, except that the components shown in Table 4 were used so that the proportions (% by mass) of each component were as shown in Table 4. Compositions (42) to (43) were obtained. The name of each component and the ratio of each component (mass% of each component when the total amount of the composition is 100) in Examples 42 to 43 are shown in Table 4 together with the results of Example 18 and Example 35. .
－評価例１～５０－
　本発明の乳化組成物（１）～（４３）および比較用の乳化組成物（１）～（７）の性能評価
　実施例および比較例の乳化組成物をそのまま皮膚外用剤として用い、以下に示す評価方法により、経時安定性、外観（ツヤ）、ならびに使用感［塗布時のみずみずしさおよび塗布（塗り広げた）後のコク感］を評価した。
＜評価方法＞
・経時安定性
　乳化直後および乳化直後から１ヶ月経過した後の乳化組成物について、該組成物が均一な乳化状態であるかを、外観から評価した。
・外観および使用感の評価
ｉ．ツヤ
　乳化直後の乳化組成物について、外観の「ツヤ」を、最高評価を５点、最低評価を１点として、１点刻みで評価した。具体的には、最もツヤがあり高級感を感じるものを「５：優れている」として、その程度が弱くなるにつれ、「４：やや優れている」、「３：普通」、「２：やや劣る」とし、ツヤがなく、高級感を感じられないものを「１：劣る」と評価した。
ｉｉ．みずみずしさ
　乳化直後の乳化組成物について、塗布時の「みずみずしさ」を、最高評価を５点、最低評価を１点として、１点刻みで評価した。具体的には、最もみずみずしさがあり、べたつかず、伸びの良いものを「５：優れている」として、その程度が弱くなるにつれ、「４：やや優れている」、「３：普通」、「２：やや劣る」とし、みずみずしさがなく、べたつき、伸びの悪いものを「１：劣る」と評価した。
ｉｉｉ．コク感
　乳化直後の乳化組成物について、塗布（塗り広げた）後の「コク感」を、最高評価を５点、最低評価を１点とし、１点刻みで評価した。具体的には、最もコク感があり、しっとりとし、保湿感が得られるものを「５：優れている」として、その程度が弱くなるにつれ、「４：やや優れている」、「３：普通」、「２：やや劣る」とし、コク感がなく、さっぱりとし、保湿感が得られないものを「１：劣る」と評価した。
　上記３項目（ツヤ、みずみずしさ、コク感）について、評価パネラー３名により評価を行い、平均点を算出し、各項目の合計点から乳化組成物の性能を評価した。合計点が最も高い乳化組成物を最も性能が高い組成物と評価した。
　各組成物の評価結果と合計点を表１～４に示す。 -Evaluation Examples 1 to 50-
Performance evaluation of emulsified compositions (1) to (43) of the present invention and emulsified compositions (1) to (7) for comparison The emulsified compositions of Examples and Comparative Examples were used as they were as skin external preparations, and are shown below. Stability over time, appearance (gloss), and feeling during use [freshness at the time of application and richness after application (spreading)] were evaluated according to the evaluation method.
<Evaluation method>
- Stability over time The emulsion composition immediately after emulsification and after 1 month from immediately after emulsification was evaluated whether the composition was in a uniform emulsified state from the appearance.
- Evaluation of appearance and feeling i. Gloss The "gloss" of the appearance of the emulsified composition immediately after emulsification was evaluated in 1-point increments, with the highest evaluation being 5 points and the lowest evaluation being 1 point. Specifically, the most glossy and luxurious feeling is "5: excellent", and as the degree becomes weaker, "4: slightly excellent", "3: normal", "2: slightly Inferior", and those lacking luster and lacking a feeling of high quality were evaluated as "1: inferior".
ii. Freshness The emulsified composition immediately after emulsification was evaluated for "freshness" at the time of application in 1-point increments, with the highest evaluation being 5 points and the lowest evaluation being 1 point. Specifically, the most fresh, non-sticky, and spreadable product is rated as "5: excellent", and as the degree becomes weaker, "4: slightly excellent", "3: normal", "2: Slightly inferior", and "1: inferior" for lack of freshness, stickiness, and poor spreadability.
iii. Body Feeling The "body feeling" after application (spreading) of the emulsified composition immediately after emulsification was evaluated in 1-point increments, with the highest evaluation being 5 points and the lowest evaluation being 1 point. Specifically, the most rich, moist, moisturizing feeling is given as "5: excellent", and as the degree becomes weaker, "4: slightly excellent", "3: normal" and "2: Slightly inferior".
The above three items (gloss, freshness, and richness) were evaluated by three evaluation panelists, the average score was calculated, and the performance of the emulsified composition was evaluated from the total score of each item. The emulsion composition with the highest total score was evaluated as the composition with the highest performance.
Tables 1 to 4 show the evaluation results and total points for each composition.
Figure JPOXMLDOC01-appb-T000031
Figure JPOXMLDOC01-appb-T000031
Figure JPOXMLDOC01-appb-T000032
Figure JPOXMLDOC01-appb-T000032
Figure JPOXMLDOC01-appb-T000033
Figure JPOXMLDOC01-appb-T000033
Figure JPOXMLDOC01-appb-T000034
Figure JPOXMLDOC01-appb-T000034
　実施例１～４３の乳化組成物（１）～（４３）（本発明の乳化組成物）は、均一な乳化状態の経時安定性を有しており、外観のツヤ、肌に塗布した時のみずみずしさ、塗布（塗り広げた）後のしっとりとしたコク感に優れていた。その一方で、比較例１～７の乳化組成物（１）～（７）（比較用の乳化組成物）は、均一な乳化状態を保持できなかったり、外観のツヤが優れないだけでなく、みずみずしさとコク感を両立することができなかった。 Emulsified compositions (1) to (43) (emulsified compositions of the present invention) of Examples 1 to 43 have stability over time in a uniform emulsified state, and have a glossy appearance and a smooth appearance when applied to the skin. It was excellent in freshness and moist and rich feeling after application (spreading). On the other hand, the emulsified compositions (1) to (7) of Comparative Examples 1 to 7 (emulsified compositions for comparison) could not maintain a uniform emulsified state, and not only did not have an excellent glossy appearance, It was not possible to achieve both freshness and richness.
　本発明の乳化組成物は、優れた特性を有する皮膚外用剤および化粧料として使用できるため、乳化状態の経時安定性に優れ、ツヤのある外観を有し、使用感としてみずみずしさとコク感を備える、外用液剤、外用ゲル剤、クリーム剤、軟膏剤、リニメント剤、ローション剤、化粧水、乳液、美容液、美容ジェル、クリーム、アイクリーム、クリームパック、クレンジングジェル、洗顔フォーム、ボディーシャンプー、ボディーローション、スタイリングジェル、アイシャドウ等の各種皮膚外用剤および化粧料を提供することができる。 Since the emulsified composition of the present invention can be used as an external preparation for skin and a cosmetic having excellent properties, it has excellent stability over time in an emulsified state, has a glossy appearance, and has a fresh and rich feeling in use. , external liquid, external gel, cream, ointment, liniment, lotion, lotion, milky lotion, serum, beauty gel, cream, eye cream, cream pack, cleansing gel, facial cleansing foam, body shampoo, body lotion , styling gels, eye shadows, and other external skin preparations and cosmetics.

Claims (15)

  1. 乳化粒子中に油性成分を含む水中油型（Ｏ／Ｗ）の乳化組成物であって、
    前記乳化組成物は、成分Ａと油性成分とを含み、
    前記成分Ａの含有量が、前記油性成分に対して０．４～２５０質量％であり、
    前記乳化組成物は界面活性剤を実質的に含まないか、
    界面活性剤を含む場合には、該界面活性剤の含有量が、前記成分Ａに対して９０質量％以下、かつ、前記油性成分に対して３質量％以下であり、
    前記乳化組成物中における前記油性成分の含有量が、１～６５質量％である、
    乳化組成物。
    成分Ａ：（ａ）一般式［１］で示されるアクリル酸エステル、ならびに（ｂ）重合性不飽和基と、カルボキシル基、スルホ基およびリン酸基からなる群から選ばれるいずれかの官能基とを分子内に有する化合物を構成成分とし、
    前記アクリル酸エステル（ａ）と前記化合物（ｂ）との割合（質量比）が、（ａ）／（ｂ）＝６．０／９４．０～３０．０／７０．０である、アクリル酸エステル（ａ）／化合物（ｂ）共重合体。
    一般式［１］：
    Figure JPOXMLDOC01-appb-I000001
    （式中、Ｒ１は、水素原子または炭素数１～６のアルキル基を表し、ｍは、２～４の整数を表す。）     An oil-in-water (O/W) emulsified composition containing an oily component in emulsified particles,
    The emulsion composition comprises component A and an oily component,
    The content of the component A is 0.4 to 250% by mass with respect to the oily component,
    the emulsified composition is substantially free of surfactants;
    When a surfactant is included, the content of the surfactant is 90% by mass or less with respect to the component A and 3% by mass or less with respect to the oily component,
    The content of the oily component in the emulsified composition is 1 to 65% by mass,
    emulsified composition.
    Component A: (a) an acrylic acid ester represented by the general formula [1], and (b) a polymerizable unsaturated group and any functional group selected from the group consisting of a carboxyl group, a sulfo group and a phosphoric acid group A compound having in the molecule is a constituent component,
    Acrylic acid, wherein the ratio (mass ratio) of the acrylic acid ester (a) and the compound (b) is (a)/(b) = 6.0/94.0 to 30.0/70.0 Ester (a)/compound (b) copolymer.
    General formula [1]:
    Figure JPOXMLDOC01-appb-I000001
    (In the formula, R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and m represents an integer of 2 to 4.)
  2. 前記界面活性剤が、アニオン性界面活性剤または非イオン性界面活性剤である、請求項１に記載の乳化組成物。 2. The emulsion composition of Claim 1, wherein the surfactant is an anionic surfactant or a nonionic surfactant.
  3. 前記界面活性剤が、アニオン性界面活性剤であって、該アニオン性界面活性剤の含有量が、前記成分Ａに対して５０質量％以下である、請求項１に記載の乳化組成物。 2. The emulsified composition according to claim 1, wherein said surfactant is an anionic surfactant, and the content of said anionic surfactant is 50% by mass or less relative to said component A.
  4. 前記界面活性剤が、非イオン性界面活性剤であって、該非イオン性界面活性剤の含有量が、前記成分Ａに対して６０質量％以下である、請求項１に記載の乳化組成物。 2. The emulsion composition according to claim 1, wherein said surfactant is a nonionic surfactant, and the content of said nonionic surfactant is 60% by mass or less relative to said component A.
  5. 前記界面活性剤が、アニオン性界面活性剤または非イオン性界面活性剤であって、該アニオン性界面活性剤または非イオン性界面活性剤の含有量が、前記成分Ａに対して３０質量％以下である、請求項１に記載の乳化組成物。 The surfactant is an anionic surfactant or a nonionic surfactant, and the content of the anionic surfactant or nonionic surfactant is 30% by mass or less with respect to the component A. The emulsion composition according to claim 1, wherein
  6. 前記乳化組成物が、界面活性剤を実質的に含まないものである、請求項１に記載の乳化組成物。 2. The emulsified composition of claim 1, wherein the emulsified composition is substantially free of surfactants.
  7. 前記乳化組成物が、更に電解質を含むものである、請求項１に記載の乳化組成物。 The emulsified composition according to claim 1, wherein said emulsified composition further comprises an electrolyte.
  8. 前記電解質が、多価電解質である、請求項７に記載の乳化組成物。 8. The emulsified composition of claim 7, wherein said electrolyte is a polyelectrolyte.
  9. 前記アクリル酸エステル（ａ）／化合物（ｂ）共重合体が、更に（ｃ）エチレン性不飽和基を２個以上有する化合物を構成成分として含むものである、請求項１に記載の乳化組成物。 2. The emulsion composition according to claim 1, wherein the acrylic acid ester (a)/compound (b) copolymer further contains (c) a compound having two or more ethylenically unsaturated groups as a constituent component.
  10. 前記化合物（ｂ）が、一般式［２］～［５］で示される化合物である、請求項１に記載の乳化組成物。
    一般式［２］：
    Figure JPOXMLDOC01-appb-I000002
    （式中、Ｒ２は、水素原子または炭素数１～６のアルキル基を表す。）
    一般式［３］：
    Figure JPOXMLDOC01-appb-I000003
    （式中、Ａは、酸素原子または－ＮＨ－基を表し、Ｔ１は、ヒドロキシル基を有していてもよい炭素数１～６のアルキレン基を表し、Ｒ３は、水素原子または炭素数１～６のアルキル基を表す。）
    一般式［４］：
    Figure JPOXMLDOC01-appb-I000004
    （式中、Ｔ２は、結合手または炭素数１～６のアルキレン基を表し、Ｒ４は、水素原子または炭素数１～６のアルキル基を表す。）
    一般式［５］：
    Figure JPOXMLDOC01-appb-I000005
    （式中、Ｔ３は、炭素数１～６のアルキレン基を表し、Ｒ５は、水素原子または炭素数１～６のアルキル基を表す。）     The emulsified composition according to claim 1, wherein the compound (b) is a compound represented by formulas [2] to [5].
    General formula [2]:
    Figure JPOXMLDOC01-appb-I000002
    (In the formula, R 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
    General formula [3]:
    Figure JPOXMLDOC01-appb-I000003
    (In the formula, A represents an oxygen atom or -NH- group, T 1 represents an alkylene group having 1 to 6 carbon atoms which may have a hydroxyl group, R 3 represents a hydrogen atom or a represents an alkyl group of 1 to 6.)
    General formula [4]:
    Figure JPOXMLDOC01-appb-I000004
    (In the formula, T 2 represents a bond or an alkylene group having 1 to 6 carbon atoms, and R 4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
    General formula [5]:
    Figure JPOXMLDOC01-appb-I000005
    (In the formula, T 3 represents an alkylene group having 1 to 6 carbon atoms, and R 5 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
  11. 前記化合物（ｂ）が、一般式［２］で示される化合物である、請求項１に記載の乳化組成物。
    一般式［２］：
    Figure JPOXMLDOC01-appb-I000006
    （式中、Ｒ２は、水素原子または炭素数１～６のアルキル基を表す。）     The emulsified composition according to claim 1, wherein the compound (b) is a compound represented by the general formula [2].
    General formula [2]:
    Figure JPOXMLDOC01-appb-I000006
    (In the formula, R 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
  12. 前記油性成分が、炭化水素類、エステル油類、高級アルコール類、シリコーン油類、ロウ類および動植物油類からなる群から選ばれる少なくとも１種である、請求項１に記載の乳化組成物。 2. The emulsion composition according to claim 1, wherein said oily component is at least one selected from the group consisting of hydrocarbons, ester oils, higher alcohols, silicone oils, waxes and animal and vegetable oils.
  13. 請求項１～１２のいずれか１項に記載の乳化組成物を含有する皮膚外用剤。 An external skin preparation containing the emulsified composition according to any one of claims 1 to 12.
  14. 請求項１～１２のいずれか１項に記載の乳化組成物を含有する化粧料。 A cosmetic containing the emulsified composition according to any one of claims 1 to 12.
  15. 成分Ａを含む水相を調製する工程と、
    油性成分を含む油相を調製する工程と、
    前記水相と前記油相を混合して乳化させる工程を含む、
    請求項１に記載の乳化組成物の製造方法。     preparing an aqueous phase comprising component A;
    A step of preparing an oil phase containing an oily component;
    A step of mixing and emulsifying the aqueous phase and the oil phase,
    A method for producing the emulsified composition according to claim 1 .
PCT/JP2022/033044 2021-09-03 2022-09-01 Emulsion composition, and skin topical agent and cosmetic containing said composition WO2023033127A1 (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04255766A (en) * 1990-08-31 1992-09-10 Herberts Gmbh Copolymer capable of being diluted by water, its manufacture and use, and water-base coating composition
JPH09328414A (en) * 1996-06-06 1997-12-22 Mitsubishi Chem Corp Hair cosmetic
JPH11158037A (en) * 1997-11-27 1999-06-15 Mitsubishi Chemical Corp Cosmetic
JP2006076900A (en) * 2004-09-08 2006-03-23 Pola Chem Ind Inc Emulsion cosmetic
JP2012220615A (en) * 2011-04-06 2012-11-12 Dainippon Printing Co Ltd Photocurable resin composition
WO2017170961A1 (en) * 2016-03-31 2017-10-05 和光純薬工業株式会社 Copolymer, thickening agent containing said copolymer, and cosmetic preparation in which said copolymer is blended
JP2021123592A (en) * 2020-01-31 2021-08-30 株式会社コスモビューティー Thickening composition
JP6953604B1 (en) * 2020-12-04 2021-10-27 株式会社コスモビューティー Ascorbic acid compound-containing composition

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04255766A (en) * 1990-08-31 1992-09-10 Herberts Gmbh Copolymer capable of being diluted by water, its manufacture and use, and water-base coating composition
JPH09328414A (en) * 1996-06-06 1997-12-22 Mitsubishi Chem Corp Hair cosmetic
JPH11158037A (en) * 1997-11-27 1999-06-15 Mitsubishi Chemical Corp Cosmetic
JP2006076900A (en) * 2004-09-08 2006-03-23 Pola Chem Ind Inc Emulsion cosmetic
JP2012220615A (en) * 2011-04-06 2012-11-12 Dainippon Printing Co Ltd Photocurable resin composition
WO2017170961A1 (en) * 2016-03-31 2017-10-05 和光純薬工業株式会社 Copolymer, thickening agent containing said copolymer, and cosmetic preparation in which said copolymer is blended
JP2021123592A (en) * 2020-01-31 2021-08-30 株式会社コスモビューティー Thickening composition
JP6953604B1 (en) * 2020-12-04 2021-10-27 株式会社コスモビューティー Ascorbic acid compound-containing composition

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