US20190290572A1 - Cosmetic raw material using core-corona type microparticles and oil-in-water emulsified cosmetic - Google Patents

Cosmetic raw material using core-corona type microparticles and oil-in-water emulsified cosmetic Download PDF

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US20190290572A1
US20190290572A1 US16/336,398 US201716336398A US2019290572A1 US 20190290572 A1 US20190290572 A1 US 20190290572A1 US 201716336398 A US201716336398 A US 201716336398A US 2019290572 A1 US2019290572 A1 US 2019290572A1
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oil
group
cosmetic
core
carbon atoms
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Yuki Sugiyama
Ryushi FUKUHARA
Yang Han
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Shiseido Co Ltd
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Shiseido Co Ltd
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241Containing particulates characterized by their shape and/or structure
    • A61K8/0245Specific shapes or structures not provided for by any of the groups of A61K8/0241
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/91Graft copolymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • A61K8/062Oil-in-water emulsions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • A61K8/068Microemulsions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8158Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86Polyethers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00Make-up preparations; Body powders; Preparations for removing make-up
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/16Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52Amides or imides
    • C08F220/54Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56Acrylamide; Methacrylamide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06Polymers provided for in subclass C08G
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06Polymers provided for in subclass C08G
    • C08F290/062Polyethers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41Particular ingredients further characterized by their size
    • A61K2800/413Nanosized, i.e. having sizes below 100 nm

Definitions

  • the present invention relates to a cosmetic raw material, and more specifically to a cosmetic raw material comprised of core-corona type microparticles and an oil-in-water emulsified cosmetic using the same.
  • Patent Literature 1 a Pickering emulsion method that emulsifies by adhering a powder to an interface between an oil phase and an aqueous phase is known (for example, Patent Literature 1 and Non-patent literature (1)).
  • Inorganic powders such as metal oxides, minerals (for example, silica) or the like are widely used as the afore-mentioned powder; however, emulsification capability of these powders is weak and the powder needs to be blended in a large amount. Thus, powdery or squeaky feeling in the resulting cosmetic was problematic. Further, since oil droplets emulsified by inorganic powders are weak against impact and are easily united by stirring or vibration, low emulsification stability of the cosmetic was problematic.
  • the core-corona type microgel is a particle formed by crosslinking one or more polymer(s) and has a structure of which the hydrophilic region is exposed to the surface of the core part where the hydrophobic region of the polymer is crosslinked and spheroidized thereto.
  • the core-corona type microgel absorbs a solvent, it swells and becomes a gel-state. Thus, it has been mainly used as thickeners or coating agents in the field of cosmetics (Non-patent Literature 2).
  • the present inventors found that the core-corona type microgel obtained by radically polymerizing a specific polyethylene oxide macromonomer, a specific acrylate derivative monomer, and a specific crosslinking monomer under a certain condition has a high swelling property to an organic solvent and can stably emulsify various types of oil components. Further, they reported that by using the afore-mentioned microgel as an emulsifier, an oil-in-water emulsified cosmetic that is excellent in emulsification stability, less in stickiness, and less in powdery or squealy feeling can be obtained (Patent Literatures 2 to 4).
  • the present invention has been made in view of the conventional art, and an object thereof is to provide an emulsifier comprised of core-corona type microparticles that emulsification capability thereof is not affected by the crosslinking level and an oil-in-water emulsified cosmetic emulsified by the afore-mentioned emulsifier.
  • the present inventors have diligently investigated on the afore-mentioned problem, and as a result, they have found that a core-corona type microparticle that can be widely used as an oil-in-water emulsifier can be obtained by radically polymerizing a specific acrylamide derivative and a specific acrylate derivative without crosslinking under certain conditions. Further, they have also found that an oil-in-water emulsified cosmetic emulsified by the afore-mentioned microparticles is excellent in emulsification stability, less in stickiness, less in powdery or squeaky feeling, and also excellent in water-washability, and completed the present invention.
  • the present invention comprises the following.
  • [1] It is comprised of core-corona type microparticles that is obtained by radical polymerization of a polyethylene oxide macromonomer represented by a chemical formula (1), and at least one hydrophobic monomer selected from a group of an acrylate derivative monomer represented by a chemical formula (2) and an acrylamide derivative monomer represented by a chemical formula (3) under the following conditions (A) to (D);
  • a molar ratio expressed by a feed molar amount of the polyethylene oxide macromonomer/a feed molar amount of (the acrylate derivative monomer and/or the acrylamide derivative monomer) is 1:10 to 1:250;
  • the macromonomer represented by the chemical formula (1) is at least one derivative selected from a group consisting of an acrylic acid derivative and a methacrylic acid derivative that have a polyethylene glycol group with 8 to 200 repeating units
  • the acrylate derivative monomer represented by the following formula (2) is at least one monomer selected from a group consisting of an acrylic acid derivative and a methacrylic acid derivative that have a substituent comprising an alkyl group having 1 to 12 carbon atoms
  • the acrylamide derivative monomer represented by the chemical formula (3) is at least one monomer selected from a group consisting of an acrylamide derivative and a methacrylamide derivative that have a substituent comprising an alkyl group having 1 to 18 carbon atoms;
  • a polymerization solvent is a mixture of alcohol and water, wherein the alcohol is at least one alcohol selected from a group consisting of ethanol, dipropylene glycol, 1,3-butylene glycol and isoprene glycol; and
  • R 1 is at least one substitute selected from a group consisting of H and an alkyl group having 1 to 3 carbon atoms, n is a number of 8 to 200, and X is at least one substitute selected from a group consisting of H and CH 3 ;
  • R 2 is at least one substitute selected from a group consisting of H and an alkyl group having 1 to 3 carbon atoms, and R 3 is a substituent that has an alkyl group having 1 to 12 carbon atoms;
  • R 4 is at least one substitute selected from a group consisting of H and an alkyl group having 1 to 3 carbon atoms
  • both R 5 and R 6 are one substitute selected from a group consisting of H and substituents that have an alkyl group having 1 to 18 carbon atoms.
  • An emulsifier comprised of the cosmetic raw material according to [1] or [2].
  • a clouding agent comprised of the cosmetic raw material according to [1] or [2].
  • the present invention provides an emulsifier comprised of uncrosslinked core-corona type microparticles. Further, by using the afore-mentioned emulsifier, an oil-in-water emulsified cosmetic that is excellent in emulsification stability, less in stickiness, less in powdery or squeaky feeling, and excellent in water-washability is provided.
  • FIG. 1 is a graph that depicts an analysis of an effect on oil/aqueous interfacial tension with respect to the core-corona type microparticles (Production Example 5) according to the present invention and the conventional crosslinked core-corona type microparticles ((Acrylates/Methoxy PEG-90 Methacrylate) Crosspolymer).
  • FIG. 2 is a graph that depicts an analysis for water-washability with respect to the cosmetics of the Examples and the comparative examples.
  • the cosmetic raw material according to the present invention is a dispersion of core-corona type microparticles obtained by radically polymerizing monomers represented by the following formulae (1) to (3) under specific conditions.
  • R 1 is an alkyl group having 1 to 3 carbon atoms, and n (the molecular weight of the polyethylene oxide part) is a number of 8 to 200.
  • X is H or CH 3 .
  • the polyethylene oxide macromonomers of chemical formula (1) is preferably an acrylic acid derivative or a methacrylic acid derivative.
  • polyethylene oxide macromonomers commercial products commercially available from Aldrich or BLEMMER® sold by NOF Corporation can be used.
  • macromonomers include PME-400, PME-1000, and PME-4000 (n values in chemical formula (1) are 9, 23 and 90, respectively, all products from NOF Corporation), which are methoxy polyethylene glycol monometalate.
  • R 2 is an alkyl group having 1 to 3 carbon atoms
  • R 3 is a substituent including an alkyl group having 1 to 12 carbon atoms.
  • the hydrophobic monomers of chemical formula (2) is preferably an acrylic acid derivative or a methacrylic acid derivative, and methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate and the like may be used, for example. Among these compounds, methyl methacrylate, butyl methacrylate, and octyl methacrylate are particularly preferable.
  • hydrophobic monomers are commodity raw materials and they can also be obtained easily as general industrial raw materials.
  • Commercial products commercially available from Aldrich or Tokyo Chemical Industry Co., Ltd may be used, for example.
  • R 4 is H or an alkyl group having 1 to 3 carbon atoms
  • R 5 and R 6 are H or a substituent including an alkyl group having 1 to 18 carbon atoms.
  • a hydrophobic monomer represented by the formula (3) is preferably an acrylamide derivative or a methacrylamide derivative.
  • t-butylacrylamide, N,N-dimethylacrylamide, N-[3-(dimethylamino)propyl]acrylamide, t-butylmethacrylamide, octylacrylamide, octylmethacrylamide, octadecylacrylamide or the like can be used preferably.
  • t-butylacrylamide, N,N-dimethylacrylamide and N-[3-(dimethylamino)propyl]acrylamide are particularly preferable.
  • hydrophobic monomers are available as commercial products or industrial raw materials.
  • the copolymer that constitutes the core-corona type microparticles according to the present invention is a copolymer obtained by copolymerizing a macromonomer represented by the formula (1) and one or two or more selected from hydrophobic monomers represented by the formulae (2) and (3) by any radical polymerization method in accordance with the following conditions of (A) to (D).
  • a molar ratio expressed by a feed molar amount of the polyethylene oxide macromonomer/a feed molar amount of (the acrylate derivative monomer and/or the acrylamide derivative monomer) is 1:10 to 1:250;
  • the macromonomer represented by the following formula (1) is an acrylic acid derivative or a methacrylic acid derivative having a polyethylene glycol group with 8 to 200 repeating units,
  • the acrylate derivative monomer represented by the following formula (2) is an acrylic acid derivative or a methacrylic acid derivative having a substituent comprising an alkyl group having 1 to 12 carbon atoms
  • the acrylamide derivative monomer represented by the following formula (3) is an acrylamide derivative or a methacrylamide derivative having a substituent comprising an alkyl group having 1 to 18 carbon atoms;
  • a polymerization solvent is a water-alcohol mixed solvent, and the alcohol is one or two or more selected from ethanol, dipropylene glycol, 1,3-butylene glycol and isoprene glycol;
  • the feed molar amount of the polyethylene oxide macromonomer and the hydrophobic monomer i.e., the sum total of the acrylate derivative monomer and/or acrylamide derivative monomer
  • it can be polymerized when the molar ratio of the feed molar amount of the polyethylene oxide macromonomer/feed molar amount of the hydrophobic monomers is in the range of 1/1 to 10/250 (molar ratio).
  • the feed molar amount is preferably in a range of 1/1 to 10/200 and more preferably in a range of 1/11 to 25/100.
  • the polymerized polymer becomes water soluble and does not form a core-corona type microgel.
  • the molar amount of the hydrophobic monomer is 250 times or more of that of the polyethylene oxide macromonomer, the dispersion stabilization by the polyethylene oxide macromonomer becomes insufficient, so that the hydrophobic polymer due to the insoluble hydrophobic monomer may aggregate and precipitate.
  • a condition (B) has the three conditions (B-1) to (B-3) as shown below.
  • the macromonomer represented by the formula (1) is an acrylic acid derivative or a methacrylic acid derivative having a polyethylene-glycol group with 8 to 200 repeating units.
  • the number of the repeating units is 7 or less, particles that are dispersed stably in a solvent may not be obtained.
  • the number of the repeating units is more than 200, particles become fine and may be unstable when the composition is blended in a cosmetic.
  • the acrylate derivative monomer represented by the formula (2) is an acrylic acid derivative or a methacrylic acid derivative having a substituent including an alkyl group having 1 to 12 carbon atoms.
  • the monomer may be too hydrophilic to be emulsion-polymerized adequately. Meanwhile, when the number of carbon atoms is 13 or more, a preferable feeling in use may not be obtained.
  • the acrylamide derivative monomer represented by the formula (3) is an acrylamide derivative or a methacrylamide derivative having substituents including an alkyl group having 1 to 18 carbon atoms.
  • the hydrophobic monomers according to the present invention need to have a monomer composition obtained by mixing one or two or more selected from an acrylate derivative monomer represented by the formula (2) and an acrylamide derivative monomer represented by the formula (3).
  • two types of a methacrylate and a butyl methacrylate or four types of a methacrylate, t-butylacrylamide, N,N-dimethylacrylamide and N-[3-(dimethylamino)propyl]acrylamide are particularly preferably used as hydrophobic monomers.
  • hydrophobic monomers it is preferred to additionally use methoxy polyethylene glycol monometalate as a macromonomer.
  • the most preferable combinations of a macromonomer and hydrophobic monomers include, but are not limited thereto:
  • methoxy polyethylene glycol monometalate having a polyethylene glycol group with 8 to 90, most preferably 15 repeating units, a methacrylate and a butyl methacrylate; methoxy polyethylene glycol monometalate having a polyethylene glycol group with 8 to 200, most preferably 90 repeating units, a methyl methacrylate, a butyl methacrylate, t-butylacrylamide and N,N-dimethylacrylamide; and N-[3-(dimethylamino)propyl]acrylamide, t-butylmethacrylamide, octylacrylamide, octylmethacrylamide and octadecylacrylamide.
  • the polymerization solvent is a water-alcohol mixed solvent.
  • the preferable alcohol is the one that can dissolve a hydrophobic monomer represented by chemical formulae (2) and (3). Therefore, one or more selected from ethanol, dipropylene glycol, 1,3-buthylene glycol, and isoprene glycol are preferable.
  • the mix volume of alcohol is lower than 10% by volume, the dissolution of the hydrophobic monomer becomes extremely poor, so that micro particle may not be formed.
  • the mix volume of alcohol exceeds 90% by volume, an emulsion of the hydrophobic monomer cannot be formed by hydrophobic interaction, so that no emulsion polymerization can proceed and micro particle may not be obtained.
  • the cosmetic raw material according to the present invention has polyethylene oxide chains, which are nonionic polymers, on its surface and thus is stably dispersed in water. Further, under a condition where both of an oil phase component and an aqueous phase component are present, the core part absorbs the oil phase component and swells and the corona part, which is a core surface, adheres to the interface of the oil phase component and the aqueous phase component because it is compatible with the aqueous component.
  • an oil-in-water emulsion system of which oil droplets having the cosmetic raw materials according to the present invention adhered to their surface are dispersed in the aqueous component can be obtained by an ordinary emulsification method (emulsification by stirring and mixing the oil phase component and the aqueous phase component). Since the afore-mentioned oil droplets do not easily unite by further stirring or impact caused by vibration, it is significantly stable compared to the conventional Pickering emulsion that uses inorganic powders.
  • the cosmetic raw material according to the present invention can preferably be used as an emulsifier for oil-in-water emulsification.
  • the cosmetic raw material according to the present invention does not cause stickiness like ordinary surfactants, and does not cause powdery or squealy feelings like inorganic powders. Furthermore, since it is a Pickering emulsion method, a wide range of types of oil components can be emulsified.
  • the oil-in-water emulsified cosmetic according to the present invention is one which is emulsified by the cosmetic raw material comprised of the afore-mentioned core-corona type microparticles. “Emulsified” as used herein can be said as “a state where the microparticles are present in the interface between the oil droplet and the aqueous phase (continuous phase)”.
  • the oil-in-water emulsified cosmetic according to the present invention is emulsified by the afore-mentioned microparticles so that it is excellent in emulsification stability, less in stickiness, and less in powdery or squeaky feeling.
  • the blending amount of the cosmetic raw material of the present invention in a cosmetic is 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and further more preferably 0.05 to 2% by mass in terms of the pure content of the core-corona type microparticles relative to the total amount of the cosmetic.
  • the blending quantity is less than 0.01%, it may be difficult to obtain a stable cosmetic.
  • the blending quantity exceeds 10%, it may not be preferable as a cosmetic in terms of stability during long term storage at high temperatures and the feeling in use may be poor.
  • the oil-in-water emulsified cosmetic according to the present invention can be produced by mixing and dispersing the cosmetic raw material into water or an aqueous phase component, adding the oil phase component and other components, stirring the mixture and applying shearing force to emulsify the mixture in a usual method.
  • oil phase components examples include hydrocarbon oils, higher fatty acids, higher alcohols, synthetic esters, silicone oils, liquid fats and oils, solid fats and oils, waxes, and perfumes that are commonly used in cosmetics, quasi-drugs, etc.
  • hydrocarbon oils examples include isododecane, isohexadecane, isoparaffin, liquid petrolatum, ozocerite, squalane, pristane, paraffin, ceresin, squalene, petrolatum, and microcrystallin wax.
  • higher fatty acids examples include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, tall oil, isostearic acid, linolic acid, linoleic acid, eicosapentaenoic acid (EPA), and docosahexaenoic acid (DHA).
  • higher alcohols examples include straight chain alcohols (for example, lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, and cetostearyl alcohol) and branched chain alcohols (for example, monostearyl glycerin ether (batyl alcohol), 2-decyltetradecynol, lanolin alcohol, cholesterol, phytosterol, hexyl dodecanol, isostearyl alcohol, and octyl dodecanol).
  • straight chain alcohols for example, lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, and cetostearyl alcohol
  • branched chain alcohols for example, monostearyl glycerin ether (batyl alcohol), 2-decyltetradecynol, lanolin alcohol, cholesterol, phytosterol, hexyl dodecanol
  • ester oils examples include octyl octanoate, nonyl nonanoate, cetyl octanoate, isopropyl myristate, octyl dodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyloctanoate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, n-alkylene glycol monoisostearate, neopentyl glycol dicaprate, tripropylene glycol pivalate, diisostearyl
  • silicone oils examples include chain polysiloxanes (for example, dimethylpolysiloxane, methylphenyl polysiloxane, and diphenyl polysiloxane), ring polysiloxanes (for example, octamethylcyclotetrasiloxane, decamethyl cyclopenta siloxane, and dodecamethyl cyclohexa siloxane), silicone resins forming a three-dimensional network structure, silicone rubbers, various modified polysiloxanes (amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, and fluorine-modified polysiloxane), and acryl silicones.
  • chain polysiloxanes for example, dimethylpolysiloxane, methylphenyl polysiloxane, and diphenyl polysiloxane
  • ring polysiloxanes for example, octamethyl
  • liquid fats and oils examples include avocado oil, tsubaki oil, turtle fatty acid, macademia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, sasanquan oil, castor oil, linseed oil, safflower oil, cotton seed oil, perilla oil, soybean oil, peanut oil, tea seed oil, Japanese nutmeg oil, rice bran oil, Chinese gimlet oil, Japanese gimlet oil, jojoba oil, germ oil, and triglycerin.
  • solid fats and oils examples include cacao butter, coconut oil, horse fat, hydrogenated coconut oil, palm oil, beef tallow, mutton tallow, hydrogenated beef tallow, palm kernel oil, lard, beef bone fat, Japanese core wax nucleus oil, hydrogenated oil, neatsfoot oil, Japanese core wax, and hydrogenated castor oil.
  • waxes examples include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, tree wax, whale wax, montan wax, bran wax, lanolin, kapok wax, lanolin acetate, liquid lanolin, sugar cane wax, lanolin fatty acid isopropyl ester, hexyl laurate, reduced lanolin, jojoba wax, hard lanolin, shellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, and POE hydrogenated lanolin ethyl alcohol ether.
  • perfume is not limited in particular; examples include natural perfumes from animals or plants, synthetic perfumes prepared by means of chemical synthesis, and perfume blends thereof. By blending perfume, a cosmetic having a superior durability of fragrance can be obtained.
  • perfumes include acetivenol, anise aldehyde, anethole, amyl acetate, amyl salicylate, allyl amyl glycolate, allyl caproate, aldehyde C6-20, ambrettolide, ambrettolide, ambroxan, ionone, Iso E Super, eugenol, auranthiol, galaxolide, calone, coumarin, geraniol, geranyl acetate, Sandalore, santalol, sandela, cyclamen aldehyde, cis-3-hexenyl acetate, cis-3-hexenol, citral, citronellyl acetate, citronellol, cineole, dihydromyrcenol, jasmolactone, cinnamic alcohol, cinnamic aldehyde, styralyll
  • the selection of water contained in the oil-in-water emulsified cosmetic of the present invention is not limited in particular; specific examples include purified water, ion-exchanged water, and tap water.
  • water soluble alcohols include lower alcohols, polyhydric alcohols, polyhydric alcohol polymers, dihydric alcohol alkyl ethers, dihydric alcohol ether esters, glycerin monoalkyl ethers, sugar alcohols, monosaccharides, oligosaccharides, polysaccharides, and derivatives thereof.
  • lower alcohols examples include ethanol (may be abbreviated as EtOH), propanol, isopropanol, isobutyl alcohol, and t-butyl alcohol.
  • polyhydric alcohols include: dihydric alcohols (for example, dipropylene glycol, 1,3-butylene glycol, ethylene glycol, trimethylene glycol, 1,2-butylene glycol, tetramethylene glycol, 2,3-butylene glycol, pentamethylene glycol, 2-butene-1,4-diol, hexylene glycol, and octylene glycol); trihydric alcohols (for example, glycerin and trimethylolpropane); tetrahydric alcohols (for example, diglycerin and pentaerythritol such as 1,2,6-hexanetriol); pentahydric alcohols (for example, xylitol and triglycerin); hexahydric alcohols (for example, sorbitol and mannitol); polyhydric alcohol polymers (for example, diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, te
  • monosaccharides include: trioses (for example, D-glyceryl aldehyde and dihydroxyacetone); tetroses (for example, D-etythrose, D-erythrulose, D-threose, and erythritol); pentoses (for example, L-arabinose, D-xylose, L-lyxose, D-arabinose, D-ribose, D-ribulose, D-xylulose, and L-xylulose); hexoses (for example, D-glucose, D-talose, D-psicose, D-galactose, D-fructose, L-galactose, L-mannose, and D-tagatose); heptoses (for example, aldoheptose and heprose); octoses (for example, octurose); deoxysugars (for example, 2-
  • oligosaccharides include sucrose, gentianose, umbelliferose, lactose, planteose, isolignoses, ⁇ , ⁇ -trehalose, raffinose, lignoses, umbilicine, stachyose and verbascoses.
  • polysaccharides include cellulose, quince seed, starch, galactan, dermatan sulfate, glycogen, gum arabic, heparan sulfate, traganth gum, keratan sulfate, chondroitin, xanthan gum, guar gum, dextran, kerato sulfate, locust bean gum, and succinoglucan.
  • polyols examples include polyoxyethylene methyl glucoside (Glucam E-10) and polyoxypropylene methyl glucoside (Glucam P-10).
  • thickeners examples include: gum arabic, carrageenan, karaya gum, gum tragacanth, carob gum, quince seed (Cydonia oblonga), casein, dextrin, gelatin, sodium pectate, sodium arginate, methyl cellulose, ethyl cellulose, CMC, hydroxy ethyl cellulose, hydroxypropyl cellulose, PVA, PVM, PVP, sodium polyacrylate, carboxy vinyl polymer, locust bean gum, guar gum, tamarind gum, cellulose dialkyl dimethylammonium sulfate, xanthan gum, aluminum magnesium silicate, bentonite, hectorite, AlMg silicate (beagum), laponite, and silicic acid anhydride.
  • natural water-soluble polymers include: plant-type polymers (for example, gum arabic, gum tragacanth, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, agar, quince seed (Cydonia oblonga), algae colloids (brown algae extract), starches (rice, corn, potato, and wheat), and glycyrrhizic acid); microorganism-type polymers (for example, xanthan gum, dextran, succinoglucan, and pullulan); and animal-type polymers (for example, collagen, casein, albumin, and gelatin).
  • plant-type polymers for example, gum arabic, gum tragacanth, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, agar, quince seed (Cydonia oblonga), algae colloids (brown algae extract), starches (rice, corn, potato, and wheat), and
  • semisynthetic water-soluble polymers include: starch-type polymers (for example, carboxymethyl starch and methylhydroxypropyl starch); cellulosic polymers (for example, methyl cellulose, ethyl cellulose, methylhydroxypropyl cellulose, hydroxyethyl cellulose, cellulose sodium sulfate, hydroxypropyl cellulose, carboxymetyl-cellulose, sodium carboxymethyl cellulose, crystal cellulose, and cellulose powder); and alginic acid-type polymers (for example, sodium alginate and propylene glycol alginate).
  • starch-type polymers for example, carboxymethyl starch and methylhydroxypropyl starch
  • cellulosic polymers for example, methyl cellulose, ethyl cellulose, methylhydroxypropyl cellulose, hydroxyethyl cellulose, cellulose sodium sulfate, hydroxypropyl cellulose, carboxymetyl-cellulose, sodium carboxymethyl cellulose, crystal cellulose, and
  • Examples of synthetic water-soluble polymers include: vinyl polymers (for example, polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, carboxy vinyl polymer); polyoxyethylene-type polymers (for example, polyethylene glycol 20,000, 40,000, 60,000, etc.); acrylic polymers (for example, sodium polyacrylate, polyethylacrylate, and polyacrylamide); polyethyleneimine; and cationic polymers.
  • vinyl polymers for example, polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, carboxy vinyl polymer
  • polyoxyethylene-type polymers for example, polyethylene glycol 20,000, 40,000, 60,000, etc.
  • acrylic polymers for example, sodium polyacrylate, polyethylacrylate, and polyacrylamide
  • polyethyleneimine for example, sodium polyacrylate, polyethylacrylate, and polyacrylamide
  • cationic polymers for example, sodium polyacrylate, polyethylacrylate, and polyacryl
  • moisturizers examples include chondroitin sulfate, hyaluronic acid, mucoitin sulfuric acid, charonic acid, atelocollagen, cholesteryl-12-hydroxy stearate, sodium lactate, bile salt, dl-pyrrolidone carboxylic acid salt, short chain soluble collagen, diglycerin (EO)PO adduct, chestnut rose fruit extract, yarrow extract, and sweet clover extract.
  • sequestering agents include 1-hydroxy ethane-1,1-diphosphonic acid, 1-hydroxy ethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, trisodium edetate, tetrasodium edetate, sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, and trisodium ethylenediaminehydroxyethyl triacetate.
  • amino acids examples include neutral amino acids (for example, threonine and cysteine) and basic amino acids (for example, hydroxylysine).
  • amino acid derivatives include sodium acyl sarcosinate (sodium N-lauroyl sarcosinate), acyl glutamate, sodium acyl ⁇ -alanine, and glutathione.
  • pH adjustment agents examples include buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate.
  • the blending quantity of the oil phase components and the water phase components in the oil-in-water emulsified cosmetic according to the present invention are not limited in particular.
  • an oil-in-water emulsified cosmetic with a wide range of oil phase components/water phase components ratios ranging from embodiments having smaller oil phase components/water phase components ratios, i.e., smaller blending ratios of the oil phase components (essences, emulsions, etc.) to embodiments having larger blending ratios of the oil phase components (cleansing creams, sunscreens, hair creams, etc.) can be obtained.
  • components normally used in external preparations such as cosmetics and quasi-drugs can be blended as necessary in the cosmetic according to the present invention as long as the effect of the present invention is not adversely affected; examples of such components include ultraviolet absorbents, powders, organic amines, polymer emulsions, vitamins, and antioxidants.
  • water soluble ultraviolet absorbents examples include benzophenone-type ultraviolet absorbents such as 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxy benzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′,4,4′-tetrahydroxy benzophenone, 2-hydroxy-4-methoxy benzophenone, 2-hydroxy-4-methoxy-4′-methylbenzophenone, 2-hydroxy-4-methoxy benzophenone-5-sulfonate, 4-phenyl benzophenone, 2-ethylhexyl-4′-phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxy benzophenone, and 4-hydroxy-3-carboxy benzophenone, the benzimidazole-type ultraviolet absorbent such as phenylbenzimidazole-5-sulfonic acid and salts thereof and phenylene-bis-benzimidazole-tetrasulfonic acid
  • oil soluble ultraviolet absorbents examples include: benzoic acid-type ultraviolet light absorbents such as paraminobenzoic acid (PABA), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester, N,N-dimethyl PABA ethyl ester, and N, N-dimethyl PABA butyl ester; anthranilic acid-type ultraviolet light absorbents such as homo menthyl-N-acetyl anthranilate; salicylic acid-type ultraviolet light absorbents such as amyl salicylate, menthyl salicylate, homo menthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, and p-isopropanol phenyl salicylate; cinnamic acid-type ultraviolet absorbents such as octyl cinnamate,
  • powder components include inorganic powders (for example, talc, kaolin, mica, sericite, muscovite, phlogopite, synthetic mica, lepidolite, biotite, vermiculite, magnesium carbonate, calcium carbonate, aluminum silicate, barium silicate, calcium silicate, magnesium silicate, strontium silicate, tungstic acid metal salt, magnesium, silica, zeolite, barium sulfate, firing calcium sulfate (calcined gypsum), calcium phosphate, fluorine-apatite, hydroxy apatite, ceramic powder, metallic soaps (for example, zinc myristate, calcium palmitate, and aluminum stearate), and boron nitride); organic powders (for example, polyamide resin powder (nylon powder), polyethylene powder, poly-methyl methacrylate powder, polystyrene powder, powders of the copolymer resin of styrene and acrylic acid, benzoguanamine
  • inorganic powders can act as Pickering emulsifiers and, in such case, the surfaces of the emulsified particles need to be completely coated with inorganic powders.
  • the emulsified particles whose surfaces are completely coated with inorganic powders are those that can be obtained by optimizing all of the conditions for formulations and stirring under the presence of a large amount of inorganic powders.
  • inorganic powders do not act as Pickering emulsifiers in most cases when they are blended in cosmetics in general.
  • organic amines examples include monoethanolamine, diethanolamine, triethanolamine, morpholine, tetrakis(2-hydroxypropyl)ethylenediamine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, and 2-amino-2-methyl-1-propanol.
  • polymer emulsions examples include acrylic resin emulsions, ethyl polyacrylate emulsions, acryl resin liquids, polyacrylic alkyl ester emulsions, polyvinyl acetate resin emulsions, and natural rubber latex.
  • vitamins examples include vitamins A, B1, B2, B6, C and E as well as their derivatives, pantothenic acid and its derivatives, and biotin.
  • antioxidants examples include tocopherols, dibutyl hydroxytoluene, butyl hydroxyanisole, and gallic acid ester.
  • antioxidation assistants include phosphoric acid, citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, fumaric acid, cephalin, hexametaphosphate, phytic acid, and ethylene diamine tetraacetic acid.
  • antiseptics methylparaben, ethylparaben, butylparaben, and phenoxyethanol
  • antiphlogistic agents for example, glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, zinc oxide, and allantoin
  • whitening agents for example, placenta extract, creeping saxifrage extract, and arbutin
  • various extracts for example, Phellodendri Cortex, goldthread, lithospermum root, Paeonia lactiflora, Swertia japonica, Birch, sage, loquat, carrot, aloe, Malva sylvestris, Iris, grape, Coix ma-yuen, sponge gourd, lily, saffron, Cnidium officinale, sheng jiang, Hypericum erectum, Ononis, garlic
  • surfactants can be blended into the aqueous phase or oil phase of the oil-in-water emulsified cosmetic of the present invention as long as the effect of the present invention is not adversely affected (for example, 2% by mass, more preferably 1% by mass, and further preferably 0.5% by mass or less).
  • An ampholytic surfactant has at least one cationic functional group and one anionic functional group, is cationic when the solution is acidic and anionic when the solution is alkaline, and assumes characteristics similar to a nonionic surfactant around the isoelectric point.
  • Ampholytic surfactants are classified, based on the type of the anionic group, into the carboxylic acid type, the sulfuric ester type, the sulfonic acid type, and the phosphoric ester type.
  • the carboxylic acid type, the sulfuric ester type, and the sulfonic acid type are preferable.
  • the carboxylic acid type is further classified into the amino acid type and the betaine type. Particularly preferable is the betaine type.
  • imidazoline type ampholytic surfactants for example, 2-undecyl-N,N,N-(hydroxyethyl carboxymethyl)-2-imidazoline sodium salt and 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy 2 sodium salt
  • betaine type surfactants for example, 2-heptadecyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkyl betaine, amide betaine, and sulfobetaine).
  • cationic surfactants include quaternary ammonium salts such as cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimehylammonium chloride, behenyldimethylhydroxyethylammonium chloride, stearyldimethylbenzylammonium chloride, and cetyltrimethylammonium methyl sulfate.
  • amide amine compounds such as stearic diethylaminoethylamide, stearic dimethylaminoethylamide, palmitic diethylaminoethylamide, palmitic dimethylaminoethylamide, myristic diethylaminoethylamide, myristic dimethylaminoethylamide, behenic diethylaminoethylamide, behenic dimethylaminoethylamide, stearic di ethylaminopropylamide, stearic dimethylaminopropylamide, palmitic diethylaminopropylamide, palmitic dimethylaminopropylamide, myristic diethylaminopropylamide, myristic dimethylaminopropylamide, behenic diethylaminopropylamide, and behenic dimethylaminopropylamide.
  • amide amine compounds such as stearic diethy
  • Anionic surfactants are classified into the carboxylate type such as fatty acid soaps, N-acyl glutamates, and alkyl ether acetates, the sulfonic acid type such as ⁇ -olefin sulfonates, alkane sulfonates, and alkylbenzene sulfonates, the sulfuric ester type such as higher alcohol sulfuric ester salts, and phosphoric ester salts.
  • the carboxylate type such as fatty acid soaps, N-acyl glutamates, and alkyl ether acetates
  • the sulfonic acid type such as ⁇ -olefin sulfonates, alkane sulfonates, and alkylbenzene sulfonates
  • the sulfuric ester type such as higher alcohol sulfuric ester salts
  • phosphoric ester salts Preferable are the carboxylate type, the sulfonic acid type, and the sulfuric ester salt type; particularly prefer
  • fatty acid soaps for example, sodium laurate and sodium palmitate
  • higher alkyl sulfuric acid ester salts for example, sodium lauryl sulfate and potassium lauryl sulfate
  • alkyl ether sulfuric acid ester salts for example, POE-triethanolamine lauryl sulfate and sodium POE-lauryl sulfate
  • N-acyl sarcosinic acids for example, sodium lauroyl sarcosinate
  • higher fatty acid amide sulfonic acid salts for example, sodium N-myristoyl N-methyl taurate, sodium cocoyl methyl taurate, and sodium laurylmethyl taurate
  • phosphoric ester salts for example, sodium POE-oleyl ether phosphate and POE stearyl ether phosphoric acid
  • sulfosuccinates for example sodium di-2-ethylhexylsulfosuccinate, sodium monolauroyl monoethanol
  • a nonionic surfactant is a surfactant that is not ionized to assume an electric charge in an aqueous solution.
  • a type that uses alkyls and a type that uses dimethyl silicone are known among others.
  • Specific examples of the former include glycerol fatty acid esters, ethylene oxide derivatives of glycerol fatty acid esters, polyglycerol fatty acid esters, propylene glycol fatty acid esters, ethylene oxide derivatives of propylene glycol fatty acid esters, polyethylene glycol fatty acid esters, polyethylene glycol alkyl ethers, polyethylene glycol alkyl phenyl ethers, polyethylene glycol castor oil derivatives, and polyethylene glycol hydrogenated castor oil derivatives.
  • Examples of the latter include polyether-modified silicone and polyglycerin-modified silicone.
  • Preferable is the type that uses alkyl for the hydrophobic group.
  • lipophilic nonionic surfactants include sorbitan fatty acid esters (for example, sorbitan mono oleate, sorbitan mono isostearate, sorbitan mono laurate, sorbitan mono palmitate, sorbitan mono stearate, sorbitan sesquioleate, sorbitan trioleate, diglycerol sorbitan penta-2-ethylhexylate, diglycerol sorbitan tetra-2-ethylhexylate); glycerin polyglycerin aliphatic acids (for example, mono cottonseed oil fatty acid glycerin, glyceryl monoerucate, glycerin sesquioleate, glyceryl monostearate, ⁇ , ⁇ ′-glycerin oleate pyroglutamate, monostearate glycerin malic acid); propylene glycol fatty acid esters (for example, propylene glycol mono
  • hydrophilic nonionic surfactants include POE-sorbitan fatty acid esters (for example, POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, and POE-sorbitan tetraoleate); POE sorbitol fatty acid esters (for example, POE sorbitol monolaurate, POE-sorbitol monooleate, POE-sorbitolpentaoleate, and POE-sorbitol monostearate); POE-glycerin fatty acid esters (for example, POE-monooleates such as POE-glycerin monostearate, POE-glycerin monoisostearate, and POE-glycerin triisostearate); POE-fatty acid esters (for example, POE-distearate, POE-monodioleate, and ethylene glycol distearate); POE-alkylethers
  • POP-alkylethers for example, POE.cndot. POP-cetyl ether, POE.cndot. POP-2-decyl tetradecyl ether, POE.cndot. POP-monobutyl ether, POE.cndot. POP-lanolin hydrate, and POE.cndot. POP-glycerin ether); tetra POE.cndot.
  • POE-castor oil hydrogenated castor oil derivatives for example, POE-castor oil, POE-hydrogenated castor oil, POE-hydrogenated castor oil monoisostearate, POE-hydrogenated castor oil triisostearate, POE-hydrogenated castor oil monopyroglutamic monoisostearic diester, and POE-hydrogenated castor oil maleic acid
  • POE-beeswax-lanolin derivatives for example, POE-sorbitol beeswax
  • alkanol amides for example, palm oil fatty acid diethanol amide, laurate monoethanolamide, and fatty acid isopropanol amide
  • POE-propylene glycol fatty acid esters for example, palm oil fatty acid diethanol amide, laurate monoethanolamide, and fatty acid isopropanol amide
  • POE-propylene glycol fatty acid esters POE-alkylamines
  • POE-fatty acid amides suc
  • the cosmetic raw material of the present invention can be used as a clouding agent.
  • White turbidity, an appearance feature, in cosmetics (especially cosmetic lotions) is strongly supported by some consumers as it evokes moisturizing feeling, moist feeling, full-bodied feeling or the like.
  • White cloudy cosmetics are generally produced by dispersing ethanol of which surfactants and oil are dissolved to an aqueous phase; however, the adjustment of the surfactant and oil balance was difficult and obtaining a white cloudy cosmetic that is excellent in stability over time was not easy.
  • White turbidity can visually be confirmed by blending only 0.01% (converted value of the pure content of the core-corona type microparticles) of the cosmetic raw material according to the present invention into water. By blending 0.01 to 0.1% thereof, the white turbidity with the L value (brightness) of 1 to 80, measured with a Macbeth color difference meter, can be obtained.
  • a white cloudy cosmetic in the present invention means a cosmetic whose appearance can be visually recognized to be turbid.
  • L value is preferably 1 to 90.
  • the clouding agent of the present invention can be used by mixing and dispersing into water (or an aqueous phase of which aqueous components are dissolved) by a usual method in a producing process of an ordinary cosmetic.
  • the blending amount as a pure content of the core-corona type microparticles, is 0.01 to 10% by mass, more preferably 0.05 to 2% by mass, and further more preferably 0.05 to 1% by mass relative to the total amount of the cosmetic.
  • white turbidity may not be sufficient.
  • the blending amount exceeds 10% by mass, it may not be preferable in terms of stability during long term storage at high temperatures and the feeling in use may be poor.
  • the oil-in-water emulsified cosmetic and the white cloudy cosmetic are preferable as skin cosmetics and skin external agents.
  • Example 1 Production Example of a Core-Corona Type Microparticle Dispersion
  • Polyethyleneoxide macro monomer and hydrophobic monomer were added into 90 g of water-alcohol mixed solvent in a three-neck flask equipped with a reflux tube and a nitrogen feeding tube. After sufficient dissolution or dispersion, dissolved oxygen was removed by nitrogen substitution for 20 minutes. Then, 1 mol % of the polymerization initiator, 2,2′-azobis(2-methylpropionamidine) dihydrochloride, with respect to the total amount of monomers, was dissolved in a small amount of water and added, and further dissolution or dispersion was carried out.
  • the uniformly dissolved or dispersed polymerization solution was put through nitrogen substitution for 20 minutes to remove dissolved oxygen, followed by 8 hours of polymerization with stirring by means of a magnetic stirrer while the temperature was maintained at 65 to 70° C. in an oil bath. After the completion of polymerization, the polymer solution was returned to room temperature; thus a core-corona type microparticle dispersion was obtained.
  • Blemmer PME-4000 produced by NOF CORPORATION
  • hydrophobic monomers methyl methacrylate (MMA), butyl methacrylate (n-BMA), t-butylacrylamide (t-BAA), N,N-dimethylacrylamide (DMAA) and N-[3-(dimethylamino)propyl]acrylamide (DMAPA) were used.
  • MMA methyl methacrylate
  • n-BMA butyl methacrylate
  • t-BAA t-butylacrylamide
  • DMAA N,N-dimethylacrylamide
  • DMAPA N-[3-(dimethylamino)propyl]acrylamide
  • the particle size of copolymers was measured using a Zetasizer manufactured by Malvern Instruments Ltd. Measurement samples of the microparticle dispersion liquid with the microparticle concentration of about 0.1% were prepared by dilution with water. After removing dust with a 0.45 ⁇ m filter, the scattering intensity at 25° C. was measured at the scattering angle of 173° (back-scattered light), the average particle size and the degree of dispersion were calculated with analysis software installed on the measurement apparatus. The particle size was analyzed by the cumulant analysis method. The degree of dispersion is a normalized value of the second-order cumulant value obtained by the cumulant analysis.
  • the degree of dispersion is a commonly used parameter, and the automatic analysis is possible by using a commercial dynamic light scattering measurement apparatus.
  • the viscosity of the solvent which was necessary for the particle size analysis, the viscosity of pure water at 25° C., i.e., 0.89 mPa ⁇ s, was used.
  • particulate polymers core-corona type microparticles
  • the particle sizes were 153.6 to 250.0 nm
  • the degrees of dispersion were 0.002 to 0.149 and the particle sizes were uniform.
  • the core-corona type microparticles having a uniform size of particles could be obtained by radically polymerizing the polyethylene oxide macromonomer represented by the above following formula (1) and one or two or more hydrophobic monomers selected from the acrylate derivative monomer represented by the above following formula (2) and the acrylamide derivative monomer represented by the above following formula (3), in conformity with the conditions ((A) to (D)):
  • a molar ratio expressed by a feed molar amount of the polyethylene oxide macromonomer/a feed molar amount of (the acrylate derivative monomer and/or the acrylamide derivative monomer) is 1:10 to 1:250;
  • the macromonomer represented by the following formula (1) is an acrylic acid derivative or a methacrylic acid derivative having a polyethylene glycol group with 8 to 200 repeating units,
  • the acrylate derivative monomer represented by the following formula (2) is an acrylic acid derivative or a methacrylic acid derivative having a substituent comprising an alkyl group having 1 to 12 carbon atoms
  • the acrylamide derivative monomer represented by the following formula (3) is an acrylamide derivative or a methacrylamide derivative having a substituent comprising an alkyl group having 1 to 18 carbon atoms;
  • a polymerization solvent is a water-alcohol mixed solvent, and the alcohol is one or two or more selected from ethanol, dipropylene glycol, 1,3-butylene glycol and isoprene glycol;
  • a droplet of the core-corona type microparticle dispersion of Production Example 5 was produced in dodecane with a syringe.
  • the dodecane/aqueous interfacial tension at an optional dispersion concentration was measured by a pendant drop method (Automatic contact angle meter DM-501, manufactured by Kyowa Interface Science Co., Ltd.) that can measure interfacial tension values by analyzing the shape of the droplet.
  • the conventional crosslinked core-corona type microparticles ((Acrylates/Methoxy PEG-90 Methacrylate) Crosspolymer) were used as a control. The results are shown in FIG. 1 .
  • the interfacial tension was substantially the same as the aforementioned crosspolymer until the addition concentration was 0.01% by weight; but thereafter, the interfacial tension remarkably decreased as the addition concentration was increased.
  • the core-corona type microparticles according to the present invention are superior in reducing the oil/aqueous interfacial tension compared to conventional crosslinked core-corona type microparticles.
  • aqueous phase components such as polyols and thickeners were added to purified water and mixed.
  • the cosmetic raw material according to the present invention was separately dispersed to purified water, added to the mixture, and stirred and mixed.
  • the cosmetic raw material and the aqueous phase components were homogeneously dispersed, to which the oil phase components were added, followed by shear mixing with a homomixer until homogeneous to obtain the oil-in-water emulsified cosmetic.
  • Samples were measured with a Spectrophotometer V-630 (manufactured by JASCO Corporation) at a wavelength of 600 nm, and the evaluation was carried out based on the visible light transmittance (light path length: 1 cm). Ion-exchanged water was used as the reference.
  • Emulsified particles of the sample were observed with an optical microscope.
  • An occlusive patch was applied to the inner upper arm of 10 sensitive skin panelists for 24 hours and the skin was evaluated based on the following criteria.
  • A The average of the 10 panelists is 0 or more and less than 0.15.
  • the average of the 10 panelists is 0.15 or more and less than 0.2.
  • the average of the 10 panelists is 0.2 or more and less than 0.3.
  • the feeling in use (“non-stickiness”, “full-bodied feeling”, and “fast blending”), when the sample was applied on the skin, was evaluated by 10 professional panelists based on the following criteria.
  • the oil-in-water emulsion cosmetic was visually observed one month after preparation.
  • A The sample was maintaining the emulsified state of the time of preparation.
  • an oil-in-water emulsified cosmetic that is excellent in emulsification stability, less in stickiness, excellent in dewy feeling, and less in powdery or squeaky feeling can be obtained.
  • the core-corona type microparticles according to the present invention can be used as the clouding agent for cosmetics.

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EP3520772A1 (en) 2019-08-07
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BR112019005771A2 (pt) 2019-06-11
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CN109715133B (zh) 2022-05-17
US11964043B2 (en) 2024-04-23
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