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WO2017057563A1 - Composition de poudre dans l'huile dans l'eau - Google Patents

Composition de poudre dans l'huile dans l'eau Download PDF

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Publication number
WO2017057563A1
WO2017057563A1 PCT/JP2016/078802 JP2016078802W WO2017057563A1 WO 2017057563 A1 WO2017057563 A1 WO 2017057563A1 JP 2016078802 W JP2016078802 W JP 2016078802W WO 2017057563 A1 WO2017057563 A1 WO 2017057563A1
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WO
WIPO (PCT)
Prior art keywords
oil
acid
water
powder
hydrophobic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2016/078802
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English (en)
Japanese (ja)
Inventor
太一 原田
松井　隆
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shiseido Co Ltd
Original Assignee
Shiseido Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shiseido Co Ltd filed Critical Shiseido Co Ltd
Priority to HK19100193.4A priority Critical patent/HK1257838A1/zh
Priority to CN201680057118.5A priority patent/CN108348443B/zh
Priority to KR1020187008672A priority patent/KR20180058727A/ko
Priority to JP2017543553A priority patent/JP6949714B2/ja
Publication of WO2017057563A1 publication Critical patent/WO2017057563A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A61K8/062—Oil-in-water emulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/29—Titanium; Compounds thereof
    • 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
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations

Definitions

  • the present invention relates to an oil-in-water powder-type composition in which oil droplets in which hydrophobic powder is dispersed are further dispersed in an aqueous phase, and particularly to an improvement in a dispersant for dispersing oil droplets in an aqueous phase.
  • Hydrophobic powder is usually used as a powder cosmetic or as a powder-in-oil cosmetic in which a hydrophobic powder is dispersed in an oil phase. If it is a phase, it is difficult to obtain a refreshing feel when applied to the skin. Therefore, a powder-in-oil-in-water composition in which oil droplets in which hydrophobic powder is dispersed is further dispersed in an aqueous phase may be used, and the continuous phase is an aqueous phase, so that it has excellent usability and is hydrophobic. Water resistance due to functional powder is also expected. However, the powder-in-oil-in-water composition has a problem that the water resistance inherent in the hydrophobic powder cannot be exhibited, although high improvement in the usability is recognized.
  • the present invention has been made in view of the prior art, and the problem to be solved is to provide a composition that does not impair the water resistance of hydrophobic powder while taking the form of an oil-in-water powder type. There is to do.
  • the use of a core-corona type microgel as a dispersant makes the powder-in-oil-in-water composition highly stable, and the composition
  • the present inventors have found that the hydrophobic powder on the coating film to which has been applied has high water resistance, and completed the present invention.
  • an oil-in-water powder-type composition is Hydrophobic powder, An oil phase in which the hydrophobic powder is dispersed; An aqueous phase in which the oil phase is dispersed; With As a dispersant for dispersing the oil phase in the aqueous phase, It is characterized in that a core-corona type microgel in which hydrophilic groups are partially provided on the surface of hydrophobic gel fine particles is used. Further, in the composition, as a core-corona type microgel, a (polymer) / (methacrylic acid methoxy PEG) crosspolymer and / or a specific acrylamide derivative and an acrylate derivative are subjected to radical polymerization under specific conditions without crosslinking.
  • a crosslinked acrylamide polymer It is preferable to use 0.5 to 10% by mass of a crosslinked acrylamide polymer.
  • a nonionic surfactant in the said composition it is suitable to set it as 0.5 mass% or less in a composition.
  • the core-corona microgel characteristic of the present invention can be used as a dispersant in so-called Pickering emulsion (powder emulsification) (Patent Documents 1 to 11, Non-Patent Documents 1 to 4).
  • this core-corona type microgel is new in that it has high dispersion stability in a powder-in-oil-in-water composition and improves the water resistance of the hydrophobic powder in the coating film when the composition is applied. We have obtained knowledge.
  • the core-corona type microgel is used as the dispersant for the powder-in-oil-in-water composition, the use of other surfactants can be suppressed, and the water resistance of the hydrophobic powder is sufficiently improved. It will be possible to demonstrate.
  • the hydrophobic powder used in the present invention is not particularly limited as long as the surface of the powder has hydrophobicity.
  • the powder itself such as silicone resin powder and fluororesin powder is used.
  • the surface of the inorganic powder particles is treated with silicones such as methyl hydrogen polysiloxane and dimethyl polysiloxane, dextrin fatty acid ester, higher fatty acid, higher alcohol, fatty acid ester, metal soap, alkyl phosphate ether, Hydrophobic treatments using a fluorine compound, or a hydrocarbon such as squalane and paraffin, by a wet method using a solvent, a gas phase method, a mechanochemical method, and the like can be given.
  • the average particle diameter of hydrophobic powder needs to be smaller than the emulsified particles that are the oil phase of the present invention.
  • the average particle size after crushing with a wet disperser is 100 nm or less.
  • the inorganic powder particles to be hydrophobized include titanium oxide, zinc oxide, talc, mica, sericite, kaolin, titanium mica, black iron oxide, yellow iron oxide, bengara, ultramarine blue, bitumen, chromium oxide, water. Examples include chromium oxide.
  • hydrophobic powders particularly when hydrophobized fine particle titanium dioxide and hydrophobized fine particle zinc oxide are blended together, it is known that remarkable emulsification particles are likely to aggregate and coalesce.
  • the dispersion stability and emulsification stability of the powder can be remarkably improved by blending the microgel as a dispersant. Become. For this reason, in the present invention, it is particularly useful when the hydrophobized fine particle titanium dioxide and the hydrophobized fine particle zinc oxide are contained as the hydrophobic powder.
  • the blending amount of the hydrophobized powder in the oil-in-water powder-type composition of the present invention is preferably 0.1 to 20% by mass relative to the total amount of the composition. If it is less than 0.1% by mass, the effect of the blending is not sufficient, and if it exceeds 20% by mass, the emulsion stability may be deteriorated.
  • Oil phase component examples include hydrocarbon oils, higher fatty acids, higher alcohols, synthetic ester oils, silicone oils, liquid fats and oils, solid fats and oils, waxes, and fragrances that are usually used in cosmetics, quasi drugs and the like.
  • hydrocarbon oil examples include isododecane, isohexadecane, isoparaffin, liquid paraffin, ozokerite, squalane, pristane, paraffin, ceresin, squalene, petrolatum, microcrystalline wax, and the like.
  • higher fatty acids examples include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, toluic acid, isostearic acid, linoleic acid, linolenic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid ( DHA) and the like.
  • Examples of the higher alcohol include straight chain alcohols (for example, lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol), branched chain alcohols (for example, monostearyl glycerol ether (batyl alcohol) ) -2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyl decanol, isostearyl alcohol, octyldodecanol, etc.).
  • straight chain alcohols for example, lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol
  • branched chain alcohols for example, monostearyl glycerol ether (batyl alcohol) ) -2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyl decano
  • Synthetic ester oils include, for example, octyl octoate, nonyl nonanoate, cetyl octanoate, isopropyl myristate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, dimethyl Hexyldecyl octoate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, monoisostearic acid N- Alkyl glycol, neopentyl glycol dicaprate, tripropylene glycol pivalate, diisosteary
  • silicone oil examples include chain polysiloxanes (for example, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.), cyclic polysiloxanes (for example, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexane).
  • chain polysiloxanes for example, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.
  • cyclic polysiloxanes for example, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexane.
  • Silicone resins, silicone rubber, various modified polysiloxanes as amino-modified polysiloxane, polyether-modified polysiloxane, alkyl
  • liquid oils examples include avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, southern castor oil, castor oil, linseed oil , Safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnagiri oil, Japanese kiri oil, jojoba oil, germ oil, triglycerin and the like.
  • solid fat examples include cacao butter, palm oil, horse fat, hydrogenated palm oil, palm oil, beef tallow, sheep fat, hydrogenated beef tallow, palm kernel oil, pork fat, beef bone fat, owl kernel oil, hydrogenated oil, cattle Leg fats, moles, hydrogenated castor oil and the like.
  • waxes examples include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibota wax, whale wax, montan wax, nuka wax, lanolin, kapok wax, lanolin acetate, liquid lanolin, sugarcane wax, lanolin fatty acid isopropyl, hexyl laurate, Examples include reduced lanolin, jojoballow, hard lanolin, shellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, and POE hydrogenated lanolin alcohol ether.
  • fragrances examples include natural fragrances obtained from animals or plants, synthetic fragrances produced by chemical synthesis means, and blended fragrances that are mixtures thereof, and are not particularly limited. By blending a fragrance, it is possible to obtain a cosmetic with excellent fragrance sustainability.
  • fragrances include acetylenol, anisaldehyde, anethole, amyl acetate, amyl salicylate, allyl amyl glycolate, allyl caproate, aldehyde C6-20, ambretride, ambretlide, ambroxan, ionone, ISOE Super, Eugenol, Auranthiol, Galaxolide, Calone, Coumarin, Geraniol, Geranyl acetate, Sandaroa, Santalol, Sandera, Cyclamenaldehyde, Cis-3-hexenyl acetate, Cis-3-hexenol, Citral, Citronellyl acetate, Citronellol , Cineol, Dihydromyrcenol, Jasmolactone, Cinamic Alcohol, Cinamic Aldehyde, Styraryl Acetate, Cedryl Acetate , Cedrol, damascon, damassenone, decalact
  • the powder-in-oil-in-water composition of the present invention is a pickering emulsion using a core-corona type microgel as a dispersant, it is less affected by the type of oil, such as emulsifiability and stability, and is wider than before.
  • Various types of oil can be blended.
  • Water phase component As the water phase component, water, water-soluble alcohols, thickeners and the like that are usually used in cosmetics, quasi drugs, and the like can be blended. Further, if desired, a humectant, chelating agent, preservative , Pigments and the like can be appropriately blended.
  • the water contained in the powder-in-oil-in-water composition of the present invention is not particularly limited, and examples thereof include purified water, ion exchange water, and tap water.
  • water-soluble alcohols include lower alcohols, polyhydric alcohols, polyhydric alcohol polymers, divalent alcohol alkyl ethers, dihydric alcohol alkyl ethers, dihydric alcohol ether esters, glycerin monoalkyl ethers, sugar alcohols, Examples thereof include monosaccharides, oligosaccharides, polysaccharides, and derivatives thereof.
  • lower alcohols examples include ethanol, propanol, isopropanol, isobutyl alcohol, t-butyl alcohol and the like.
  • polyhydric alcohol examples include dihydric alcohols (eg, 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, octylene glycol, etc.), trihydric alcohol (eg, glycerin, trimethylolpropane, etc.), tetrahydric alcohol (eg, diglycerin, 1,2, , 6-hexanetriol, etc.), pentahydric alcohol (eg, xylitol, triglycerin, etc.), hexahydric alcohol (eg, sorbitol, mannitol, etc.), polyhydric alcohol polymer (eg, diethylene glycol) Dipropylene glycol-triethylene glycol, polypropylene glycol, tetra
  • monosaccharides include tricarbon sugars (for example, D-glyceryl aldehyde, dihydroxyacetone, etc.), tetracarbon sugars (for example, D-erythrose, D-erythrose, D-threoose, erythritol, etc.), Pentose sugars (for example, L-arabinose, D-xylos, L-lyxose, D-arabinose, D-ribose, D-ribose, D-xylulose, L- Xylose, etc.), hexose (eg D-glucose, D-talose, D-bucikose, D-galactose, D-fructose, L-galactose, L- Mannose, D-tagatose, etc.), heptose sugar (eg, aldoheptose, heproose, etc.), octose sugar (eg
  • Oligosaccharides include, for example, sucrose, guntianose, umbelliferose, lactose, planteose, isoliquinoses, ⁇ , ⁇ -trehalose, raffinose, lycnose, umbilicin, stachyose verbus courses, and the like.
  • polysaccharide examples include cellulose, quince seed, starch, galactan, dermatan sulfate, glycogen, gum arabic, heparan sulfate-tragacanth gum, keratan sulfate, chondroitin, xanthan gum, guar gum, dextran, kerato sulfate, locust bean gum, saxino glucan, etc. Is mentioned.
  • polystyrene resin examples include polyoxyethylene methyl glucoside (Glucam E-10), polyoxypropylene methyl glucoside (Glucam P-10) and the like.
  • thickeners examples include gum arabic, carrageenan, colored gum, tragacanth gum, carob gum, quince seed (malmello), casein, dextrin, gelatin, sodium pectate, sodium alginate, methylcellulose, ethylcellulose, CMC, hydroxyethylcellulose, hydroxypropyl Cellulose, PVA, PVM, PVP, sodium polyacrylate, carboxyvinyl polymer, locust bean gum, guar gum, tamarind gum, cellulose dialkyldimethylammonium sulfate, xanthan gum, magnesium aluminum silicate, bentonite, hectorite, silicate A1Mg (bee gum), Examples thereof include laponite and silicic anhydride.
  • natural water-soluble polymers include plant-based polymers (for example, gum arabic, gum tragacanth, galactan, guar gum, carob gum, colored yam, carrageenan, pectin, agar, quince seed (malmello), alge colloid (guckweed extract), starch (Rice, corn, potato, wheat), glycyrrhizic acid), microbial polymers (eg, xanthan gum, dextran, succinoglucan, pullulan, etc.), animal polymers (eg, collagen, casein, albumin, gelatin, etc.), etc. Is mentioned.
  • plant-based polymers for example, gum arabic, gum tragacanth, galactan, guar gum, carob gum, colored yam, carrageenan, pectin, agar, quince seed (malmello), alge colloid (guckweed extract), starch (Rice, corn, potato, wheat), glycyrrhizic acid),
  • semi-synthetic water-soluble polymers include starch polymers (eg, carboxymethyl starch, methylhydroxypropyl starch, etc.), cellulose polymers (methylcellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate). Hydroxypropylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, crystalline cellulose, cellulose powder, etc.), alginic acid polymers (for example, sodium alginate, propylene glycol alginate, etc.) and the like.
  • starch polymers eg, carboxymethyl starch, methylhydroxypropyl starch, etc.
  • cellulose polymers methylcellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate. Hydroxypropylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, crystalline cellulose, cellulose powder, etc.
  • alginic acid polymers for example, sodium alginate
  • Examples of the synthetic water-soluble polymer include vinyl polymers (for example, polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, carboxyvinyl polymer, etc.) and polyoxyethylene polymers (for example, polyethylene glycol 20,000, 40). , 000, 60,000, etc.), acrylic polymers (for example, sodium polyacrylate, polyethyl acrylate, polyacrylamide, etc.), polyethyleneimine, cationic polymers and the like.
  • vinyl polymers for example, polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, carboxyvinyl polymer, etc.
  • polyoxyethylene polymers for example, polyethylene glycol 20,000, 40. , 000, 60,000, etc.
  • acrylic polymers for example, sodium polyacrylate, polyethyl acrylate, polyacrylamide, etc.
  • polyethyleneimine for example, sodium polyacrylate, polyethyl acrylate, polyacrylamide, etc.
  • humectant examples include chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-12-hydroxystearate, sodium lactate, bile salt, DL-pyrrolidone carboxylate, short chain soluble collagen, Diglycerin (EO) PO adduct, Izayoi rose extract, Achillea millefolium extract, Merirot extract and the like can be mentioned.
  • EO Diglycerin
  • sequestering agent examples include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, trisodium edetate, and tetrasodium edetate.
  • amino acids examples include neutral amino acids (eg, threonine, cysteine, etc.), basic amino acids (eg, hydroxylysine, etc.), and the like.
  • amino acid derivatives include acyl sarcosine sodium (lauroyl sarcosine sodium), acyl glutamate, acyl ⁇ -alanine sodium, glutathione and the like.
  • Examples of the pH adjuster include buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate.
  • buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate.
  • core-corona type microgel both a crosslinked type and a non-crosslinked type can be used.
  • core-corona type microgels as shown below, (acrylates / methoxymethacrylate PEG) crosspolymer [crosslinked core-corona type microgel] and acrylamide-based core corona type microgel [non-crosslinked type core-corona type microgel] ] Is exemplified. 1.
  • cross-linked core-corona-type microgel [(Acrylates / Methoxymethacrylate PEG-90) crosspolymer]]
  • the crosslinked core-corona microgel according to the present invention can be obtained by radical polymerization of monomers represented by the following formulas (1) to (3) under specific conditions.
  • polyethylene oxide macromonomer represented by the formula (1) for example, a commercially available product commercially available from Aldrich, or a commercially available product such as BLEMMER (registered trademark) sold by NOF Corporation may be used.
  • Examples of such a macromonomer include Blemmer (registered trademark) PME-400, Blemmer (registered trademark) PME-1000, and Blemmer (registered trademark) PME-4000 manufactured by NOF Corporation.
  • R 1 is an alkyl group having 1 to 3 carbon atoms, and n is a number of 8 to 200.
  • X is H or CH 3 .
  • hydrophobic monomer represented by the formula (2) for example, a commercially available product commercially available from Aldrich or Tokyo Kasei can be used.
  • R 2 is an alkyl group having 1 to 3 carbon atoms.
  • R 3 is an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms.
  • hydrophobic monomer examples include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, methacryl
  • examples include methyl acid, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, and the like.
  • These hydrophobic monomers are general-purpose raw materials and can be easily obtained as general industrial raw materials.
  • the crosslinkable monomer represented by the formula (3) can be obtained as a commercial product or an industrial raw material.
  • This crosslinkable monomer is preferably hydrophobic.
  • the value of m is preferably 0-2.
  • EGDMA ethylene glycol dimethacrylate
  • Blemmer registered trademark
  • R 4 and R 5 each independently represents an alkyl group having 1 to 3 carbon atoms, and m is a number from 0 to 2.
  • the core-corona microgel according to the present invention is obtained by radical polymerization of the above monomers under the following conditions (A) to (E).
  • (A) The molar ratio represented by the charged molar amount of the polyethylene oxide macromonomer / the charged molar amount of the hydrophobic monomer is 1:10 to 1: 250.
  • (B) The charge amount of the crosslinkable monomer is 0.1 to 1.5% by mass with respect to the charge amount of the hydrophobic monomer.
  • the hydrophobic monomer represented by the formula (2) has a monomer composition in which one or more methacrylic acid derivatives having an alkyl group having 1 to 8 carbon atoms are mixed.
  • the polymerization solvent is a mixed solvent of water and an organic solvent
  • a polyol is used as the organic solvent
  • one or more selected from dipropylene glycol, 1,3-butylene glycol, and isoprene glycol are used.
  • the charged amount of the crosslinkable monomer relative to the charged amount of the hydrophobic monomer is defined as a crosslinking density (mass%).
  • the crosslinking density of the core-corona type microgel used in the present invention is such that the amount of the crosslinkable monomer charged is 0.1 to 1.5% by mass based on the amount of the hydrophobic monomer, depending on the condition (B). Must.
  • the dispersion stabilization by the polyethylene oxide macromonomer becomes incomplete, and the hydrophobic polymer by the insoluble hydrophobic monomer aggregates and precipitates.
  • composition (B) By copolymerizing the crosslinkable monomer, it is possible to polymerize the microgel in which the hydrophobic polymer in the core portion is crosslinked.
  • the charge amount of the crosslinkable monomer is less than 0.1% by mass of the charge amount of the hydrophobic monomer, the crosslink density is low, and the microgel collapses when swollen.
  • the charged amount exceeds 1.5% by mass, aggregation of microgel particles occurs, and suitable microgel particles having a narrow particle size distribution cannot be polymerized.
  • the amount of the crosslinkable monomer charged is preferably 0.2 to 1.0, more preferably 0.2 to 0.8, and most preferably 0.2 to 0.5% by mass.
  • the hydrophobic monomer represented by the formula (2) needs to have a monomer composition in which one or more methacrylic acid derivatives having an alkyl group having 1 to 8 carbon atoms are mixed. If the number of carbon atoms is 0 (a monomer having no terminal ester bond), the monomer may be too hydrophilic to perform emulsion polymerization well. On the other hand, when the number of carbon atoms is 9 or more, there may be a steric hindrance during polymerization, and a crosslinked structure may not be successfully constructed.
  • the polymerization solvent needs to be a mixed solvent of water-organic solvent.
  • the organic solvent ethanol, propanol, butanol, polyol, and the like can be used.
  • the polyol is used, the hydrophobic monomer represented by the formula (2) and the crosslinkable monomer represented by the formula (3) are dissolved. What can be done is preferred.
  • the polyol used in the present invention needs to be dipropylene glycol, 1,3-butylene glycol, or isoprene glycol.
  • the solvent mixed with water is ethanol, propanol, butanol, etc. when applied to the skin It is preferably an polyol that can be blended into cosmetics for general purposes, not an organic solvent in which irritation is a concern.
  • the mixing ratio of the organic solvent is 10 to 90 volume ratio.
  • the mixing ratio of the organic solvent When the mixing ratio of the organic solvent is lower than 10 volume ratio, the dissolving ability of the hydrophobic monomer becomes extremely low, polymerization proceeds in a monomer droplet state, and a huge mass is formed, and a microgel is not generated.
  • the mixing ratio of the organic solvent exceeds 90 volume ratio, an emulsion of a hydrophobic monomer due to hydrophobic interaction is not generated, emulsion polymerization does not proceed, and a microgel cannot be obtained.
  • the core-corona-type microgel according to the present invention obtained by using a polyol is a water-polyol mixed solvent as a polymerization solvent, and does not contain ethanol. Can get to.
  • polymerization initiator used in the polymerization system a commercially available polymerization initiator used for usual water-soluble thermal radical polymerization can be used. In this polymerization system, even if the polymerization is carried out without strictly controlling the stirring conditions, it is possible to obtain a polymer having a very narrow particle size distribution.
  • Non-crosslinked core-corona microgel [acrylamide core corona]
  • a non-crosslinked core corona microgel suitably used in the present invention is a dispersion of core-corona microparticles obtained by radical polymerization of monomers represented by the following formulas (1) to (3) under specific conditions. is there.
  • R 1 is an alkyl group having 1 to 3 carbon atoms, and n (molecular weight of the polyethylene oxide portion) is a number of 8 to 200.
  • X is H or CH 3 .
  • the polyethylene oxide macromonomer represented by the above formula (1) is preferably an acrylic acid derivative or a methacrylic acid derivative.
  • a commercial product commercially available from Aldrich or a commercial product such as Bremer (registered trademark) marketed by NOF Corporation may be used.
  • R 2 represents an alkyl group having 1 to 3 carbon atoms
  • R 3 represents a substituent containing an alkyl group having 1 to 12 carbon atoms.
  • the hydrophobic monomer represented by the above formula (2) is preferably an acrylic acid derivative or a methacrylic acid derivative.
  • methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, acrylic Hexyl acrylate, heptyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, methacryl Octyl acid, decyl methacrylate, dodecyl methacrylate and the like can be used.
  • methyl methacrylate also known as methyl methacrylate
  • butyl methacrylate also known as butyl methacrylate
  • octyl methacrylate are particularly suitable.
  • These hydrophobic monomers are general-purpose raw materials and can be easily obtained as general industrial raw materials. For example, you may use the commercial item marketed from Aldrich or Tokyo Kasei.
  • R 4 represents H or an alkyl group having 1 to 3 carbon atoms
  • R 5 and R 6 represent H or a substituent containing an alkyl group having 1 to 12 carbon atoms.
  • the hydrophobic monomer represented by the above 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 and the like can be suitably used.
  • t-butylacrylamide, N, N-dimethylacrylamide, and N- [3- (dimethylamino) propyl] acrylamide are particularly preferable.
  • These hydrophobic monomers are available as commercial products or industrial raw materials.
  • the copolymer constituting the core-corona type microparticles according to the present invention comprises a macromonomer represented by the above formula (1) by any radical polymerization method according to the following conditions (A) to (D): One or two or more selected from the hydrophobic monomers represented by the above formulas (2) and (3) are copolymerized.
  • A) The molar ratio represented by the charged molar amount of the polyethylene oxide macromonomer / (the acrylate derivative monomer and / or 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 having a repeating unit of 8 to 200
  • the acrylate derivative monomer represented by the following formula (2) is an acrylic acid derivative or a methacrylic acid derivative having a substituent containing 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 containing an alkyl group having 1 to 12 carbon atoms
  • the polymerization solvent is a water-alcohol mixed solvent, and the alcohol is one or more selected from ethanol, dipropylene glycol, 1,3-butylene glycol, and isoprene glycol.
  • the charged molar amount is preferably 1:10 to 1: 200, more preferably 1:25 to 1: 100.
  • the molar amount of the hydrophobic monomer is less than 10 times the molar amount of the polyethylene oxide macromonomer, the polymer to be polymerized becomes water-soluble and does not form core-corona type particles.
  • the dispersion stabilization by the polyethylene oxide macromonomer becomes incomplete, and the hydrophobic polymer by the insoluble hydrophobic monomer aggregates and precipitates. To do.
  • Condition (B) consists of the following three conditions (B-1) to (B-3).
  • the macromonomer represented by the formula (1) is an acrylic acid derivative or a methacrylic acid derivative having a polyethylene glycol group having 8 to 200 repeating units. When the repeating unit is 7 or less, particles stably dispersed in the solvent may not be obtained, and when it exceeds 200, the particles may be made fine and unstable when 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 containing an alkyl group having 1 to 12 carbon atoms.
  • the acrylamide derivative monomer represented by the formula (3) is an acrylamide derivative or a methacrylamide derivative having a substituent containing an alkyl group having 1 to 18 carbon atoms.
  • the hydrophobic monomer according to the present invention has a monomer composition in which one or more selected from the acrylate derivative monomer represented by the above formula (2) and the acrylamide derivative monomer represented by the formula (3) are mixed. is required.
  • hydrophobic monomers methacrylate and butyl methacrylate, or four types of methacrylate, t-butylacrylamide, N, N-dimethylacrylamide, and N- [3- (dimethylamino) propyl] acrylamide are used. It is particularly preferable to use In the combination of these hydrophobic monomers, it is further preferable to use methoxypolyethylene glycol monometalate as a macromonomer.
  • Methoxypolyethylene glycol monometalates having a repeating unit of polyethylene glycol groups of 8 to 200, most preferably 90, methacrylate, t-butylacrylamide, N, N-dimethylacrylamide, and N- [3- (dimethylamino) propyl Acrylamide, t-butyl methacrylamide, octyl acrylamide, octyl methacrylamide, and octadecyl acrylamide.
  • the polymerization solvent needs to be a water-alcohol mixed solvent.
  • alcohol what can melt
  • one or more selected from ethanol, dipropylene glycol, 1,3-butylene glycol, and isoprene glycol are preferable.
  • the mixing ratio of alcohol is lower than 10 volume ratio, the dissolving ability of the hydrophobic monomer becomes extremely low, and microparticles may not be generated.
  • the mixing ratio of alcohol exceeds 90 volume ratio, an emulsion of a hydrophobic monomer due to hydrophobic interaction may not be generated, and emulsion polymerization may not proceed and microparticles may not be obtained.
  • the core-corona type microgel according to the present invention is a microgel stabilized with a polyethylene oxide chain which is a nonionic polymer, and its dispersion stability in water can be expected to have acid resistance and salt resistance.
  • the microgel used in the present invention is a core-corona type in which hydrophilic macromonomer and hydrophobic monomer are ordered in a solvent, the particle diameter is almost constant, and the core part is crosslinked or non-crosslinked. It is thought that a polymer microgel is formed.
  • the blending amount of the core-corona microgel of the present invention in cosmetics is preferably 0.01 to 10% by mass (pure content, hereinafter simply expressed as%) with respect to the total amount of the composition. If the blending amount is less than 0.01% (pure content), it may be difficult to obtain a stable cosmetic. If the blending amount exceeds 10% (pure content), it may not be preferable as a composition from the viewpoint of stability during long-term storage under high temperature conditions, or it may be inferior in usability.
  • the core-corona type microgel of the present invention has a structure in which an oil phase component and an aqueous phase component are emulsified, and the core-corona type microgel emulsifier is adsorbed on oil droplets of the oil phase component dispersed in the aqueous phase component.
  • a powder-in-oil-in-water composition is formed. Therefore, the core-corona type microgel emulsifier of the present invention is excellent in emulsifying power, and if the core-corona type microgel of the present invention is used as an emulsifier, a powder-in-oil-in-water composition having extremely excellent emulsification stability can be obtained. Can be manufactured.
  • the core-corona type microgel can obtain sufficient strength against the behavior of the hydrophobic powder having a large specific gravity present in the oil phase.
  • a core-corona type microgel is mixed and dispersed in water or an aqueous phase component, and an oil phase component and other components in which hydrophobic powder is dispersed by a conventional method are added. It is produced by emulsifying by applying stirring and shearing force.
  • the blending amount of the oil phase component and the water phase component blended in the powder-in-oil-in-water composition of the present invention is not particularly limited.
  • A By using a core-corona type microgel as an emulsifier, an embodiment having a small oil phase component / water phase component ratio, that is, an embodiment having a small amount of oil phase component blended (beauty liquid, emulsion, etc.) It is possible to obtain a powder-in-oil-in-water composition having a wide oil phase component / water phase component ratio (cleansing cream, sunscreen, hair cream, sheet, aerosol, foundation, etc.).
  • composition according to the present invention includes other components usually used in cosmetics, quasi-drugs and the like, for example, ultraviolet absorbers, powders, organic amines, polymer emulsions, as long as the effects of the present invention are not impaired. , Vitamins, antioxidants and the like can be appropriately blended.
  • water-soluble ultraviolet absorber examples include 2,4-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4, 4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4′-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, Benzophenone ultraviolet absorbers such as 2-ethylhexyl-4′-phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone, phenylbenzimidazole-5- Sulfonic acid and Benzimidazole ultraviolet absorbers such as salts thereof, phenylene-bis-benzimidazole-tetrasulfonic acid and salts thereof,
  • oil-soluble ultraviolet absorber examples include paraaminobenzoic acid (PABA), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester, N, N-dimethyl PABA ethyl ester, N Benzoic acid UV absorbers such as N-dimethyl PABA butyl ester; Anthranilic acid UV absorbers such as homomenthyl-N-acetylanthranilate; Amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl Salicylic acid UV absorbers such as salicylate and p-isopropanolphenyl salicylate; octylcinnamate, ethyl-4-isopropylcinnamate, methyl-2,5-diisopropylcin Mate,
  • the powder component examples include inorganic powders (for example, talc, kaolin, mica, sericite (sericite), muscovite, phlogopite, synthetic mica, saucite, biotite, permiculite, magnesium carbonate, calcium carbonate, silicic acid.
  • inorganic powders for example, talc, kaolin, mica, sericite (sericite), muscovite, phlogopite, synthetic mica, saucite, biotite, permiculite, magnesium carbonate, calcium carbonate, silicic acid.
  • Organic pigment Red No. 3, Red No. 104, Red No. 106, Red No. 227, Red No. 230, Red No. 401, Red No. 505, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203 , Green No. 3 and Blue No. 1
  • natural pigments for example, chlorophyll, ⁇ -carotene, etc.
  • organic amine examples include monoethanolamine, diethanolamine, triethanolamine, morpholine, tetrakis (2-hydroxypropyl) ethylenediamine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino Examples include -2-methyl-1-propanol.
  • polymer emulsion examples include acrylic resin emulsion, polyethyl acrylate emulsion, acrylic resin liquid, polyacryl alkyl ester emulsion, polyvinyl acetate resin emulsion, natural rubber latex, and the like.
  • vitamins examples include vitamins A, B1, B2, B6, C, E and derivatives thereof, pantothenic acid and derivatives thereof, and biotin.
  • antioxidants examples include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid esters and the like.
  • antioxidant assistant examples include phosphoric acid, citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, fumaric acid, kephalin, hexametaphosphate, phytic acid, and ethylenediaminetetraacetic acid.
  • ingredients that can be blended include, for example, preservatives (methylparaben, ethylparaben, butylparaben, phenoxyethanol, etc.), anti-inflammatory agents (for example, glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, zinc oxide, allantoin, etc.), Whitening agents (eg, placenta extract, yukinoshita extract, arbutin, etc.), various extracts (eg, buckwheat, auren, shikon, peonies, assembly, birch, sage, loquat, carrot, aloe, mallow, iris, grape, yokoinin , Loofah, lily, saffron, senkyu, ginger, hypericum, onionis, garlic, pepper, chimpanchi, seaweed, etc.), activator (eg, royal jelly, photosensitizer
  • oil-in-water-in-oil powder type composition of the present invention is not intended as an emulsifier, but is controlled for use feeling, control of drug penetration, etc., or cleansing properties when blended with a skin or hair cleaning agent.
  • a surfactant can be blended as an aqueous phase or oil phase component.
  • the amphoteric surfactant has at least one cationic functional group and one anionic functional group, becomes cationic when the solution is acidic, and anionic when the solution is alkaline, and is close to a nonionic surfactant near the isoelectric point. It has properties.
  • Amphoteric surfactants are classified into carboxylic acid type, sulfate ester type, sulfonic acid type and phosphate ester type depending on the type of anionic group.
  • the carboxylic acid type, sulfate type and sulfonic acid type are preferred in the present invention.
  • Carboxylic acid types are further classified into amino acid types and betaine types. Particularly preferred is a betaine type.
  • imidazoline-based amphoteric surfactants for example, 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide) 1-carboxyethyloxy disodium salt
  • betaine surfactants for example, 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkylbetaine, amide betaine, sulfone) Betaine
  • cationic surfactant examples include quaternary ammonium salts such as cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, behenyldimethylhydroxyethylammonium chloride, stearyldimethylbenzylammonium chloride, and cetyltriethylammonium methylsulfate. Is mentioned.
  • stearic acid diethylaminoethylamide stearic acid dimethylaminoethylamide, palmitic acid diethylaminoethylamide, palmitic acid dimethylaminoethylamide, myristic acid diethylaminoethylamide, myristic acid dimethylaminoethylamide, behenic acid diethylaminoethylamide, behenic acid dimethyl Aminoethylamide, stearic acid diethylaminopropylamide, stearic acid dimethylaminopropylamide, palmitic acid diethylaminopropylamide, palmitic acid dimethylaminopropylamide, myristic acid diethylaminopropylamide, myristic acid dimethylaminopropylamide, behenic acid diethylaminopropylamide, behenine Amidoamino such as dimethylaminopropylamide Compounds
  • Anionic surfactants include fatty acid soap, N-acyl glutamate, carboxylate type such as alkyl ether acetic acid, sulfonic acid type such as ⁇ -olefin sulfonate, alkane sulfonate, alkylbenzene sulfonic acid, higher alcohol sulfuric acid It is classified into a sulfate ester salt type such as an ester salt and a phosphate ester salt type. Carboxylate type, sulfonic acid type and sulfate ester type are preferred, and sulfate ester type is particularly preferred.
  • fatty acid soap eg, sodium laurate, sodium palmitate, etc.
  • higher alkyl sulfate ester salt eg, sodium lauryl sulfate, potassium lauryl sulfate
  • alkyl ether sulfate ester salt eg, POE- Lauryl sulfate triethanolamine, POE-sodium lauryl sulfate, etc.
  • N-acyl sarcosine acid eg, sodium lauroyl sarcosine, etc.
  • higher fatty acid amide sulfonate eg, sodium N-myristoyl-N-methyltaurine, coconut oil fatty acid
  • phosphoric acid ester salts POE-oleyl ether sodium phosphate, POE-stearyl ether phosphoric acid etc.
  • sulfosuccinates eg di-2-ethy
  • the nonionic surfactant is a surfactant that is ionized in an aqueous solution and has no charge.
  • a type using alkyl and a type using dimethyl silicone are known.
  • the former for example, glycerin fatty acid ester, ethylene oxide derivative of glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, ethylene oxide derivative of propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, polyethylene glycol alkyl ether, Examples include polyethylene glycol alkylphenyl ether, polyethylene glycol castor oil derivatives, polyethylene glycol hydrogenated castor oil derivatives, and the like. Examples of the latter include polyether-modified silicone and polyglycerin-modified silicone.
  • a type using alkyl as a hydrophobic group is preferred.
  • sorbitan fatty acid esters for example, sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, Sorbitan sesquioleate, sorbitan trioleate, diglycerol sorbitan penta-2-ethylhexylate, diglycerol sorbitan tetra-2-ethylhexylate), glycerin polyglycerin fatty acids (eg mono cottonseed oil fatty acid glycerin, glyceryl monoerucate, sesquiolein) Acid glycerin, glyceryl monostearate, ⁇ , ⁇ '-oleic acid pyroglutamate glycerin, monostearate glycerin malate, etc.), propylene glycol fatty acid ester And the like (
  • hydrophilic nonionic surfactants include POE-sorbitan fatty acid esters (for example, POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, POE-sorbitan tetraoleate).
  • POE-sorbitan fatty acid esters for example, POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, POE-sorbitan tetraoleate.
  • POE sorbite fatty acid esters eg, POE-sorbite monolaurate, POE-sorbite monooleate, POE-sorbite pentaoleate, POE-sorbite monostearate, etc.
  • POE-glycerin fatty acid esters eg, POE- Glycerol monostearate, POE-glycerol monoisostearate, POE-monooleate such as POE-glycerol triisostearate
  • POE-fatty acid esters for example, POE-distearate, OE-monodiolate, ethylene glycol distearate, etc.
  • POE-alkyl ethers for example, POE-lauryl ether, POE-oleyl ether, POE-stearyl ether, POE-behenyl ether, POE-2-octyldodecyl ether, POE-core
  • Stanol ether etc.
  • oil-in-water powder-in-water composition of the present invention is not limited, but since the stability is high and the water resistance of the hydrophobic powder is not easily affected, skin cosmetics such as sunscreen cosmetics and emulsion foundations, It can be commercialized as a hair cosmetic, a skin external preparation, or the like.
  • skin cosmetics such as sunscreen cosmetics and emulsion foundations, It can be commercialized as a hair cosmetic, a skin external preparation, or the like.
  • the present inventors examined oil-in-water powder-in-water cosmetics mainly with respect to the blending form of hydrophobic powder, system stability, and water resistance during application. The results are shown in Table 1. Evaluation was performed as follows. [water resistant] Apply 2mg / cm 2 of sample to resin plate and measure UV spectrum from 290 to 400nm.
  • the plate is attached to the wall of a 20L container containing water with double-sided tape, exposed to a water flow of 30min at 500rpm, and the spectrum is measured again in the same way.
  • the ratio% of the integral value of the spectrum before and after bathing is water resistance, and if it is 100%, it indicates that the protective effect is not lowered at all even if bathing.
  • each test example is as follows.
  • Component 27 is dispersed and emulsified in components 18, 19, and 20.
  • Oil phases A and B are mixed in water phase.
  • Aqueous components 1, 2, 3, 4, 5, 8, 30, 33, 34, 35 are mixed into the liquid oil of mixed oil phase A components 14, 15, 16, 17, and components 11, 12, 13, 21, 22, 22. 23, 24 solid oil component dissolved oil phase B component 18, 19, 20 component 27 dispersed emulsified water phase mixed with oil phase B, A in this order
  • emulsion stability and water resistance can be obtained by selecting an appropriate surfactant, but the continuous phase is the oil phase. Therefore, it is not possible to obtain a fresh feeling of use.
  • Core-corona emulsification is also considered as a kind of so-called powder emulsification (Pickering emulsion), and is considered to be a similar technique in terms of stabilizing the emulsification by adhesion of fine particles to the oil / water interface. "And compared.
  • Emulsification was attempted using PEG-10 hydrogenated castor oil that forms vesicles, which is one of the particles used for three-phase emulsification (1-6), but hydrophobic powder popped out of the inner phase and aggregated. Therefore, it was difficult to prepare a stable emulsion composition.
  • the present inventors proceeded with the study of a POW emulsified composition by core-corona emulsification. First, the present inventors examined the amount of core-corona dispersant added. The results are shown in Table 2.
  • the core-corona type microgel exhibits excellent stability at 0.5% by mass or more (pure content) in the composition, although it depends on the blending amount of the oil phase containing the hydrophobic powder. .
  • the dispersant is up to about 2% by mass, but 10% by mass. % Blending is also possible.
  • the present inventors examined addition of a nonionic surfactant. The results are shown in Table 3.
  • Nonionic surfactants may improve emulsification stability by appropriate blending even in core-corona emulsification, but there is no problem with the stability when the blending amount is 0.8% by mass or more. However, the water resistance is significantly reduced. For this reason, the nonionic surfactant is not necessarily blended, but is preferably 0.5% by mass or less even when blended.
  • Method 1 The production method conformed to Test Example 1-1.
  • Nonionic surfactants may improve emulsification stability by appropriate blending even in core-corona emulsification, but there is no problem with the stability when the blending amount is 0.8% by mass or more. However, the water resistance is significantly reduced. For this reason, the nonionic surfactant is not necessarily blended, but is preferably 0.5% by mass or less even when blended.
  • Method 1 The macromonomer and hydrophobic monomer described in Table 4 were radically polymerized under the polymerization conditions described in Table 4 and Table 5 according to the following production method (Method 1). The appearance of
  • ⁇ Method 1 Manufacturing method of core-corona type microparticle> Polyethylene oxide macromonomer and hydrophobic monomer were added to 90 g of a water-alcohol mixed solvent in a three-necked flask equipped with a reflux tube and a nitrogen introduction tube. After sufficiently dissolving or dispersing, 1 mol% of the polymerization initiator 2,2′-azobis (2-methylpropionamidine dihydrochloride) is dissolved in a small amount of water and added to the total amount of monomers, and further dissolved or dispersed. Dispersed.
  • the uniformly dissolved or dispersed polymerization solution was purged with nitrogen for 20 minutes to remove dissolved oxygen, and then stirred at a magnetic stirrer and kept at 65 to 70 ° C. for 8 hours in an oil bath to carry out a polymerization reaction. After completion of the polymerization, the polymerization solution was returned to room temperature to obtain a core-corona type microparticle dispersion.
  • BLEMMER PME-4000 manufactured by NOF Corporation
  • Hydrophobic monomers include methyl methacrylate (MMA), butyl methacrylate (n-BMA), t-butyl acrylamide (t-BAA), N, N-dimethylacrylamide (DMAA), N- [3- (dimethylamino).
  • DMAPA Propyl] acrylamide
  • ⁇ Method 2 Measuring method of particle diameter and degree of dispersion>
  • the particle size of the copolymer was measured using a Zetasizer manufactured by Malvern.
  • a measurement sample having a microparticle concentration of about 0.1% in the microparticle dispersion was prepared by dilution with water, and after removing dust with a 0.45 micrometer filter, the scattering intensity at 25 ° C was measured with a scattering angle of 173 ° (backward).
  • the average particle size and the degree of dispersion were calculated using analysis software installed in the measuring device.
  • the particle diameter is analyzed by a cumulant analysis method, and the degree of dispersion is a numerical value obtained by standardizing the value of the secondary cumulant obtained by the cumulant analysis.
  • This degree of dispersion is a commonly used parameter and can be automatically analyzed by using a commercially available dynamic light scattering measurement device.
  • the viscosity of the solvent necessary for the particle size analysis the viscosity of pure water at 25 ° C., that is, a value of 0.89 mPa ⁇ s was used.
  • methoxypolyethylene glycol monometalate (macromonomer) and methyl methacrylate, butyl methacrylate, t-butylacrylamide, N, N-dimethyl having a substituent containing an alkyl group having 1 to 4 carbon atoms
  • the diameter and degree of dispersion could be evaluated. That is, formation of particulate polymer (core-corona type microparticle) was confirmed.
  • the core-corona type microparticles of Production Examples 1 to 10 were shown to have a particle diameter of 150 to 250 nm and a uniform particle diameter.
  • the macromonomer represented by the formula (1) is an acrylic acid derivative or a methacrylic acid derivative having a polyethylene glycol group having a repeating unit of 8 to 200
  • the acrylate derivative monomer represented by the formula (2) is an acrylic acid derivative or a methacrylic acid derivative having a substituent containing an alkyl group having 1 to 12 carbon atoms
  • the acrylamide derivative monomer represented by the formula (3) is an acrylamide derivative or a methacrylamide derivative having a substituent containing an alkyl group having 1 to 12 carbon atoms

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Abstract

Le problème à résoudre par la présente invention est de proposer une composition qui ne dégrade pas la résistance à l'eau d'une poudre hydrophobe tout en prenant la forme d'un type de poudre dans l'huile dans l'eau. Une composition de poudre dans l'huile dans l'eau caractérisée en ce qu'elle est pourvue d'une poudre hydrophobe, une phase huileuse dans laquelle la poudre hydrophobe est dispersée, et une phase aqueuse dans laquelle la phase huileuse est dispersée, un microgel de type noyau-couronne partiellement pourvu de groupes hydrophiles sur la surface de microparticules de gel hydrophobe étant utilisées en tant que dispersant pour disperser la phase huileuse dans la phase aqueuse.
PCT/JP2016/078802 2015-09-30 2016-09-29 Composition de poudre dans l'huile dans l'eau Ceased WO2017057563A1 (fr)

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WO2018180179A1 (fr) * 2017-03-29 2018-10-04 株式会社 資生堂 Produit cosmétique de type huile dans l'eau
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JP2021075488A (ja) * 2019-11-08 2021-05-20 株式会社 資生堂 水中油型組成物
US20220151884A1 (en) * 2019-03-04 2022-05-19 Shiseido Company, Ltd. Cosmetic emulsion for self-tanning
WO2023105363A1 (fr) 2021-12-09 2023-06-15 Shiseido Company, Ltd. Composition cosmétique
CN116322629A (zh) * 2020-10-21 2023-06-23 株式会社资生堂 油包水型组合物

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KR102221666B1 (ko) * 2018-07-31 2021-03-02 주식회사 엘지생활건강 공융 혼합물을 포함하는 화장료 조성물
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