JPWO2017057563A1 - Oil-in-water powder-type composition - Google Patents

Abstract

The problem to be solved by the present invention is to provide a composition that does not impair the water resistance of a hydrophobic powder while taking the form of an oil-in-water powder type. Hydrophobic powder, an oil phase in which the hydrophobic powder is dispersed, and an aqueous phase in which the oil phase is dispersed, and as a dispersant for dispersing the oil phase in the aqueous phase, A powder-in-oil-in-water composition comprising a core-corona microgel partially provided with a hydrophilic group.

Description

  The present invention relates to a powder-in-oil-in-water composition in which oil droplets in which a 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.

In particular, in the cosmetics field, increasing the water resistance of the powder applied on the skin is a conventional means for increasing so-called makeup retention. 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.

Japanese Patent No. 2656226 JP-T-2001-518111 JP 2007-332037 A JP 2006-36763 A JP 2008-291026 A Japanese Patent Laid-Open No. 11-158030 Special table 2009-501256 Japanese Patent No. 5207424 Japanese Patent No. 45777721 JP 2006-161026 A JP 2006-161027 A

B. Binks et. al, Advances in Colloid and Interface Science, 100-102 (2003). Mukul M, Sharma et. al, Journal of Colloid and Interface Science, 157, 244-253 (1993). J. et al. Agric. Food Chem. 59, 2636-2645 (2011). J. Colloid Interface Sci. , 274, 49 (2004).

  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.

As a result of studies conducted by the present inventors in order to solve the above-mentioned problems, the use of a core-corona type microgel as a dispersant makes the oil-in-water powder-type composition highly stable, and the composition. As a result, 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.
That is, an oil-in-water powder-type composition according to the present invention 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 by using a core-corona type microgel partially provided with a hydrophilic group on the surface of hydrophobic gel fine particles.
Further, in the composition, as the core-corona type microgel, a non-crosslinked (acrylates / methoxymethacrylate methacrylate) crosspolymer and / or a specific acrylamide derivative and an acrylate derivative are subjected to radical polymerization under specific conditions without crosslinking. It is preferable to use 0.5 to 10% by mass of a crosslinked acrylamide polymer.
Moreover, when using a nonionic surfactant in the said composition, it is suitable to set it as 0.5 mass% or less in a composition.
Note that “dispersion” or “dispersing agent” in the present specification is a concept including “emulsification” or “emulsifier”, respectively.
The core-corona type microgel characteristic in 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). However, this core-corona type microgel is new in that it has a 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.

  In the present invention, since 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 increased. It will be possible to demonstrate.

Hereinafter, embodiments of the present invention will be described in detail.
[Hydrophobic powder]
The hydrophobic powder used in the present invention is not particularly limited as long as the surface of the powder has hydrophobicity. For example, the powder itself such as silicone resin powder and fluororesin powder is used. In addition to those having hydrophobic properties, 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. In addition, the average particle diameter of hydrophobic powder needs to be smaller than the emulsified particles that are the oil phase of the present invention. In particular, when powder is used as an ultraviolet scattering agent, it is preferable that the average particle size after crushing with a wet disperser is 100 nm or less. Examples of 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.

  Further, among these 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. However, in the powder-in-oil-in-water composition according to the present invention, 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 powder-in-oil-in-water composition of the present invention is preferably 0.1 to 20% by mass with respect 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 of the oil phase component 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.

  Examples of the hydrocarbon oil include isododecane, isohexadecane, isoparaffin, liquid paraffin, ozokerite, squalane, pristane, paraffin, ceresin, squalene, petrolatum, microcrystalline wax, and the like.

  Examples of the higher fatty acid 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 and the like.

  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, diisostearyl malate, di-2-heptyl unde Glyceryl acid, glyceryl diisostearate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexanoate, glycerin tri-2-ethylhexanoate, glyceryl trioctanoate, tri Glyceryl isopalmitate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate-2-ethylhexyl palmitate, glyceryl trimyristate, glyceride tri-2-heptylundecanoate, castor oil fatty acid methyl ester, oleyl oleate, Acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, azide Di-2-heptyl undecylate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebacate, succinic acid 2 -Ethylhexyl, triethyl citrate and the like.

  Examples of the silicone oil include chain polysiloxanes (for example, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.), cyclic polysiloxanes (for example, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexane). Silicone resins, silicone rubber, various modified polysiloxanes (amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane, etc.), acrylic silicone And the like.

  Examples of liquid oils 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.

  Examples of the solid fat 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.

  Examples of waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibota wax, whale wax, montan wax, nuka wax, lanolin, kapok wax, lanolin acetate, liquid lanolin, sugarcane wax, lanolin fatty acid isopropyl, hexyl laurate, Examples include reduced lanolin, jojoba wax, hard lanolin, shellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether, and the like.

  Examples of the fragrances 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.

  Specific examples of the fragrance 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, damacenone, decalactone, terpinyl acetate, terpineol, tonalid, tonalide, tripral, nerol, bacdanol, vanillin, hydroxycitronellal, phenylethyl acetate, phenylethyl alcohol, hexyl salicylate, betiberyl acetate, hedion, Heliotropin, helional, belt fix, benzyl acetate, benzyl salicylate, benzyl benzoate, pentalid, pentalide, bornyl acetate, myol, musk ketone, methyl anthranilate, methyl dihydrojasmonate, yarayara, lime oxide, linalyl acetate, linalool Limonene, Lilar, Lilianar, Rose oxide, Rosinol, Angeli Oil, anise oil, alumose oil, basil oil, bay oil, bergamot oil, columnus oil, camphor oil, cananga oil, cardamom oil, cassia oil, cedarwood oil, celery oil, chamomile oil, cinnamon oil, clove oil, coriander oil , Cumin oil, dill oil, elemi oil, estragon oil, eucalyptus oil, fennel oil, fenugreek oil, galvanum oil, geranium oil, ginger oil, grapefruit oil, gayakwood oil, hiba oil, hinoki oil, juniper berry oil, lavandin oil, Lavender oil, lemon oil, lime oil, mandarin oil, ziram oil, momiza oil, peppermint o Ile, Spearmint oil, Mill oil, Miltor oil, Nutmeg oil, Oak moss oil, Olivenum oil, Opoponax oil, Orange oil, Parsley oil, Patchouli oil, Pepper oil, Perilla oil, Petit glen oil, Neroli oil, Orange flower oil, Pimento oil, Allspice oil, pine oil, rose oil, rosemary oil, clari sage oil, sage oil, sandalwood oil, stylax oil, tage oil, thyme oil, valerian oil, vetiver oil, violet leaf oil, winter green oil, Wormwood oil, Ylang Ylang oil, Yuzu oil, Cassie absolute, Geneva absolute, Hyacinthua Soryuto, in mol Tel absolute, jasmine absolute, Jonquil Absolute, Narcissus absolute, rose absolute, violet leaf absolute, Ben benzoin, and the like.

In emulsified compositions obtained with conventional surfactants, the physical properties of the surfactant and the oil content greatly affect the emulsifying properties, and when changing the oil phase component, the type of surfactant is also changed. A response was necessary. However, since 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.

  Examples of 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.

  Examples of the lower alcohol include ethanol, propanol, isopropanol, isobutyl alcohol, t-butyl alcohol and the like.

  Examples of the polyhydric alcohol 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, octylene glycol, etc.), trihydric alcohol (eg, glycerin, trimethylolpropane, etc.), tetrahydric alcohol (eg, diglycerin, 1,2, , 6-hexanetriol, etc.), pentahydric alcohol (eg, xylitol, triglycerin, etc.), hexavalent alcohol (eg, sorbitol, mannitol, etc.), polyhydric alcohol polymer (eg, diethylene glycol, Propylene glycol-triethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin-triglycerin, tetraglycerin, polyglycerin, etc.), divalent alcohol alkyl ethers (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol) Monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, ethylene glycol mono 2-methylhexyl ether, ethylene glycol isoamyl ether, ethylene glycol benzyl ether, ethylene glycol isopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol Djibouti Ethers), dihydric alcohol alkyl ethers (for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl ether, diethylene glycol methyl ethyl ether triethylene glycol monomethyl ether triethylene glycol monoethyl) Ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol isopropyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol Butyl ether), dihydric alcohol ether esters (for example, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diazebate, ethylene glycol disuccine) , Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monophenyl ether acetate, etc.), glycerin monoalkyl ether (example) Xyl alcohol, ceralkyl alcohol, batyl alcohol, etc.), sugar alcohol (eg, maltotriose, mannitol, sucrose, erythritol, glucose, fructose, amylolytic sugar, maltose, amylolytic sugar reduction) Alcohol, etc.), glycolide, tetrahydrofurfuryl alcohol, POE-tetrahydrofurfuryl alcohol, POP-butyl ether, POP / POE-butyl ether tripolyoxypropylene glycerin ether, POP-glycerin ether, POP-glycerin ether phosphate, POP. POE-pentane erythritol ether, polyglycerol, etc. are mentioned.

  Examples of monosaccharides include tricarbon sugars (for example, D-glyceryl aldehyde, dihydroxyacetone, etc.), tetracarbon sugars (for example, D-erythrose, D-erythrose, D-toreose, erythritol, etc.), Pentose sugars (for example, L-arabinose, D-xylosose, L-lyxose, D-arabinose, D-ribose, D-ribose, D-xylulose, L- Xylose, etc.), hexose (e.g., D-glucose, D-talose, D-busicoose, D-galactose, D-fructose, L-galactose, L- Mannose, D-tagatose, etc.), heptosaccharide (eg, aldoheptose, heproose, etc.), octose sugar (eg, octulose, etc.), deoxy sugar (eg, 2-deoxy-D Ribose, 6-deoxy-L-galactose, 6-deoxy-L Mannose, etc.), amino sugars (eg, D-glucosamine, D-galactosamine, sialic acid, aminouronic acid, muramic acid, etc.), uronic acids (eg, D-glucuronic acid, D-mannuronic acid, L-guluronic acid, D-galacturonic acid, L-iduronic acid and the like).

  Examples of the oligosaccharides include sucrose, gnocyanose, umbelliferose, lactose, planteose, isoliquinoses, α, α-trehalose, raffinose, lycnose, umbilicin, stachyose verbusose and the like.

  Examples of the polysaccharide 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, succinoglucan, etc. Is mentioned.

  Examples of other polyols include polyoxyethylene methyl glucoside (Glucam E-10) and polyoxypropylene methyl glucoside (Glucam P-10).

  Examples of thickeners 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.

  Examples of 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.

  Examples of 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.

  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.

  Examples of the humectant 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.

  Examples of the sequestering agent include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, trisodium edetate, and tetrasodium edetate. Sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, trisodium ethylenediaminehydroxyethyl triacetate and the like.

  Examples of amino acids include neutral amino acids (eg, threonine, cysteine, etc.), basic amino acids (eg, hydroxylysine, etc.), and the like. Examples of amino acid derivatives include acyl sarcosine sodium (lauroyl sarcosine sodium), acyl glutamate, acyl β-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.

[Core-corona microgel]
In the present invention, as the core-corona type microgel, both a crosslinked type and a non-crosslinked type can be used.
As particularly suitable 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 / Methoxy methacrylate 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.

  As the 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) available from NOF Corporation can be used.

The molecular weight (that is, the value of n) of the polyethylene oxide portion needs to be n = 8 to 200.
Examples of such a macromonomer include NOF Blemmer (registered trademark) PME-400, Blemmer (registered trademark) PME-1000, Blemmer (registered trademark) PME-4000, and the like.

（１）
Ｒ_１は炭素数１〜３のアルキル基であり、ｎは８〜２００の数である。ＸはＨまたはＣＨ_３である。

(1)
R ₁ is an alkyl group having 1 to 3 carbon atoms, and n is a number from 8 to 200. X is H or CH ₃ .

  As the hydrophobic monomer represented by the formula (2), for example, a commercially available product commercially available from Aldrich or Tokyo Kasei can be used.

（２）
Ｒ_２は炭素数１〜３のアルキル基である。
Ｒ_３は炭素数１〜１２のアルキル基であって、炭素数１〜８のアルキル基であることがより好ましい。

(2)
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.

Examples of the hydrophobic monomer 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. In particular, it is preferable to use methyl methacrylate, butyl methacrylate, or octyl methacrylate.
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. Specifically, it is preferable to use ethylene glycol dimethacrylate (hereinafter sometimes abbreviated as EGDMA) marketed by Aldrich, Blemmer (registered trademark) PDE-50 marketed by NOF Corporation, or the like.

（３）
Ｒ_４とＲ_５はそれぞれ独立に炭素数１〜３のアルキル基を表し、ｍは０〜２の数である。

(3)
R ₄ and R ₅ each independently represent an alkyl group having 1 to 3 carbon atoms, and m is a number from 0 to 2.

The core-corona type 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 charging amount of the crosslinkable monomer is 0.1 to 1.5% by mass with respect to the charging amount of the hydrophobic monomer.
(C) 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.
(D) When the polymerization solvent is a water-organic solvent mixture and a polyol is used as the organic solvent, one or more selected from dipropylene glycol, 1,3-butylene glycol, and isoprene glycol are used. There is.
(E) The solvent composition of the mixed solvent of water and organic solvent is water: organic solvent = 90 to 10:10 to 90 at a mass ratio of 20 ° C.

  In the present invention, “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 relative to the amount of the hydrophobic monomer charged depending on the condition (B). Must.

(Condition (A))
Polymerization is possible in the charged molar amount of the polyethylene oxide macromonomer and the hydrophobic monomer in the range of polyethylene oxide macromonomer: hydrophobic monomer = 1: 10 to 1: 250 (molar ratio). The charged molar amount is preferably 1:10 to 1: 200, and more preferably 1:25 to 1: 100.
When the molar amount of the hydrophobic monomer is 10 times or less with respect to the molar amount of the polyethylene oxide macromonomer, the polymer to be polymerized becomes water-soluble and no core-corona polymer microgel is formed. In addition, when the molar amount of the hydrophobic monomer exceeds 250 times the molar amount of the polyethylene oxide macromonomer, the dispersion stabilization by the polyethylene oxide macromonomer becomes incomplete, and the hydrophobic polymer by the insoluble hydrophobic monomer aggregates and precipitates. .

(Condition (B))
By copolymerizing the crosslinkable monomer, it is possible to polymerize the microgel in which the hydrophobic polymer in the core portion is crosslinked.
When 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. On the other hand, when 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 charge amount of the crosslinkable monomer is preferably 0.2 to 1.0, more preferably 0.2 to 0.8, and most preferably 0.2 to 0.5 mass%.

(Condition (C))
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.

(Condition (D))
The polymerization solvent needs to be a mixed solvent of water-organic solvent. As the organic solvent, ethanol, propanol, butanol, polyol, and the like can be used. When 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.
It is possible to manufacture industrially, that is, when considering using the polymerization solution as a raw material as it is without requiring a purification step such as dialysis, 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.

(Condition (E))
The solvent composition of the mixed solvent of water and organic solvent that is a polymerization solvent needs to be water: organic solvent = 90 to 10:10 to 90 at a mass ratio of 20 ° C. The solvent composition of the mixed solvent of water-organic solvent is preferably water: organic solvent = 90 to 10:10 to 90 (volume ratio at 20 ° C.), and water: organic solvent = 80 to 20:20 to 80 ( More preferably, the volume ratio is 20 ° C.
As the polymerization solvent, it is necessary to add an organic solvent in order to uniformly dissolve the hydrophobic monomer. The mixing ratio of the organic solvent is 10 to 90 volume ratio. 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. On the other hand, when 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, which makes it easy to make cosmetics that are not irritating to sensitive skin users. Can get to.

  As the 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.

2. Non-crosslinked core-corona microgel [acrylamide core corona]
The 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は炭素数１〜３のアルキル基であり、ｎ（ポリエチレンオキサイド部分の分子量）は８〜２００の数である。ＸはＨまたはＣＨ_３である。

R ₁ is an alkyl group having 1 to 3 carbon atoms, and n (molecular weight of the polyethylene oxide moiety) 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. For example, a commercial product commercially available from Aldrich or a commercial product such as Bremer (registered trademark) marketed by NOF Corporation may be used. As an example, PME-400, PME-1000, and PME-4000 which are methoxypolyethylene glycol monometalates (n values in formula (1) are n = 9, n = 23, n = 90, respectively, NOF Corporation) May be used.

Ｒ_２は炭素数１〜３のアルキル基を表し、Ｒ_３は炭素数１〜１２のアルキル基を含む置換基を表す。

R ₂ represents an alkyl group having 1 to ₃ carbon atoms, and 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. For example, 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. Of these, methyl methacrylate (also known as methyl methacrylate), butyl methacrylate (also known as butyl methacrylate), and 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はＨまたは炭素数１〜３のアルキル基を表し、Ｒ_５及びＲ_６はＨまたは炭素数１〜１２のアルキル基を含む置換基を表す。

R ₄ represents H or an alkyl group having 1 to 3 carbon atoms, and 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. For example, t-butylacrylamide, N, N-dimethylacrylamide, N- [3- (dimethylamino) propyl] acrylamide, t-butylmethacrylamide, octylacrylamide, octylmethacrylamide, octadecylacrylamide and the like can be suitably used. . Of these, 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 is 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.
(B) 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,
(C) 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.
(D) The solvent composition of the water-alcohol mixed solvent is water: alcohol = 90 to 10:10 to 90 at a mass ratio of 20 ° C.

Below, each condition is explained in full detail.
(Condition (A))
The charged molar amount of the polyethylene oxide macromonomer and the hydrophobic monomer (that is, the total of acrylate derivative monomer and / or acrylamide derivative monomer) is polyethylene oxide macromonomer: hydrophobic monomer = 1: 10 to 1: 250 (mol) Ratio). The charged molar amount is preferably 1:10 to 1: 200, and more preferably 1:25 to 1: 100.
When the molar amount of the hydrophobic monomer relative to the molar amount of the polyethylene oxide macromonomer is less than 10 times, the polymer to be polymerized becomes water-soluble and does not form core-corona type particles. Moreover, when the molar amount of the hydrophobic monomer with respect to the molar amount of the polyethylene oxide macromonomer exceeds 250 times, 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))
Condition (B) consists of the following three conditions (B-1) to (B-3).
(B-1)
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. 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.
(B-2)
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. 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 13 or more, a preferable feeling of use may not be obtained.
(B-3)
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 necessary.

In the present invention, two types of 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.
Although not limited by this, as the most preferred combination of macromonomer and hydrophobic monomer in the present invention,
Methoxypolyethylene glycol monometalate, methacrylate, and butyl methacrylate having a repeating unit of polyethylene glycol groups of 8 to 90, most preferably 15.
Methoxypolyethylene glycol monometalate having a repeating unit of polyethylene glycol group 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.

(Condition (C))
The polymerization solvent needs to be a water-alcohol mixed solvent. As alcohol, what can melt | dissolve the hydrophobic monomer shown by Formula (2) and (3) is preferable. Accordingly, one or more selected from ethanol, dipropylene glycol, 1,3-butylene glycol, and isoprene glycol are preferable.

(Condition (D))
The solvent composition of the water-alcohol mixed solvent as the polymerization solvent is preferably water: alcohol = 90 to 10:10 to 90 at a mass ratio of 20 ° C., more preferably water: alcohol = 80 to 20:20. ~ 80. When 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. In addition, when 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.
In addition, all the conventional microgels made of synthetic polymers are those using a polymer electrolyte such as polyacrylic acid, and have no acid resistance or salt resistance in water dispersibility. However, when considering application as a compounding ingredient of pharmaceuticals and cosmetics, acid resistance and salt resistance are very important performances in adaptation under physiological conditions. 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 the 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 substantially 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 type microgel of the present invention in the cosmetic is preferably 0.01 to 10% by mass (pure content, hereinafter simply indicated by%) 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 a core-corona type microgel emulsifier is adsorbed onto 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.
The powder-in-oil-in-water composition of the present invention is prepared by mixing and dispersing a core-corona type microgel in water or an aqueous phase component, and adding an oil phase component and other components in which hydrophobic powder is dispersed by a conventional method. It is produced by emulsifying by applying stirring and shearing force.

  The blending amounts of the oil phase component and the water phase component blended in the powder-in-oil-in-water composition of the present invention are 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.).

[Other ingredients]
The 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.

Examples of the water-soluble ultraviolet absorber 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, 3- (4′-methylbenzylidene) -d, l-camphor, 3-benzylidene-d, l-camphor , Urocanic acid, urocanic acid ethyl ester and the like.
Examples of the oil-soluble ultraviolet absorber 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 ultraviolet absorbers such as N, N-dimethyl PABA butyl ester; Anthranilic acid ultraviolet absorbers such as homomenthyl-N-acetylanthranilate; Amyl salicylate, menthyl salicylate, homomentyl salicylate, octyl salicylate, phenyl salicylate Salicylic acid-based UV absorbers such as salicylate and p-isopropanolphenyl salicylate; octylcinnamate, ethyl-4-isopropylcinnamate, methyl-2,5-diisopropylcin Mate, ethyl-2,4-diisopropylcinnamate, methyl-2,4-diisopropylcinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate, octyl-p- Methoxycinnamate, 2-ethylhexyl-p-methoxycinnamate, 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β-phenylcinnamate, 2-ethylhexyl-α -Cyano-β-phenylcinnamate, glyceryl mono-2-ethylhexanoyl-diparamethoxycinnamate, 3-methyl-4- [methylbis (trimethylsiloxy) silyl] 3,4,5-trimethoxycinnamate Cinnamic acid ultraviolet rays such as butyl Absorbent; 2-phenyl-5-methylbenzoxazole, 2,2′-hydroxy-5-methylphenylbenzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- ( 2'-hydroxy-5'-methylphenylbenzotriazole, dibenzalazine, dianisoylmethane, 4-methoxy-4'-tert-butyldibenzoylmethane, 5- (3,3-dimethyl-2-norbornylidene) -3-pentane -2-one, octocrylene and the like.

  Examples of the powder component include inorganic powders (for example, talc, kaolin, mica, sericite (sericite), muscovite, phlogopite, synthetic mica, saucite, biotite, permiculite, magnesium carbonate, calcium carbonate, silicic acid. Aluminum, barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate (baked gypsum), calcium phosphate, fluorine apatite, hydroxyapatite, ceramic powder , Metal soap (eg, zinc myristate, calcium palmitate, aluminum stearate), boron nitride, etc.), organic powder (eg, polyamide resin powder (nylon powder), polyethylene powder, polymethyl methacrylate powder, Styrene powder, copolymer resin powder of styrene and acrylic acid, benzoguanamine resin powder, polytetrafluoroethylene powder, cellulose powder, etc.), inorganic white pigment (eg, titanium dioxide, zinc oxide, etc.), inorganic red pigment (eg, , Iron oxide (Bengara), iron titanate, etc.), inorganic brown pigments (eg, γ-iron oxide, etc.), inorganic yellow pigments (eg, yellow iron oxide, loess, etc.), inorganic black pigments (eg, black) Iron oxide, low-order titanium oxide, etc.), inorganic purple pigments (eg, mango violet, cobalt violet, etc.), inorganic green pigments (eg, chromium oxide, chromium hydroxide, cobalt titanate, etc.), inorganic blue pigments (eg, For example, ultramarine blue, bitumen, etc.), pearl pigments (eg titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide coated tar) , Colored titanium oxide coated mica, bismuth oxychloride, fish scale foil, etc.), metal powder pigments (eg, aluminum powder, copper powder, etc.), organic pigments such as zirconium, barium or aluminum lake (eg, red 201, Red 202, Red 204, Red 205, Red 220, Red 226, Red 228, Red 405, Orange 203, Orange 204, Yellow 205, Yellow 401, Blue 404, etc. 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 etc.), natural pigments (eg chlorophyll, β-carotene etc.) and the like.

  Examples of the organic amine include monoethanolamine, diethanolamine, triethanolamine, morpholine, tetrakis (2-hydroxypropyl) ethylenediamine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, and 2-amino. -2-methyl-1-propanol and the like.

  Examples of the polymer emulsion include an acrylic resin emulsion, a polyethyl acrylate emulsion, an acrylic resin liquid, a polyacryl alkyl ester emulsion, a polyvinyl acetate resin emulsion, and a natural rubber latex.

  Examples of vitamins include vitamins A, B1, B2, B6, C, E and derivatives thereof, pantothenic acid and derivatives thereof, biotin and the like.

Examples of the antioxidant include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid esters and the like.
Examples of the antioxidant assistant include phosphoric acid, citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, fumaric acid, kephalin, hexametaphosphate, phytic acid, and ethylenediaminetetraacetic acid.

  Other 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, cholesterol derivative, etc.), blood circulation promoter (eg, Nyl acid wallenyl amide, nicotinic acid benzyl ester, nicotinic acid β-butoxyethyl ester, capsaicin, gingerone, cantalis tincture, ictamol, tannic acid, α-borneol, nicotinic acid tocopherol, inositol hexanicotinate, cyclandrate, cinnarizine, trazoline Acetylcholine, verapamil, cephalanthin, γ-oryzanol, etc.), antiseborrheic agents (eg, sulfur, thianthol, etc.), anti-inflammatory agents (eg, tranexamic acid, thiotaurine, hypotaurine, etc.).

  Further, the 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. For the purpose of improvement, 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.
Specifically, for example, an imidazoline-based amphoteric surfactant (for example, 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide) 1-carboxyethyloxy disodium salt, etc.); betaine surfactants (for example, 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkylbetaine, amide betaine, sulfone) Betaine) and the like.

  Examples of the cationic surfactant include quaternary ammonium salts such as cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, behenyldimethylhydroxyethylammonium chloride, stearyldimethylbenzylammonium chloride, and cetyltriethylammonium methylsulfate. Is mentioned. Also, 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, and the like.

Examples of anionic surfactants include fatty acid soaps, N-acyl glutamates, carboxylate types such as alkyl ether acetic acids, sulfonic acid types such as α-olefin sulfonates, alkane sulfonates, alkylbenzene sulfonic acids, and higher alcohol sulfates. 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.
Specifically, for example, fatty acid soap (for example, sodium laurate, sodium palmitate, etc.), higher alkyl sulfate ester salt (for example, sodium lauryl sulfate, potassium lauryl sulfate, etc.), alkyl ether sulfate ester salt (for example, 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-methyl taurate, coconut oil fatty acid) Methyl tauride sodium, lauryl methyl tauride sodium, etc.), phosphate ester salts (POE-oleyl ether sodium phosphate, POE-stearyl ether phosphate, etc.), sulfosuccinate (eg, di-2-ethyl Sodium xylsulfosuccinate, monolauroyl monoethanolamide polyoxyethylene sodium sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate, etc.), alkyl benzene sulfonates (eg, linear dodecyl benzene sulfonate sodium, linear dodecyl benzene sulfonate triethanolamine, linear Dodecylbenzene sulfonic acid, etc.), higher fatty acid ester sulfate ester salts (for example, hydrogenated coconut oil fatty acid sodium glycerol sulfate, etc.), N-acyl glutamate (for example, monosodium N-lauroyl glutamate, disodium N-stearoyl glutamate, N- Myristoyl-L-monoglutamate monosodium, etc.), sulfated oil (eg funnel oil etc.), POE-alkyl ether cal Acid, POE-alkyl allyl ether carboxylate, α-olefin sulfonate, higher fatty acid ester sulfonate, secondary alcohol sulfate, higher fatty acid alkylolamide sulfate, lauroyl monoethanolamide sodium succinate, N-palmitoyl aspartate ditriethanolamine, sodium caseinate and the like.

  The nonionic surfactant is a surfactant that is not ionized in an aqueous solution and has no electric charge. As the hydrophobic group, a type using alkyl and a type using dimethyl silicone are known. Specifically, as 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.

  Specifically, as the lipophilic nonionic surfactant, for example, 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, α, α'-oleic acid pyroglutamate glycerin, monostearate glycerin malate, etc.), propylene glycol fatty acid ester (For example, propylene glycol monostearate), hydrogenated castor oil derivative, glycerin alkyl ether and the like.

  Examples of the hydrophilic nonionic surfactant include POE-sorbitan fatty acid esters (for example, POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, POE-sorbitan tetraoleate). POE sorbite fatty acid esters (for example, POE-sorbite monolaurate, POE-sorbite monooleate, POE-sorbite pentaoleate, POE-sorbite monostearate, etc.), POE-glycerin fatty acid esters (for example, POE- Glycerol monostearate, POE-glycerol monoisostearate, POE-monooleate such as POE-glycerol triisostearate, etc.), POE-fatty acid esters (for example, POE-distearate, P E-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.), pluronic types (for example, pluronic, etc.), POE • POP-alkyl ethers (for example, POE • POP-cetyl ether, POE • POP-2-decyltetradecyl ether, POE • POP-monobutyl ether, POE / POP-hydrogenated lanolin, POE / POP-glycerin ether, etc.), tetra-POE / tetra-POP-ethylenediamine condensates (eg, Tetronic, etc.), POE-castor oil hardened castor oil derivatives For example, POE-castor oil, POE-hardened castor oil, POE-hardened castor oil monoisostearate, POE-hardened castor oil triisostearate, POE-hardened castor oil monopyroglutamic acid monoisostearic acid diester, POE-hardened castor Oil maleic acid etc.), POE-beeswax lanolin derivatives (eg POE-sorbite beeswax etc.), alkanolamides (eg coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide etc.), POE-propylene glycol fatty acid Examples include esters, POE-alkylamines, POE-fatty acid amides, sucrose fatty acid esters, alkylethoxydimethylamine oxide-trioleyl phosphoric acid, and the like.

The use of the 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.

First, 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.

なお、各試験例の製造方法は以下の通りである。
＜製造工程(1-1、2、3、4)＞
水相 成分１，２，３，４，５，７，９，３０、３３，３４，３５を混合
油相Ａ 成分１４，１５，１６，１７の液状油分に成分１１，１２，１３、２１，２２，２３，２４の固形油分を溶解
油相Ｂ 成分１８，１９，２０に成分２７を分散
乳化 水相に油相Ａ、Ｂを混合
＜製造工程(1-5)＞
油相 成分１０，１４，１７，１８，１９，２５，２６を混合し、まず成分６、その後に２８、３１，３２を分散する。
水相 成分１に３３を混合し、よく分散させ、さらに成分２，４を混合する
乳化 油相に水相を混合
＜製造工程(1-6)＞
水相 成分１，２，３，４，５、８，３０、３３，３４，３５を混合
油相Ａ 成分１４，１５，１６，１７の液状油分に成分１１，１２，１３、２１，２２，２３，２４の固形油分を溶解
油相Ｂ 成分１８，１９，２０に成分２７を分散
乳化 水相に、油相Ｂ，Ａの順番で混合

In addition, the manufacturing method of each test example is as follows.
<Manufacturing process (1-1, 2, 3, 4)>
Aqueous components 1, 2, 3, 4, 5, 7, 9, 30, 33, 34, and 35 are mixed into the liquid oil of mixed oil phase A components 14, 15, 16, and 17, and components 11, 12, 13, 21, Solid oil of 22, 23, 24 is dissolved oil phase B. Component 27 is dispersed and emulsified in components 18, 19, and 20. Oil phases A and B are mixed in water phase. <Production process (1-5)>
Oil phase Components 10, 14, 17, 18, 19, 25, and 26 are mixed, and component 6 is first dispersed, and then 28, 31, and 32 are dispersed.
Aqueous phase Mix 33 with component 1 and disperse well, then mix components 2 and 4. Mix the aqueous phase with the oil phase <Production process (1-6)>
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

As apparent from Table 1, when a powder-in-oil-in-water (POW) sunscreen cosmetic containing hydrophobic powder is prepared by core-corona emulsification (1-1), the emulsion stability and use Good evaluation was obtained for both feel and water resistance.
On the other hand, although a POW sunscreen cosmetic can be prepared even when a nonionic surfactant is used (1-2, 1-3), a significant decrease in water resistance was observed in both cases.
Moreover, even if it is a core-corona emulsified sunscreen cosmetic, in the case of the O / W type (1-4) from which the hydrophobic powder is removed, the water resistance is not exhibited.
In addition, when a normal water-in-oil sunscreen cosmetic is prepared (1-5), emulsification 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 considered to be 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 forming vesicles, which is one of the particles used for three-phase emulsification (1-6), but the hydrophobic powder jumped out of the inner phase and aggregated. Therefore, it was difficult to prepare a stable emulsion composition.
Based on the above results, 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.

なお、製造方法は、試験例１−１に準じた。
表２に示す結果より、コア−コロナ型ミクロゲルは、疎水性粉体を含む油相の配合量にもよるが、組成物中０．５質量％以上(純分)で優れた安定性を示す。なお、常識的な範囲で配合量を増量した場合にも、安定性、使用感、耐水性等に悪影響を及ぼすことはほとんどなく、分散剤として２質量％程度までが好適であるが、１０質量％程度の配合も可能である。
さらに本発明者らは非イオン性界面活性剤の添加について検討を行った。結果を表３に示す。

In addition, the manufacturing method was based on Test Example 1-1.
From the results shown in Table 2, the core-corona-type microgel exhibits excellent stability at 0.5% by mass or more (pure component) in the composition, although it depends on the blending amount of the oil phase containing the hydrophobic powder. . In addition, even when the blending amount is increased within a common sense range, there is almost no adverse effect on stability, feeling of use, water resistance, etc., and it is preferable that the dispersant is up to about 2% by mass, but 10% by mass. % Blending is also possible.
Furthermore, the present inventors examined addition of a nonionic surfactant. The results are shown in Table 3.

なお、製造方法は、試験例１−１に準じた。
非イオン性界面活性剤は、コア−コロナ乳化においても適度の配合により乳化安定性の向上が図られることがあるが、その配合量が０．８質量％以上となる安定性には何ら問題ないものの、耐水性の顕著な低下がみられる。このため、非イオン性界面活性剤は配合が必須ではないが、配合する場合にも０．５質量％以下とすることが好ましい。

［非架橋型コア−コロナ型ミクロ粒子分散液の製造例］
表４に記載したマクロモノマー及び疎水性モノマーを、表４及び表５に記載した重合条件で、下記製造方法（手法１）に従ってラジカル重合した。得られたコポリマー分散液の外観を目視によって評価し、コポリマーの粒子径及び分散度を手法２に従って評価した。結果を表３に示す。

In addition, the manufacturing method was based on Test Example 1-1.
The nonionic surfactant may improve the emulsion stability by appropriate blending even in the core-corona emulsification, but there is no problem with the stability where 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.

[Production Example of Non-crosslinked Core-Corona Type Microparticle Dispersion]
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 the obtained copolymer dispersion was visually evaluated, and the particle size and degree of dispersion of the copolymer were evaluated according to Method 2. The results are shown in Table 3.

<Method 1: Core-corona type microparticle production method>
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. 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 polymer solution was returned to room temperature to obtain a core-corona type microparticle dispersion.

  In addition, as a polyethylene oxide macromonomer, BLEMMER PME-4000 (manufactured by NOF Corporation) was used. Examples of the hydrophobic monomer include methyl methacrylate (MMA), butyl methacrylate (n-BMA), t-butyl acrylamide (t-BAA), N, N-dimethylacrylamide (DMAA), N- [3- (dimethylamino). ) Propyl] acrylamide (DMAPA) was used.

<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. As 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.

※表４中の数値の単位はいずれもｇ（グラム）である。

* The unit of numerical values in Table 4 is g (grams).

  As shown in Table 6, 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 One or more hydrophobic monomers selected from acrylamide and N- [3- (dimethylamino) propyl] acrylamide are mixed in a water-ethanol mixed solvent (water: ethanol = 40-60: 18-82). In Production Examples 1 to 10 polymerized under the condition that the value of “Mole amount of macromonomer / Mole amount of hydrophobic monomer” was 1:50 to 100, a cloudy solution-like dispersion was obtained, The diameter and degree of dispersion could be evaluated. That is, the production | generation of the particulate polymer (core-corona type microparticle) has been confirmed. And it was shown that the core-corona type microparticles of Production Examples 1 to 10 have a particle diameter of 150 to 250 nm and a uniform particle diameter.

Therefore, one or two kinds selected from the polyethylene oxide macromonomer represented by the formula (1), the acrylate derivative monomer represented by the formula (2), and the acrylamide derivative monomer represented by the following formula (3) With the above hydrophobic monomer,
(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,
(B) 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,
(C) 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,
(D) The solvent composition of the water-alcohol mixed solvent is water: alcohol = 90 to 10:10 to 90 at a mass ratio of 20 ° C.
It was revealed that core-corona type microparticles having a uniform particle diameter can be obtained by radical polymerization in accordance with the following conditions ((A) to (D)).
Table 7 below shows a comparison between a composition using a crosslinked core corona microgel and a composition using a non-crosslinked core corona microgel.

上記表７より明らかなように、架橋型コアコロナ型ミクロゲルを用いた場合（試験例７−１）と同様、非架橋型コアコロナ型ミクロゲルを用いた場合にも、優れた乳化安定性を得ることができた。

As is clear from Table 7 above, as in the case of using the cross-linked core corona microgel (Test Example 7-1), even when the non-cross-linked core corona microgel is used, excellent emulsion stability can be obtained. did it.

Claims (4)

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,
A powder-in-oil-in-water composition comprising a core-corona type microgel having hydrophilic groups partially provided on the surface of hydrophobic gel fine particles.   2. The oil-in-water composition according to claim 1, wherein 0.5 to 10 mass% of (acrylates / methoxymethacrylate methacrylate) crosspolymer and / or non-crosslinked acrylamide polymer is used as the core-corona type microgel. Medium powder type composition.   The composition according to claim 1 or 2, wherein a nonionic surfactant is blended, and the blending amount is 0.5% by mass or less in the composition. . The composition of claim 1, wherein the core-corona microgel is
One or more kinds selected from a polyethylene oxide macromonomer represented by the following formula (1), an acrylate derivative monomer represented by the following formula (2), and an acrylamide derivative monomer represented by the following formula (3) Powder-in-oil-in-water composition comprising core-corona type microparticles made of non-crosslinked acrylamide polymer obtained by radical polymerization of a hydrophobic monomer under the following conditions (A) to (D) object;
(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,
(B) 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,
(C) 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;
(D) The solvent composition of the water-alcohol mixed solvent is water: alcohol = 90 to 10:10 to 90 at a mass ratio of 20 ° C.

R ₁ represents H or an alkyl group having 1 to 3 carbon atoms, and n is a number from 8 to 200. X represents H or CH ₃ .

R ₂ represents H or an alkyl group having 1 to ₃ carbon atoms, and R ₃ represents a substituent containing an alkyl group having 1 to 12 carbon atoms.

R ₄ represents H or an alkyl group having 1 to 3 carbon atoms, and R ₅ and R ₆ represent H or a substituent containing an alkyl group having 1 to 12 carbon atoms.