TW201717892A - Powder-oil-in-water composition - Google Patents

Abstract

An objective of this invention is to provide a composition that does not deteriorate the hydrophobic properties of a hydrophobic powder even in a powder-oil-in-water state. The powder-oil-in-water composition of the present invention contains: a hydrophobic powder, an oil phase for dispersing the hydrophobic powder, and a water phase for dispersing the oil phase, and a core-corona micro gel having hydrophilic groups partially provided on a surface of a hydrophobic gel is used as a dispersant for dispersing the oil phase into the water phase.

Description

Powder composition in water oil

The present invention relates to a powder-type composition in which oil droplets of a hydrophobic powder are dispersed and redispersed in an aqueous phase of an oil, in particular, a dispersant for dispersing oil droplets in an aqueous phase is improved.

In particular, in the field of cosmetics, the water resistance of the powder applied to the skin is improved, and it is a conventional method for improving the durability of the so-called makeup. The hydrophobic powder is usually used as a powder cosmetic or as a powder type cosmetic in which oil is dispersed as a hydrophobic powder in an oil phase, but in the case where the latter continuous phase is an oil phase, it is used on the skin. It will not be easy to get a refreshing feeling.

Therefore, there is a powder type composition in water which is obtained by dispersing oil droplets which disperse the hydrophobic powder in the water phase, and since the continuous phase is an aqueous phase, the feeling of use is good, and it is also expected to be hydrophobic. It has water resistance and is water-resistant.

However, the powdery composition of the oil in water does not have a high improvement in the feeling of use, but it does not have the problem of the water resistance originally possessed by the hydrophobic powder.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Patent No. 2656226

Patent Document 2: Special Table 2001-518111

Patent Document 3: JP-A-2007-332037

Patent Document 4: JP-A-2006-36763

Patent Document 5: JP-A-2008-291026

Patent Document 6: Japanese Patent Publication No. 11-158030

Patent Document 7: Special Table 2009-501256

Patent Document 8: Patent No. 5207244

Patent Document 9: Patent No. 4577721

Patent Document 10: JP-A-2006-161026

Patent Document 11: JP-A-2006-161027

Non-patent literature

Non-Patent Document 1: B. Binks et al. , Advances in Colloid and Interface Science, 100-102 (2003).

Non-Patent Document 2: Mukul M, Sharma et al. , Journal of Colloid and Interface Science, 157, 244-253 (1993).

Non-Patent Document 3: J. Agric. Food Chem., 59, 2636-2654 (2011).

Non-Patent Document 4: J. Colloid Interface Sci., 274, 49 (2004).

The present invention has been made in view of the foregoing prior art, and in order to solve the problems, it is possible to provide a composition which can have a water-resistant powder form in water and which does not impair the water resistance of the hydrophobic powder.

In order to solve the above problems, the inventors of the present invention conducted a review and found that by using a core-crown type microgel as a dispersing agent, the stability of the powder type composition in oil can be improved, and the composition can be coated with the composition. The hydrophobic powder on the film has high water resistance, and the present invention has been completed.

That is, the powder type composition in the oil in the present invention is characterized in that it contains a hydrophobic powder, an oil phase in which the hydrophobic powder is dispersed, and an aqueous phase in which the oil phase is dispersed, and is used. A core-crown type microgel having a hydrophilic group partially provided on the surface of the hydrophobic colloidal particles is used as a dispersing agent for dispersing the oil phase in the aqueous phase.

Further, in the above composition, as a core-crown type microgel, 0.5 to 10% by mass of (acrylate/methacrylic acid methoxy PEG) is used to crosslink the polymer and/or to make a specific acrylamide. A non-crosslinked acrylamide-based polymer obtained by radically polymerizing a derivative and an acrylate derivative without crosslinking under specific conditions is preferred.

Further, when a nonionic surfactant is used in the above composition, the composition is preferably 0.5% by mass or less.

In addition, the term "dispersion" and "dispersant" as used in the description of the present invention respectively include the concepts of "emulsification" and "emulsifier".

A core-crown type microgel characterized by the present invention can be used as a dispersing agent in a so-called Pickering emulsion (powder emulsification) (patent text) 1 to 11, non-patent documents 1 to 4). However, the core-crown microgel has high dispersion stability in a powdery composition in oil, and at the same time, when the composition is used, the water resistance of the hydrophobic powder in the coating film can be improved. New findings.

Since the dispersant of the powder type composition in the oily oil of the present invention uses a core-crown type microgel, it is possible to eliminate the use of other surfactants and to sufficiently exhibit the water resistance of the hydrophobic powder.

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 it has hydrophobicity on the surface of the powder, and examples thereof include a polyoxyxylene resin powder, a fluorine resin powder, and the like, and the powder itself. If it is hydrophobic, it can also be used on the surface of inorganic powder particles, using: methyl hydrogenated polyoxyalkylene, polydimethylene oxide, such as decyl alkane, dextrin fatty acid ester, higher fatty acid, higher alcohol, a fatty acid ester, a metal soap, an alkyl phosphate, a fluorine-containing compound, or a hydrocarbon such as a triacon or a paraffin, and is hydrophobized by a wet method, a gas phase method, a mechanochemical method, or the like using a solvent. Processor. Further, the average particle diameter of the hydrophobic powder must be smaller than that of the emulsified particles of the oil phase of the present invention. In particular, when the powder is used as a UV scattering agent, it is passed through a wet disperser powder. The average particle diameter after the crushing is preferably 100 nm or less. Examples of the hydrophobized inorganic powder particles include titanium oxide, zinc oxide, talc, mica, sericite, kaolin, titanium mica, black iron oxide, yellow iron oxide, red iron oxide, ultramarine blue, indigo, Chromium oxide, chromium hydroxide, etc.

Further, in such a hydrophobic powder, it is known that the emulsified particles are liable to undergo significant aggregation and bonding particularly in the case of co-dispensing the hydrophobized particulate titanium dioxide and the hydrophobized particulate zinc oxide, and the present invention In the oil-based powder composition, by dispersing the above microgel as a dispersing agent, the dispersion stability and emulsion stability of the powder may be remarkably improved. Therefore, in the present invention, when the hydrophobized fine particle titanium oxide and the hydrophobized fine particle zinc oxide are contained as the hydrophobic powder, they are particularly highly usable.

The amount of the hydrophobized powder in the powdery composition of the aqueous oil of the present invention is preferably from 0.1 to 20% by mass based on the total amount of the composition. When the amount is less than 0.1% by mass, the effect of blending is insufficient, and when it exceeds 20% by mass, the emulsion stability may be deteriorated.

[oil phase composition]

The oil phase component is usually used, for example, as a hydrocarbon oil such as a cosmetic or a non-pharmaceutical product, a higher fatty acid, a higher alcohol, a synthetic ester oil, a polyoxygenated oil, a liquid fat, a solid fat, a wax, a perfume, or the like.

Hydrocarbon oils such as: isododecane, isohexadecane, isoparaffin, liquid paraffin, ozokerite, triacontane, pristane, paraffin, refined ceresin, squalene, petrolatum, Microcrystalline wax, etc.

Higher fatty acids such as: lauric acid, myristic acid, brown Palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, tall oil acid, isostearic acid, linoleic acid, linoleic acid, eicosapentaenoic acid ( EPA), docosahexaenoic acid (DHA), and the like.

Higher alcohols are, for example, linear alcohols (for example: lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetearyl alcohol, etc.), branched alcohols (for example: monostearyl groups) Glycerol ether (salostol)-2-mercaptotetradecyl alcohol, sheep oleyl alcohol, cholesterol, phytosterol, hexyldodecanol, isostearyl alcohol, octyldodecanol, etc.).

Synthetic ester oils such as: octyl octanoate, decyl decanoate, cetyl octanoate, isopropyl myristate, octyl dodecanoate, isopropyl palmitate, butyl stearate, hexyl laurate , myristate myristate, decyl oleate, hexyl decyl dimethyl octanoate, cetyl lactate, myristyl lactate, lanyl acetate, isocetyl stearate, isostearic acid Isocetyl ester, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, fatty acid pentaerythritol ester, monoisostearic acid-N-alkyl glycol ester, two Neopentyl glycol citrate, tripropylene glycol trimethylacetate, diisostearyl malate, glyceryl di-2-heptyl undecanoate, glyceryl diisostearate, tri-2-ethyl Trimethylolpropyl hexanoate, trimethylolpropyl triisostearate, neopentyl glycol tetra-2-ethylhexanoate, glycerol tris-2-ethylhexanoate, glyceryl tricaprylate , triiso palmitate, trishydroxypropyl propyl triisostearate, cetyl 2-ethylhexanoate - 2-ethylhexyl palmitate, glyceryl trimyristate, three-2 -heptyl undecanoate, castor oil fatty acid Ester, oleic acid ester, glycerol acetate, 2-heptylundecyl myristate, diisobutyl adipate, N-lauryl-L-glutamic acid-2-octyldodecanate , di-2-heptylundecyl adipate, Ethyl laurate, di-2-ethylhexyl sebacate, 2-hexadecyl myristate, 2-hexadecyl palmitate, 2-hexadecyl adipate, diisopropyl sebacate , 2-ethylhexyl succinate, triethyl citrate, and the like.

Polyoxygenated oils are, for example, linear polyoxyalkylenes (for example: polydimethylsiloxane, polymethylphenyloxane, polydiphenylphosphoxane, etc.), cyclic polyoxyalkylenes (for example) : octamethylcyclotetraoxane, decamethylcyclopentaoxane, dodecamethylcyclohexaoxane, etc.), a three-dimensional network structure of polyoxynoxy resin, polyoxyxene rubber, various modifications Polyoxyalkylene oxide (amine modified polyoxyalkylene oxide, polyether modified polyoxyalkylene oxide, alkyl modified polyoxyalkylene oxide, fluorine modified polyoxyalkylene, etc.), propylene fluorenyl polyoxyl Wait.

Liquid fats such as: avocado oil, camellia oil, sea turtle oil, macadamia nut oil, corn oil, oyster sauce, olive oil, rapeseed oil, egg butter, sesame oil, almond oil, wheat germ oil, camellia oil, castor oil, flax Kernel oil, safflower seed oil, cottonseed oil, perilla oil, soybean oil, peanut oil, tea seed oil, polar oil, rice bran oil, Chinese tung oil, Japanese tung oil, jojoba oil, germ oil, triglyceride, etc.

Solid oils such as: cocoa butter, coconut oil, horse fat, hydrogenated coconut oil, palm oil, butter, sheep fat, hydrogenated butter, palm kernel oil, lard, beef bone oil, wood wax nuclear oil, hydrogenated oil, cattle Foot oil, wood wax, hydrogenated castor oil, etc.

Waxes such as: beeswax, candelilla wax, cotton wax, carnauba wax, laurel wax, white wax, cetyl wax, montan wax, rice bran wax, sheep oil, kapok wax, acetic acid sheep oil, liquid sheep oil, sugar cane Wax, wool oil fatty acid isopropyl ester, hexyl laurate, hydrogenated lanolin, jojoba wax, hard Sheep oil, shellac wax, POE sheep oleyl alcohol ether, POE sheep oleyl acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol ester, POE hydrogenated lanyl ether ether, and the like.

The flavoring agent may, for example, be a natural flavor obtained from an animal or a plant, a synthetic flavor produced by chemical synthesis, or a blending flavor thereof, and is not particularly limited. When the fragrance is blended, a cosmetic having excellent aroma persistence can be obtained.

In terms of perfume, specific examples include: acetylene alcohol, anisaldehyde, anethole, amyl acetate, amyl salicylate, allyl pentyl glycolate, allyl hexanoate, C _6-20 aldehyde, musk Ester, scorpion lactone, alkalin, ionone, iso E super essence, eugenol, Oulan thiol, Jiale musk, Calone, coumarin, geranium Oxalol, geranyl acetate, Sandalore, sandalwood, salamarin, cyclamen aldehyde, 3-hexenyl cis-acetate, cis-3-hexenol, citral, acetic acid Terpene, citronellol, eucalyptol, dihydrogeranol, jasmine lactone, cinnamyl alcohol, cinnamaldehyde, sulphate acetate, cedar acetate, cedarol, damascus, damask ketene, azlactone, Rosin acetate, rosin alcohol, duna musk, tonallide, cresol, nerol, bacdanol, vanillin, hydroxycitronellal, phenylethyl acetate, phenylethyl alcohol, Hexyl salicylate, eugenyl acetate, hedione, geranyl aldehyde, new jasmine aldehyde, methyl ketone (vertofix) Benzyl acetate, benzyl salicylate, benzyl benzoate, pentalide, borneol acetate, equivial, musk ketone, methyl benzoate, dihydrojasmonate Ester, neroli, oxidized lyme, acetal, linalool, limonene, new lilanin, lilacin, oxidized rose ketone, citronellol, angelica oil, anise oil, wormwood oil, basil oil, laurel Oil, bergamot oil, calamus oil, camphor oil, perfume tree oil, cardamom oil, cinnamon oil, cedar wood oil, celery seed oil, chamomile oil, cinnamon oil, clove oil, alfalfa seed oil, cumin oil, alfalfa oil Rose oil, eucalyptus oil, citrus oil, eucalyptus oil, anise oil, fenugreek oil, white rosin oil, geranium oil, ginger oil, grapefruit oil, guaiac oil, cedar leaf oil, Japan Tarpaulin, juniper oil, striking lavender oil, lavender oil, lemon oil, lime oil, tangerine oil, slipper orchid oil, acacia oil, peppermint oil, spearmint oil, myrrh oil, myrtle oil, cardamom Oil, eucalyptus oil, mastic oil, windproof root oil, orange oil, parsley oil, scorpio Peppermint oil, pepper oil, perilla oil, bitter orange leaf oil, neroli oil, sweet pepper oil, fragrant oil, rosin oil, rose oil, rosemary oil, happy sage oil, sage oil, white sandalwood oil, Benzoin oil, marigold oil, thyme oil, night primrose oil, yoghurt oil, vetiver oil, violet leaf oil, wintergreen oil, absinthe oil, perfume tree oil, Japanese grapefruit oil, acacia essential oil, gorse Essential oils, hyacinth essential oils, helichrysum oil, jasmine essential oil, huangxinxin oil, narcissus essential oil, rose essential oil, violet leaf essential oil, benzoin and the like.

Since the physical properties of the surfactant and the physical properties of the oil phase component have a great influence on the emulsification property in the emulsified composition obtained by the prior surfactant, the change of the corresponding oil phase component also needs to change the kind of the surfactant. However, the powder-type composition of the oil in the present invention is a Pickering emulsion emulsion using a core-crown type microgel as a dispersing agent, so that the emulsifiability/stability is less affected by the type of the oil phase component, and The blending of the oil phase components is more extensive than before.

[Water phase composition]

In terms of the water phase component, water, a water-soluble alcohol, a tackifier, and the like which are generally used in cosmetics, non-pharmaceuticals, and the like may be blended, and a moisturizer, a chelating agent, a preservative, a coloring matter, or the like may be appropriately formulated as desired.

The water contained in the powdery composition in the oil of the present invention is not particularly limited, and examples thereof include purified water, ion-exchanged water, and tap water.

Water-soluble alcohols such as: lower alcohols, polyols, polyol polymers, 2-member alcohol alkyl ethers, 2-alcohol alkyl ethers, 2-valent alcohol ether esters, glycerol monoalkyl ethers, sugar alcohols, monosaccharides , oligosaccharides, polysaccharides and their derivatives.

Lower alcohols are, for example, ethanol, propanol, isopropanol, isobutanol, tert-butanol and the like.

Polyols such as: 2-alcohols (for example: dipropylene glycol, 1,3-butanediol, ethylene glycol, propylene glycol, 1,2-butanediol, butanediol, 2,3-butanediol, pentanediol , 2-butane-1,4-diol, hexanediol, octanediol, etc.), 3-hydric alcohol (for example, glycerol, trimethylolpropane, etc.), 4-alcohol (for example: diglycerin, 1, 2) , pentaerythritol such as 6-hexanetriol, etc.), 5-alcohol (for example, xylitol, triglycerin, etc.), 6-valent alcohol (for example, sorbitol, mannitol, etc.), polyol polymer (for example: diethylene glycol, dipropylene glycol-triethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin-triglycerin, tetraglycerin, polyglycerol, etc.), 2-alcohol alkyl ethers (for example: ethylene two) Alcohol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-methylhexyl ether, B Glycol isoamyl ether, ethylene glycol benzyl ether, ethylene glycol isopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol Butyl ether, etc.), 2-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 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, etc.), 2-valent alcohol ether ester (for example: B Glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diadipate Ester, ethylene glycol disuccinate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Ester, propylene glycol monopropyl ether acetate, propylene glycol monophenyl ether acetate, etc.), glycerol monoalkyl ether (for example: xylene alcohol, squalyl alcohol, shark liver alcohol, etc.), sugar alcohol (for example: wheat) Bud trisaccharide, mannitol, sucrose , erythritol, glucose, fructose, starch-decomposing sugar, maltose, starch-decomposing sugar-reducing alcohol, etc.), glysolid, tetrahydrofuran methanol, POE-tetrahydrofuran methanol, POP-butyl ether, POP‧POE-butyl ether trimer Propylene glyceryl ether, POP-glyceryl ether, POP-glyceryl ether phosphate, POP/POE-neopentitol ether, polyglycerin, and the like.

Monosaccharides such as: trisaccharides (eg, D-glyceraldehyde, dihydroxyacetone, etc.), and four carbon sugars (eg, D-erythrose, D-erythrulose, D-threitol, erythritol, etc.) , five-carbon sugar (for example: L-arabinose, D-xylose, L-lyxose, D-arabinose, D-ribose, D-ribulose, D-xylulose, L-xylulose Etc., six-carbon sugar (eg D-glucose, D-talose, D-psicose, D-galactose, D-fructose, L-galactose, L-mannose, D-tower Glucose, etc.), seven carbon sugars (eg, heptaldose, heptose, etc.), eight carbon sugars (eg, octulose, etc.), deoxy sugars (eg, 2-deoxy-D-ribose, 6-go Oxy-L-galactose, 6-deoxy-L-mannose, etc., amino sugars (eg D-glucosamine, D-galactosamine, sialic acid, aminouronic acid, muramic acid) Etc.), uronic acid (for example: D-glucuronic acid, D-mannuronic acid, L-glucuronic acid, D-galacturonic acid, L-iduronic acid, etc.) and the like.

Oligosaccharides such as: sucrose, gentiotriose, umbelliferous, lactose, psyllium, xylose, alpha, alpha-trehalose, raffinose, chervil, umbilicin, Stachyose - mullein sugar, etc.

Polysaccharides such as: cellulose, hazelnut seed extract, starch, galactan, chondroitin sulfate, glycogen, gum arabic, acesulfate heparin-xanthine, keratan sulfate, chondroitin sulfate, sanxian gum, Guanhua bean gum, cyclodextrin, keratin sulfate, locust bean gum, amber glucoside and the like.

Other polyols are, for example, polyoxyethylene methyl glucoside (Glucam E-10), polyoxypropylene methyl glucoside (Glucam P-10) and the like.

Adhesives such as: gum arabic, carrageenan, locust gum, scutellaria gum, locust bean gum, hazelnut seed extract (榅桲), casein, dextrin, gelatin, sodium pectinate, sodium alginate, Methyl cellulose, ethyl cellulose, CMC, hydroxyethyl cellulose, hydroxypropyl cellulose, PVA, PVM, PVP, sodium polyacrylate, carboxyvinyl polymer, locust bean gum, Guanhua bean gum, tamarind Glue, dialkyldimethylammonium sulfate cellulose, Sanxian gum, aluminum magnesium niobate, bentonite, lithium bentonite, arnic acid AlMg (Veegum), LAPONITE, phthalic anhydride, and the like.

Natural water-soluble polymers such as: plant-based polymers (for example: acacia, scutellaria, galactan, Guanhua Bean Gum, locust bean gum, locust gum, carrageenan, pectin, acacia , husk seed extract (榅桲), algin (a brown algae extract), starch (rice, corn, potato, wheat), glycyrrhizic acid), microbial polymers (eg: Sanxian gum, dextran, amber An egg-based polymer (for example, collagen, casein, albumin, gelatin, etc.) or the like.

The semi-synthetic water-soluble polymer is, for example, a starch-based polymer (for example, carboxymethyl starch or methyl hydroxypropyl starch) or a cellulose-based polymer (for example, methyl cellulose, ethyl cellulose, and methyl group). Hydroxypropyl cellulose, hydroxyethyl cellulose, sodium cellulose sulfate, hydroxypropyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, crystalline cellulose, cellulose powder, etc.), high alginic acid Molecules (for example, sodium alginate, propylene glycol alginate, etc.) and the like.

The water-soluble polymer to be synthesized is, for example, an ethylene-based polymer (for example, polyvinyl alcohol, polyvinyl methyl ether, polyvinylpyrrolidone, or a carboxyvinyl polymer) or a polyoxyethylene-based polymer (for example, polyethylene glycol 20,000). 40,000, 60,000, etc.), an acrylic polymer (for example, sodium polyacrylate, polyethyl acrylate, polypropylene decylamine, etc.), polyethyleneimine, a cationic polymer or the like.

Humectants such as chondroitin sulfate, hyaluronic acid, sialic acid, carnitine, linoleic acid collagen, cholesteryl-12-hydroxystearate, sodium lactate, bile salts, DL-pyrrolidone carboxylate , short-chain soluble collagen, diglycerin (EO) PO adduct, thorn pear extract, yarrow extract, yellow hibiscus extract, and the like.

Metal ion chelating agents such as: 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium ethylenediaminetetraacetate, ethylenediaminetetraacetic acid Trisodium, tetrasodium ethylenediaminetetraacetate, sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, ethylenediaminetetraacetic acid, ethylenediamine hydroxyethyltriacetic acid Trisodium and the like.

The amino acid is, for example, a neutral amino acid (for example, threonine, cysteine, etc.), a basic amino acid (for example, a hydroxylic acid, etc.), or the like. Further, the amino acid derivative is, for example, sodium decyl sarcosinate (sodium lauryl sarcosinate), thiol glutamate, thiol-β-alanine sodium, glutathione or the like.

The pH adjuster is, for example, a buffer such as lactic acid-sodium lactate, citric acid-sodium citrate or sodium succinate-succinate.

[nuclear-crown microgel]

In the present invention, the core-crown type microgel may be either a crosslinked type or a non-crosslinked type.

The core-crown type microgel is particularly used as follows (acrylate/methacrylic methoxy PEG) crosslinked polymer [crosslinked core-crown microgel] and acrylamide amine core-crown A type of microgel [non-crosslinked core-crown microgel] is preferred.

1. Crosslinked core-crown microgel [(acrylate/methacrylic acid methoxy-PEG-90) crosslinked polymer]

The crosslinked core-crown type microgel in the present invention can be obtained by radical polymerization of a monomer represented by the following formulas (1) to (3) under specific conditions.

The polyoxyethylene macromonomer represented by the formula (1) may be, for example, a product sold by Aldrich, or a BLEMMAR sold by Nippon Oil Co., Ltd. (registered trademark) and other products.

The molecular weight of the polyoxyethylene moiety (i.e., the value of n) must be n = 8 to 200.

Such macromonomers are, for example, BLEMMAR (registered trademark) PME-400, BLEMMAR (registered trademark) PME-1000, BLEMMAR (registered trademark) PME-4000, and the like manufactured by Nippon Oil Corporation.

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 product sold by Aldrich Co., Ltd. or Tokyo Chemical Industry Co., Ltd. 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 an alkyl group having 1 to 8 carbon atoms is more preferable.

Hydrophobic monomers such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, Heptyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, methacrylic acid Hexyl ester, heptyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, and the like. In particular, it is preferred to use methyl methacrylate, butyl methacrylate or octyl methacrylate.

Such hydrophobic monomers are widely used raw materials and can be easily obtained from general industrial raw materials.

The crosslinkable monomer represented by the formula (3) can be obtained from a commercial or industrial raw material. The crosslinkable monomer is preferably hydrophobic.

The value of m is preferably 0 to 2. Specifically, ethylene glycol dimethacrylate (hereinafter sometimes abbreviated as EGDMA) sold by Aldrich Co., Ltd., BLEMMAR (registered trademark) PDE-50 sold by Nippon Oil Co., Ltd., and the like are preferably used.

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

The core-crown microgel of the present invention is obtained by subjecting the above monomers to radical polymerization under the conditions (A) to (E) below.

(A) The molar ratio in terms of the amount of added moles of the aforementioned polyethylene oxide macromonomer/the molar amount of the aforementioned hydrophobic monomer is from 1:10 to 1:250.

(B) The amount of the crosslinkable monomer added is 0.1 to 1.5% by mass based on the amount of the hydrophobic monomer added.

(C) The hydrophobic monomer represented by the formula (2) is composed of one or a mixture of two or more kinds of methacrylic acid derivatives having an alkyl group having 1 to 8 carbon atoms.

(D) The solvent to be polymerized is a mixed solvent of a water-organic solvent, and when the polyol is used as the organic solvent, one or two or more selected from the group consisting of dipropylene glycol, 1,3-butylene glycol, and isoprene glycol.

(E) The solvent composition of the water-organic solvent mixed solvent is a mass ratio of 20 ° C, which is water: organic solvent = 90:10 to 10:90.

In the present invention, the "addition amount of the crosslinkable monomer to the amount of the hydrophobic monomer added" is defined as the crosslinking density (% by mass). The crosslink density of the core-crown type microgel used in the present invention, the amount of the crosslinkable monomer to be added is 0.1 to 1.5, based on the condition of (B), relative to the amount of the hydrophobic monomer added. quality%.

(Condition (A))

The molar amount of the polyoxyethylene macromonomer and the hydrophobic monomer can be polymerized in the range of the polyoxyethylene macromonomer: hydrophobic monomer = 1:10 to 1:250 (mole ratio). The aforementioned molar amount is preferably from 1:10 to 1:200, more preferably from 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 polyoxyethylene macromonomer, the polymer to be polymerized becomes water-soluble and the core-crown polymer microgel cannot be formed. Moreover, the molar amount of the hydrophobic monomer is 250 times or more relative to the molar amount of the polyoxyethylene macromonomer. At the time, the dispersion stability by the polyethylene oxide macromonomer may be incomplete and the hydrophobic polymer of the insoluble hydrophobic monomer may aggregate and precipitate.

(Condition (B))

The microgel polymerization of the hydrophobic polymer which crosslinks the core portion by copolymerizing the crosslinkable monomer.

When the amount of the crosslinkable monomer is less than 0.1% by mass of the amount of the hydrophobic monomer added, the crosslinking density is lowered, so that the microgel disintegrates when it swells. On the other hand, when the amount is more than 1.5% by mass, aggregation occurs between the microgel particles, and thus it is impossible to polymerize into microgel particles having a small particle size distribution and being preferable. The amount of the crosslinkable monomer to be added is preferably 0.2 to 1.0% by mass, more preferably 0.2 to 0.8% by mass, and most preferably 0.2 to 0.5% by mass.

(Condition (C))

The hydrophobic monomer represented by the formula (2) must be one or a mixture of two or more kinds of methacrylic acid derivatives having an alkyl group having 1 to 8 carbon atoms. When the carbon number is 0 (the monomer having no ester bond at the end), the hydrophilicity of the monomer may be too high to be favorably emulsified and polymerized. On the other hand, when the carbon number is 9 or more, steric hindrance occurs during polymerization, and thus it is impossible to construct a favorable crosslinked structure.

(Condition (D))

The polymerization solvent must be a mixed solvent of a water-organic solvent. Organic solvents can be used: ethanol, propanol, butanol, polyols, etc., and in the use of polyols In the case of dissolving the hydrophobic monomer represented by the formula (2) and the crosslinkable monomer represented by the formula (3), it is preferred. The polyol used in the present invention must be dipropylene glycol, 1,3-butylene glycol or isoprene glycol.

In consideration of industrial production, that is, when the polymerization liquid is directly used as a raw material without a purification step such as dialysis, the solvent mixed with water is not ethanol, propanol or butanol, and it is not necessary to worry about the stimulation of the organic solvent when applied to the skin. Sex, can be widely used and blended with the polyol in the cosmetic material.

(Condition (E))

The solvent composition of the mixed solvent of the water-organic solvent of the polymerization solvent, the mass ratio of 20 ° C, is necessary with water: organic solvent = 90 to 10:10 to 90. The solvent composition of the water-organic solvent mixed solvent is preferably water: organic solvent = 90 to 10: 10 to 90 (20 ° C volume ratio), water: organic solvent = 80 to 20: 20 to 80 (20 ° C Volume ratio) is better.

The polymerization solvent must be further added with an organic solvent in order to uniformly dissolve the hydrophobic monomer. The mixing ratio of the organic solvent is from 10 to 90 by volume. When the organic solvent mixture is lower than the 10 volume ratio, the solubility of the hydrophobic monomer is extremely low, and thus it progresses to polymerization into a large clot in a monomer dropping state, and it is impossible to form a microgel. Further, when the organic solvent mixing ratio is higher than the 90 volume ratio, the emulsion of the hydrophobic monomer cannot be formed due to the hydrophobic interaction, and thus the emulsion is not subjected to emulsion polymerization, and the microgel cannot be obtained.

The core-crown type microgel of the present invention obtained by using a polyol, since the polymerization solvent is a water-polyol mixed solvent and does not contain ethanol, it is easy to obtain a makeup which is free from skin irritation to users of sensitive skin. material.

As the polymerization initiator used in the polymerization, a commercially available polymerization initiator which is usually used in water-soluble heat-radical polymerization can be used. This polymerization system can be polymerized to obtain microgel particles having a very small particle size distribution even if polymerization is carried out without particularly controlling the stirring conditions.

2. Non-crosslinked core-crown microgel [acrylamide amine core-crown]

A preferred non-crosslinked core-crown type microgel which can be used in the present invention is a core obtained by radical polymerization of a monomer represented by the following formulas (1) to (3) under specific conditions - A dispersion of crown particles.

R ₁ is an alkyl group having 1 to 3 carbon atoms, and n (molecular weight of the polyoxyethylene moiety) is from 8 to 200. X is H or CH ₃ .

The polyoxyethylene macromonomer represented by the above formula (1) is preferably an acrylic acid derivative or a methacrylic acid derivative. For example, a product sold by Aldrich or a BLEMMAR (registered trademark) sold by Nippon Oil Co., Ltd. may be used. For example, methoxy polyethylene glycol monomethacrylate can be used: PME-400, PME-1000, PME-4000 (the values of n in the formula (1) are: n=9, n=23, n= 90, all manufactured by Nippon Oil Corporation).

R ₂ represents an alkyl group having 1 to 3 carbon atoms, and R ₃ represents a substituent having 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, and for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate or amyl acrylate may be used. Hexyl acrylate, heptyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate , hexyl methacrylate, heptyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, and the like. Among them, methyl methacrylate (alias: methyl methacrylate), butyl methacrylate (alias: butyl methacrylate), octyl methacrylate (alias: octyl methacrylate) ) Better.

Such hydrophobic monomers are widely used raw materials and are generally industrial raw materials and thus are readily available. For example, goods sold by Aldrich Corporation or Tokyo Chemical Industry Co., Ltd. can be used.

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

The hydrophobic monomer represented by the above formula (3) is preferably a acrylamide derivative or a methacrylamide derivative. For example, use: butyl butyl decylamine, N,N-dimethyl acrylamide, N-[3-(dimethylamino)propyl] acrylamide, and butyl butyl methacrylate , octyl acrylamide, octyl methacrylamide, octadecyl acrylamide, etc. are preferred. Among them, particularly preferred is t-butyl acrylamide, N,N-dimethyl acrylamide, and N-[3-(dimethylamino)propyl]acrylamide.

Such hydrophobic monomers can be obtained from commercial or industrial raw materials.

The copolymer constituting the core-crown type fine particles of the present invention is a macromonomer selected from the above formula (1) by any of the following radical polymerization methods under the conditions of the following formulas (A) to (D) And one or more types of the hydrophobic monomers represented by the above formulas (2) and (3) are copolymerized.

(A) The molar ratio of the molar amount of the addition of the aforementioned polyethylene oxide macromonomer / (the aforementioned 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 of 8 to 200 repeating units, which is represented by the following formula (2) The acrylate derivative monomer is an acrylic acid derivative or a methacrylic acid derivative having a substituent having an alkyl group having 1 to 12 carbon atoms, and an acrylamide derivative monomer represented by the following formula (3). An acrylamide derivative or a methacrylium oxime having a substituent having an alkyl group having 1 to 12 carbon atoms Amine derivative.

(C) The polymerization solvent is a water-alcohol mixed solvent, and the alcohol is one or more selected from the group consisting of ethanol, dipropylene glycol, 1,3-butylene glycol, and isoprene glycol.

(D) The solvent composition of the water-alcohol mixed solvent, the mass ratio of 20 ° C is water: alcohol = 90: 10 to 10: 90.

Hereinafter, each condition will be further described in detail.

(Condition (A))

The molar amount of the aforementioned polyoxyethylene macromonomer and the aforementioned hydrophobic monomer (that is, the sum of the acrylate derivative monomer and/or the acrylamide derivative monomer) is in the polyethylene oxide macromolecule The polymerization can be carried out when the hydrophobic monomer is in the range of from 1:10 to 1:250 (mole ratio). The aforementioned molar amount is preferably from 1:10 to 1:200, more preferably from 1:25 to 1:100.

When the amount of molybdenum of the hydrophobic monomer is less than 10 times relative to the molar amount of the polyoxyethylene macromonomer, the polymerized polymer becomes water-soluble and cannot form core-crown particles. Further, when the amount of molybdenum of the hydrophobic monomer is 250 times or more relative to the molar amount of the polyoxyethylene macromonomer, the dispersion stability by the polyethylene oxide macromonomer may be incomplete and insoluble. The hydrophobic polymer of the hydrophobic monomer aggregates and precipitates.

(Condition (B))

Condition (B) is composed of three conditions (B-1) to (B-3) below.

(B-1)

The macromonomer represented by the formula (1) is a polyethylene glycol-based acrylic acid derivative or a methacrylic acid derivative containing 8 to 200 repeating units. Heavy When the number of the plurality of units is seven or less, the particles which are stably dispersed in the solvent may not be obtained. When the number of the particles is more than 200, it may be unstable when the particles are finely blended in the cosmetic.

(B-2)

The acrylate derivative monomer represented by the above formula (2) is an acrylic acid derivative or a methacrylic acid derivative having a substituent of an alkyl group having 1 to 12 carbon atoms. When the carbon number is 0 (the monomer having no terminal ester bond), the hydrophilicity of the monomer may be too high to be favorably emulsified and polymerized. On the other hand, when the carbon number is 13 or more, a good feeling of use cannot be obtained.

(B-3)

The acrylamide derivative monomer represented by the above formula (3) is an acrylamide derivative or a methacrylamide derivative having a substituent having an alkyl group having 1 to 18 carbon atoms.

The hydrophobic monomer in the present invention must be one or two selected from the group consisting of an acrylate derivative monomer represented by the above formula (2) and a acrylamide derivative monomer represented by the above formula (3). The monomer composition of the above mixture.

In the present invention, the hydrophobic monomer is particularly used: methacrylate and butyl methacrylate, or methacrylate, t-butyl acrylamide, N,N-dimethyl decylamine And 4 kinds of N-[3-(dimethylamino)propyl]propenylamine are preferred. In the combination of such hydrophobic monomers, it is more preferable to use methoxypolyethylene glycol monomethacrylate as a macromonomer.

However, it is not limited thereto, and a combination of the macromonomer and the hydrophobic monomer which are optimal in the present invention may be exemplified by: ‧ 8 to 90 repeating units of polyethylene glycol, and 15 of the best methoxy polyethylene glycol monomethacrylate, methacrylate, and butyl methacrylate, ‧ The polyethylene glycol-based repeating unit is 8 to 200, and the 90 best methoxy polyethylene glycol monomethacrylate, methacrylate, t-butyl acrylamide, N, N - dimethyl methacrylate, and N-[3-(dimethylamino) propyl] acrylamide, tert-butyl methacrylamide, octyl acrylamide, octyl methacrylamide, Octadecyl acrylamide.

(Condition (C))

The polymerization solvent must be a water-alcohol mixed solvent. The alcohol is preferably one which dissolves the hydrophobic monomer represented by the formulas (2) and (3). Therefore, one or two or more selected from the group consisting of ethanol, dipropylene glycol, 1,3-butylene glycol, and isoprene glycol are preferred.

(Condition (D))

The solvent composition of the water-alcohol mixed solvent of the polymerization solvent is preferably 20 ° C by mass: alcohol = 90 to 10: 10 to 90, and water: alcohol = 80 to 20: 20 to 80. When the mixing ratio of the alcohol is lower than the volume ratio of 10, the solubility of the hydrophobic monomer is extremely low, and there is a case where microparticles cannot be formed. Further, when the mixing ratio of the alcohol is higher than the 90 volume ratio, the emulsion of the hydrophobic monomer cannot be formed due to the hydrophobic interaction, and the emulsion polymerization cannot be performed, and the fine particles cannot be obtained.

Moreover, the microgels of synthetic polymers in the past are all made by using polymer electrolytes, such as polyacrylic acid, so they are not acid resistant to water dispersibility. Sex and alkali resistance. However, it is considered that when applied as a blending component of pharmaceuticals and cosmetics, it is extremely important to adapt to acid resistance and alkali resistance under physiological conditions. In the core-crown type microgel of the present invention, since it is a microgel which is stabilized by a polyoxyethylene chain of a nonionic polymer, its dispersion stability in water can be expected to have acid resistance and alkali resistance. .

The microgel used in the present invention is characterized in that the hydrophilic macromonomer and the hydrophobic monomer are ordered in a solvent to make the particle size substantially constant, and the core portion can be crosslinked or non-crosslinked. The core-crown polymer microgel.

The amount of the core-crown type microgel of the present invention in the cosmetic is usually 0.01 to 10% by mass (pure component, hereinafter, expressed in %), based on the total amount of the composition. When the blending amount is less than 0.01% (pure component), there is a case where it is difficult to obtain a stable cosmetic. When the blending amount exceeds 10% (pure component), there are cases where the composition is unsatisfactory and the feeling of use is poor from the viewpoint of stability in long-term storage under high temperature conditions.

The core-crown type microgel of the present invention can emulsify the oil phase component and the water phase component to form a core-crown type microgel emulsifier having oil phase components dispersed in the water phase component. A powdery composition of oil in the structure of water. Therefore, the core-crown type microgel emulsifier of the present invention has strong emulsifying power, and when the core-crown type microgel of the present invention is used as an emulsifier, it can be made into an oily oil having excellent emulsion stability. Powder type composition. At the same time, since the core-crown type microgel is present in the oil phase, sufficient strength can be obtained by the variation of the comparatively important hydrophobic powder.

The powder type composition in the oil of the present invention is a core-crown type microgel which is mixed and dispersed in water or a water phase component, and then added according to a general method. The oil phase component and other components of the hydrophobic powder are dispersed and emulsified by stirring and applying a shearing force.

The amount of the oil phase component and the water phase component to be blended in the powdery oil composition of the present invention is not particularly limited. (a) Since the core-crown microgel is used as an emulsifier, the ratio of the oil phase component to the water phase component is small, and the embodiment (beauty liquid, emulsion, etc.) having a small amount of the oil phase component can be obtained. A multi-component oil-based powder composition of a wide range of oil phase components/aqueous phase components in a wide range of embodiments (cleansing cream, sunscreen lotion, hair lotion, mask, aerosol, foundation cream, etc.).

[other ingredients]

The composition of the present invention may be used in other components such as cosmetics and non-pharmaceuticals, and may be appropriately formulated, for example, a UV absorber, a powder, an organic amine, or a polymer emulsion, insofar as the effects of the present invention are not impaired. , vitamins, antioxidants, etc.

Water-soluble UV absorbers such as 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy Dibenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methyl two Benzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4'-phenylbenzophenone-2-carboxylate a benzophenone-based ultraviolet absorber such as 2-hydroxy-4-n-octyloxybenzophenone or 4-hydroxy-3-carboxybenzophenone; phenylbenzimidazole-5-sulfonic acid and its salt, and benzene stretching Benzimidazole-based UV absorbers such as bisbenzimidazole-tetrasulfonic acid and its salts; 3-(4'-methylbenzylidene)-d,l-camphor, 3-benzylidene-d, L-樟 Brain, urinary acid, urinary acid ethyl ester, etc.

Oil-soluble ultraviolet absorbers such as p-aminobenzoic acid (PABA), PABA monoglyceride, N,N-dipropoxy-PABA-ethyl ester, N,N-diethoxy-PABA-ethyl ester, N, Benzoic acid-based ultraviolet absorbers such as N-dimethyl-PABA-ethyl ester and N,N-dimethyl-PABA-butyl ester; and amine anthranilic acid such as menthyl-N-acetamide anisole Amyl salicylate, methyl salicylate, methyl menthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, salicylic acid, phenyl isopropanol, etc. Salicylic acid ultraviolet absorber; octyl cinnamate, cinnamic acid-ethyl-4-isopropyl ester, cinnamic acid methyl-2,5-diisopropyl ester, cinnamic acid ethyl-2,4-diisopropyl ester , methyl 2,4-diisopropyl cinnamate, propyl p-methoxycinnamate, isopropyl p-methoxycinnamate, isoamyl p-methoxycinnamate, octyl p-methoxycinnamate Ester, p-methoxycinnamic acid-2-ethylhexyl ester, p-methoxycinnamic acid-2-ethoxyethyl ester, p-methoxycinnamic acid cyclohexyl ester, cinnamic acid ethyl-α-cyano group -β-phenyl ester, cinnamic acid-2-ethylhexyl-α-cyano-β-phenyl ester, glyceryl mono-2-ethylhexyl-di-pair Cinnamate-based ultraviolet absorber such as cinnamate, 3,4,5-trimethoxycinnamic acid 3-methyl-4-[methylbis(trimethyldecyloxy)indolyl]butyl; 2- Phenyl-5-methylbenzoxazole, 2,2'-hydroxy-5-methylphenylbenzotriazole, 2-(2'-hydroxy-5'-trioctylphenyl)benzo Triazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, benzaldehyde oxime, bismuth oxime methane, 4-methoxy-4'-tert-butyl benzophenone Mercapto methane, 5-(3,3-dimethyl-2-indanyl)-3-pentan-2-one, octocrylene acrylate, and the like.

Powder components such as inorganic powders (eg talc, kaolin, mica, sericite, muscovite, phlogopite, synthetic cloud) Mother, red mica, biotite, vermiculite, magnesium carbonate, calcium carbonate, aluminum citrate, barium strontium citrate, calcium citrate, magnesium citrate, barium strontium citrate, metal tungstate, magnesium, cerium oxide, zeolite, sulfuric acid Strontium, calcined calcium sulphate (calcined gypsum), calcium phosphate, fluoridated apatite, hydroxyapatite, ceramic powder, metal soap (eg zinc zinc myrate, calcium palmitate, aluminum stearate), nitriding Boron, etc.; organic powder (for example: polyamide resin powder (nylon powder), polyethylene powder, polymethyl methacrylate powder, polystyrene powder, styrene and acrylic copolymer resin powder, benzoguanamine resin Powder, polytetrafluoroethylene powder, cellulose powder, etc.); inorganic white pigments (for example: titanium dioxide, zinc oxide, etc.); inorganic red pigments (for example: iron oxide (iron), iron titanate, etc.); inorganic brown Pigments (for example, γ-iron oxide, etc.); inorganic yellow pigments (for example, yellow iron oxide, loess, etc.); inorganic black pigments (for example, black iron oxide, low-grade titanium oxide, etc.); inorganic purple pigments (for example) : Mango violet, cobalt violet, etc.; inorganic green pigments (eg oxidation , chromium hydroxide, cobalt titanate, etc.; inorganic blue pigments (eg, ultramarine, indigo, etc.); pearlescent pigments (eg, coated with titanium oxide mica, coated titanium oxide bismuth oxychloride, coated with titanium oxide talc, Color coated titanium oxide mica, bismuth oxychloride, fish scale foil, etc.; metal powder pigments (for example: aluminum powder, copper powder, etc.); organic pigments such as zirconium, hafnium or aluminum lake (for example: red 201, red 202 Organic pigments such as red 204, red 205, red 220, red 226, red 228, red 405, orange 203, orange 204, yellow 205, yellow 401, and blue 404; Red 3, Red 104, Red 106, Red 227, Red 230, Red 401, Red 505, Orange 205, Yellow 4, Yellow 5, Yellow 202, Yellow 203 No., green No. 3 and blue No. 1, etc.; natural pigments (for example: chlorophyll, β-carotene, etc.).

Organic amines such as monoethanolamine, diethanolamine, triethanolamine, morphine, tetrakis(2-hydroxypropyl)ethylenediamine, triisopropanolamine, 2-amino-2-methyl-1,3-propane Glycol, 2-amino-2-methyl-1-propanol, and the like.

The polymer emulsion is, for example, an acrylic resin emulsion, a polyethyl acrylate emulsion, an acrylic resin liquid, a polyalkyl acrylate emulsion, a polyvinyl acetate resin emulsion, a natural rubber latex, or the like.

Vitamins such as: vitamin A, B ₁ , B ₂ , B ₆ , C, E and derivatives thereof, pantothenic acid and its derivatives, biotin and the like.

Antioxidants are, for example, tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid esters and the like.

The antioxidant auxiliary agent is, for example, phosphoric acid, citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, fumaric acid, cephalin, hexametaphosphate, phytic acid, ethylenediaminetetraacetic acid or the like.

Other adjustable ingredients such as preservatives (methyl paraben, ethyl paraben, butyl paraben, phenoxyethanol, etc.); anti-inflammatory agents (eg glycyrrhizin derivatives, glycyrrhizic acid) Derivatives, salicylic acid derivatives, hinokitiol, zinc oxide, allantoin, etc.; whitening agents (eg, placenta extract, saxifrage extract, arbutin, etc.); various extracts (eg, cork) , berberine, comfrey root, peony, medicine, birch, sage, medlar, carrot, aloe, geranium, iris, grape, coix seed, loofah, lily, crocus, Chuanxiong, burdock, small Forsythia, formononet, garlic, pepper, dried tangerine peel, seaweed, etc.; immunostimulating agents (eg royal jelly, Photoreceptors, cholesterol derivatives, etc.; circulatory improvers (eg, vanillyl phthalate, benzyl nicotinic acid, nicotinic acid-β-butoxyethyl ester, capsaicin, zingerone, cantharidin, Fish fat, tannic acid, alpha-borneol, nicotinic acid tocopherol, phytate hexanicotinic acid ester, cyclomandelic acid ester, cinnarizine, tolazoline, acetylcholine, pan Vespa (verapamil, cephalosporin, γ-glutenol, etc.); anti-lipid leakage agents (eg, sulfur, thianthol, etc.); anti-inflammatory agents (eg tranexamic acid, sulfur) Regeneration of taurine, hypotaurine, etc.).

Further, in the powdery oil composition of the present invention, it is not used as an emulsifier for the purpose of controlling the feeling of use, controlling the permeability of the drug, or the like, or improving the cleaning of the skin and hair detergent. For the purpose of sex, etc., it is also possible to formulate a surfactant of an aqueous phase or an oil phase component.

The amphoteric surfactant contains at least one of a cationic functional group and an anionic functional group, and is cationic when the solution is acidic, anionic when alkaline, and close to nonionic interfacial activity near the isoelectric point. The nature of the agent.

Amphoteric surfactants can be classified into carboxylic acid type, sulfate type, sulfonic acid type and phosphate type according to the type of anionic group. The present invention is preferably a carboxylic acid type, a sulfate type, and a sulfonic acid type. The carboxylic acid type can be reclassified into an amino acid type and a betaine type. Especially the betaine type is better.

Specifically, for example, an imidazoline-based amphoteric surfactant (for example, 2-undecyl-N,N,N-(hydroxyethylcarboxymethyl)-2-imidazolinium, 2-cocoathione- 2-imidazolinium hydroxide--1-carboxyethoxy disodium salt, etc.; betaine-based surfactant (for example: 2-heptyl-N-carboxymethyl-N-hydroxyethyl) Oxazolinium betaine, lauryl dimethylaminoacetic acid betaine, alkyl betaines, betaine decylamine, sulfonic acid betaine, etc.).

Cationic surfactants such as: cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, benzalkonium chloride, benzalkonium hydroxyethylammonium chloride, stearyl dimethyl chloride A quaternary ammonium salt such as benzalkonium chloride or cetyltriethylammonium sulfate. Also, it may be: diethylaminoethyl decylamine stearate, dimethylaminoethyl decylamine stearate, diethylaminoethyl decyl palmitate, dimethylamine palmitate Ethyl decylamine, diethylaminoethyl decyl myristate, dimethylaminoethyl decyl myristate, diethylaminoethyl amide, behenic acid Aminoethyl decylamine, diethylaminopropyl decylamine stearate, dimethylaminopropyl decylamine stearate, diethylaminopropyl decyl palmitate, dimethyl palmitate Aminopropyl decylamine, diethylaminopropyl decylamine myristate, dimethylaminopropyl decylamine myristic acid, diethylaminopropyl decyl amide, behenic acid A guanamine-based compound such as dimethylaminopropylamine.

In terms of anionic surfactants, it can be classified into: a fatty acid soap, a N-mercapto glutamate, an alkyl ether acetate, and the like; an α-olefin sulfonate, an alkane sulfonate, an alkylbenzene sulfonic acid; A sulfonic acid type such as a sulfonic acid type; a higher alcohol sulphate salt; a phosphate salt type. Further, a carboxylate type, a sulfonate type, and a sulfate type are preferable, and a sulfate type is particularly preferable.

Specific examples thereof include fatty acid soaps (for example, sodium laurate and sodium palmitate), higher alkyl sulfate salts (for example, sodium lauryl sulfate, potassium lauryl sulfate, etc.), and alkyl ether sulfates. (Example: POE-lauryl triethanolamine lauryl sulfate, POE-sodium lauryl sulfate, etc.), N-mercaptocreatine (for example: month Sodium citrate, etc., higher fatty acid decyl sulfonate (for example: N-myristyl-N-methyl tauroate, coconut oil fatty acid methyl tauroxamide, lauryl Sodium tauroxamide, etc.), phosphate salts (eg, POE-oleyl ether phosphate, POE-stearyl ether phosphate, etc.), sulfosuccinates (eg, di-2-ethylhexyl sulfonate) Sodium oxalate succinate, monolaurinyl monoethanol decylamine polyoxyethylene sulfosuccinate sodium succinate, sodium laureth propylene glycol sulfosuccinate, etc., alkylbenzene sulfonate (eg linear 12 Sodium benzenesulfonate, triethanolamine linear dodecylbenzenesulfonate, linear dodecylbenzenesulfonic acid, etc.), higher fatty acid ester sulfate salt (for example: hydrogenated coconut oil fatty acid glyceride sodium sulfate, etc.), N - mercapto glutamate (for example: N-lauryl glutamic acid monosodium, N-stearyl glutamic acid disodium, N-myristyl-L-glutamic acid monosodium, etc.), Sulfated oil (for example: sulfonated castor oil, etc.), POE-alkyl ether carboxylic acid, POE-alkyl allyl ether carboxylate, α-olefin sulfonate, higher fatty acid ester sulfonate, secondary Alcohol sulfate salt, higher fatty acid Amides sulfate ester group, acyl monoethanolamide lauryl Amides sodium succinate, N- palmitoyl two acyl aspartic acid - triethanolamine, sodium caseinate.

Nonionic surfactants are surfactants that do not have an electrical charge when ionized in aqueous solution. The type of alkyl group used in the case of a hydrophobic group and the type using dimethyl polyfluorene are known. Specific examples of the former include glycerin fatty acid esters, oxyethylene derivatives of glycerin fatty acid esters, polyglycerin fatty acid esters, propylene glycol fatty acid esters, propylene oxide derivatives of propylene glycol fatty acid esters, and polyethylene glycol fatty acids. Ester, polyethylene glycol alkyl ether, polyethylene glycol alkyl phenyl ether, polyethylene glycol castor oil derivative, polyethylene glycol hydrogenated castor oil derivative and the like. The latter, for example: polyether modified poly-oxygen, polyglycerol 聚聚矽 oxygen and so on. The type in which the alkyl group is used as the hydrophobic group is preferred.

Specifically, lipophilic nonionic surfactants such as: sorbitan fatty acid esters (eg, sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate) Ester, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, penta-2-ethylhexanoic acid diglycerol Ester sorbitan, tetra-2-ethylhexanoic acid diglyceride sorbitan, etc.), glycerol polyglycerol fatty acid esters (eg, cottonseed oil fatty acid glyceride, mono erucic acid glyceride, sesquioleic acid) Glyceryl ester, glyceryl monostearate, α,α'-glycerol glyceryl glutamate, glyceryl monostearate malate, etc.), propylene glycol fatty acid esters (for example, propylene glycol monostearate, etc.) , hydrogenated castor oil derivatives, glyceryl alkyl ethers, and the like.

Hydrophilic nonionic surfactants such as POE-sorbitan fatty acid esters (for example: POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitol) An anhydride monooleate, POE-sorbitan tetraoleate, etc., a POE-sorbitol fatty acid ester (for example: POE-sorbitol monolaurate, POE-sorbitol monooleate, POE-sorbitol pentaoleate, POE-sorbitol monostearate, etc., POE-glycerol fatty acid esters (for example: POE-glycerol monostearate, POE-glycerol monoisostearate) , POE-glycerol triisostearate, etc. POE-monooleate, etc., POE-fatty acid esters (for example: POE-distearate, POE-mono-oleate, ethylene distearate) Alcohol esters, etc., POE-alkyl ethers (for example: POE-lauryl ether, POE-oleyl ether, POE-stearyl ether, POE-behenyl ether, POE-2-octyldodecyl ether , POE-dihydrocholesterol ether, etc.), Pullonic type (eg, Pullonic, etc.), POE ‧ POP-alkyl ethers (eg POE ‧ POP-cetyl ether, POE ‧ -2- meryl-tetradecyl ether, POE POP- Monobutyl ether, POE‧POP-hydrogenated lanolin, POE‧POP-glyceryl ether, etc.), four POE/tetra-POP-ethylenediamine condensate (eg, Tetronic, etc.), POE-castor oil hydrogenated castor oil derivative (Example: POE-castor oil, POE-hydrogenated castor oil, POE-hydrogenated castor oil monoisostearate, POE-hydrogenated castor oil triisostearate, POE-hydrogenated castor oil monofocal glutamic acid mono Stearic acid diester, POE-hydrogenated castor oil maleic acid, etc.), POE-beeswax/levine oil derivatives (for example: POE-sorbitol beeswax, etc.), alkyl alcohol decylamine (for example: coconut Oil fatty acid diethanolamine, lauric acid monoethanolamine, fatty acid isopropanolamine, etc.), POE-propylene glycol fatty acid ester, POE-alkylamine, POE-fatty acid decylamine, sucrose fatty acid ester, alkyl Oxydimethylamine oxide-trioleylphosphoric acid or the like.

[Examples]

The use of the powder-type composition in the oil of the present invention is not limited, and since it has high stability and does not impair the water resistance of the hydrophobic powder, it can be used as a skin cosmetic such as a sunscreen cosmetic or an emulsified foundation cream. , hair cosmetics, skin external preparations, etc., and product.

First, the inventors of the present invention first reviewed the blending form of the hydrophobic powder in the oily type in the oily oil, the stability of the hydrophobic powder, and the water resistance at the time of coating. The results are shown in Table 1.

Among them, the evaluation is carried out as follows.

[Water resistance]

The sample was first coated on a resin plate at 2 mg/cm ² , and the UV spectrum at 290 to 400 nm was measured. Then, the plate was attached to the wall surface of a container containing about 20 L of water with a double-sided tape, and immersed in a water flow of 500 rpm for 30 minutes, and then the spectrum was measured in the same manner. The ratio % of the integral value of the spectrum before and after immersion is water resistance, and if it is 100%, it means that the impregnation effect is hardly reduced even if immersed.

Moreover, the manufacturing method of each test example is as follows.

<manufacturing steps (1-1, 2, 3, 4)>

Aqueous phase: Mixing ingredients 1, 2, 3, 4, 5, 7, 9, 30, 33, 34, 35 Combined

Oil phase A: dissolved in the liquid oil phase components of components 14, 15, 16, and 17 Solid oil phase composition of 11, 12, 13, 21, 22, 23, 24

Oil phase B: Dispersion component 27 in components 18, 19, 20

Emulsification Mixing oil phases A, B in the aqueous phase

<Manufacturing Step (1-5)>

Oil phase: ingredients 10, 14, 17, 18, 19, 25, 26 are first mixed, then component 6, and then 28, 31, 32 are dispersed.

Aqueous phase: first mix 33 in component 1, disperse evenly, then mix components 2, 4

Emulsification: mixing the aqueous phase in the oil phase

<Manufacturing Steps (1-6)>

Aqueous phase: Mixing ingredients 1, 2, 3, 4, 5, 8, 30, 33, 34, 35

Oil phase: A dissolves the solid oil phase components of components 11, 12, 13, 21, 22, 23, 24 in the liquid oil phase components of components 14, 15, 16, and 17.

Oil phase B: Dispersion component 27 in components 18, 19, 20

Emulsification: in the aqueous phase, sequentially mix the oil phase B, A

It can be seen from the above Table 1 that when the powder-type (POW) sunscreen cosmetic in water oil containing a hydrophobic powder is prepared by core-crown emulsification, emulsification stability, use feeling, and water resistance can be obtained. Both are excellent.

On the other hand, the POW sunscreen cosmetic (1-2, 1-3) can be prepared even if a nonionic surfactant is used, but it can be confirmed that the water resistance is largely lowered.

Moreover, even for the core-crown emulsified sunscreen cosmetic, the hydrophobic powder is removed. In the case of the O/W type (1-4), the water resistance cannot be exhibited.

At the same time, in the preparation of water-based sunscreen cosmetics in normal oils (1-5), emulsion stability and water resistance can be obtained by selecting an appropriate surfactant, but since the continuous phase is an oil phase, it is not possible to obtain a refreshing Use sense.

In addition, the core-crown emulsification should also be one of the so-called powder emulsification (picolin emulsion), which should be similar to the "three-phase emulsification" technique in which the particles adhere to the oil/water interface to stabilize the emulsion. Comparison. When the PEG-10 hydrogenated castor oil test emulsification (1-6) using a vesicle which can form one of the three-phase emulsified particles, the hydrophobic powder is ejected from the inner phase and aggregated, so that it is difficult to prepare a stable emulsified composition.

Based on the above results, the inventors of the present invention further reviewed the core-crown emulsified POW emulsified composition.

First, the inventors reviewed the amount of the core-crown dispersant added. The results are shown in Table 2.

Further, the method of production was in accordance with Test Example 1-1.

As a result of the results of Table 2, the core-crown type microgel, although depending on the amount of the oil phase containing the hydrophobic powder, exhibits excellent stability when it is 0.5% by mass or more (pure component) in the composition. . In addition, even if the amount of the conventional knowledge is increased in the range of the conventional knowledge, there is almost no adverse effect on the stability, the feeling of use, the water resistance, etc., and the dispersant is preferably about 2% by mass, but it is still possible to mix about 10% by mass.

Furthermore, the present inventors also reviewed the addition of a nonionic surfactant. The results are shown in Table 3.

Further, the production method was in accordance with Test Example 1-1.

Although the nonionic surfactant can also improve the emulsion stability when it is moderately formulated in the core-crown emulsification, the stability is not problematic when the blending amount is 0.8% by mass or more, but water resistance can still be observed. Significantly lower. Therefore, there is no need to prepare a nonionic surfactant, and it is preferably 0.5% by mass or less in blending.

[Production Example of Non-Crosslinked Core-Crown Type Microparticle Dispersion]

The macromonomer and the hydrophobic monomer described in Table 4 were subjected to radical polymerization in accordance with the following production method (operation method 1) under the polymerization conditions shown in Tables 4 and 5. The obtained copolymer dispersion was visually evaluated for appearance, and the particle size and dispersion of the copolymer were evaluated in accordance with the operation method 2. The results are shown in Table 3.

<Operation Method 1: Manufacturing Method of Core-Crown Particles>

First, in a three-necked flask equipped with a reflux condenser and a nitrogen gas inlet tube, a water-alcohol mixed solvent containing 90 g of a polyoxyethylene macromonomer, hydrophobicity monomer. After being sufficiently dissolved or dispersed, 2,2'-azobis(2-methylpropionamidine dihydrochloride), which is 1 mol% of the total monomer, is dissolved in a small amount of water, and then added. Dissolved or dispersed. After the uniformly dissolved or dispersed polymerization solution was subjected to nitrogen displacement for 20 minutes to remove dissolved oxygen, the polymerization was carried out for 8 hours while maintaining the temperature in the oil bath at 65 to 70 ° C under stirring with an electromagnetic stirring granule. After the completion of the polymerization, the polymerization solution is returned to room temperature to obtain a dispersion of core-crown particles.

Further, a polyethylene oxide macromolecular single system was used by BLEMMAR-PME-4000 (manufactured by NOF Corporation). Also, a hydrophobic single system is used: methyl methacrylate (MMA), butyl methacrylate (n-BMA), t-butyl acrylamide (t-BAA), N,N-dimethyl propylene Indoleamine (DMAA), N-[3-(dimethylamino)propyl]acrylamide (DMAPA).

<Operation 2: Method for measuring particle size and dispersion>

The particle size of the copolymer was measured using a Zetasizer manufactured by Malvern. First, a microparticle dispersion prepared by diluting with water to a particle concentration of about 0.1% was used as a measurement sample, and then impurities were removed by a 0.45 μm filter, and the scattering intensity at 25 ° C was measured at a scattering angle of 173° (backlight scattered light). The analytical software equipped with the device calculates the average particle size and dispersion. The particle size is further analyzed by a cumulative amount analysis method, and the degree of dispersion is a value normalized by the second cumulative amount obtained by the cumulative amount analysis. Since the degree of dispersion is a commonly used parameter, it can be automatically analyzed using a commercial dynamic light scattering measuring device. The viscosity of the solvent required for particle size analysis is a pure water viscosity of 25 ° C, that is, a value of 0.89 mPa ‧ is used.

As shown in Table 6, methoxypolyethylene glycol monomethacrylate (macromonomer) and methyl methacrylate selected from the group consisting of a substituent having an alkyl group having 1 to 4 carbon atoms, A One or more of butyl acrylate, butyl butyl decylamine, N,N-dimethyl decylamine, and N-[3-(dimethylamino)propyl] decylamine Hydrophobic monomer, in the water-ethanol mixed solvent (water: ethanol = 40 to 60: 18 to 82), the value of "addition of molar amount of macromonomer / molar amount of hydrophobic monomer" In Production Examples 1 to 10 which were a conditional polymerization of 1:50 to 100, a dispersion in the form of a white turbid solution was obtained, and the particle diameter and the degree of dispersion were evaluated. That is, it is confirmed that a particulate polymer (core-crown particle) is formed. Further, the core-crown type particles of Examples 1 to 10 were produced, and the particle diameter was 150 to 250 nm, and the particle diameter was also uniform.

Therefore, it is understood that the polyoxyethylene macromonomer represented by the above formula (1), the acrylate derivative monomer represented by the above formula (2), and the acrylamide represented by the following formula (3) are obtained. One or two or more kinds of hydrophobic monomers of the derivative monomer, according to: (A) the amount of molybdenum added by the aforementioned polyoxyethylene macromonomer / (pre The molar amount of the acrylate derivative monomer and/or the acrylamide derivative monomer is 1:10 to 1:250, and (B) the macromolecule represented by the above formula (1) The monomer is a polyethylene glycol-based acrylic acid derivative or a methacrylic acid derivative containing 8 to 200 repeating units, and the acrylate derivative monomer represented by the above formula (2) has a carbon number of 1 An acrylic acid derivative or a methacrylic acid derivative of a substituent of an alkyl group of 12, and the acrylamide derivative monomer represented by the above formula (3) is a substituent having an alkyl group having 1 to 12 carbon atoms. The acrylamide derivative or the methacrylamide derivative, (C) the polymerization solvent is a water-alcohol mixed solvent, and the alcohol is selected from the group consisting of: ethanol, dipropylene glycol, 1,3-butylene glycol, and isopentylene glycol The solvent composition of one or two or more (D) water-alcohol mixed solvents, at a mass ratio of 20 ° C, is water: alcohol = 90 to 10: 10 to 90 ((A) to (D)) By performing radical polymerization, core-crown particles having a uniform particle size can be obtained.

A comparison of the composition using the crosslinked core-crown type microgel with the composition using the non-crosslinked type core-crown type microgel is shown in Table 7 below.

As is apparent from the above Table 7, as in the case of using the crosslinked type core-crown type microgel (Test Example 7-1), it is also excellent when a non-crosslinked type core-crown type microgel is used. Emulsification stability.

Claims (4)

An oil-in-water powder composition comprising: a hydrophobic powder, an oil phase in which the hydrophobic powder is dispersed, and an aqueous phase in which the oil phase is dispersed, wherein the surface of the hydrophobic colloidal particle is used A core-crown type microgel having a hydrophilic group is provided as a dispersing agent for dispersing the aforementioned oil phase in the aqueous phase. The powdery water-borne powder composition according to claim 1, wherein 0.5 to 10% by mass of (acrylate/methacrylic acid methoxy PEG) crosslinked polymer and/or non-crossing are used. A propylene amide amine polymer is used as a core-crown type microgel. The powdery water-borne powder composition according to the first or second aspect of the invention, wherein the nonionic surfactant is formulated in an amount of 0.5% by mass or less in the composition. The powdery-type composition in water oil according to the first aspect of the invention, wherein the core-crown type microgel is selected from the group consisting of polyoxyethylene macromonomers represented by the following formula (1), One or two or more kinds of hydrophobic monomers of the acrylate derivative monomer represented by the formula (2) and the acrylamide derivative monomer represented by the following formula (3) are as follows (A) to a core-crown type microparticle composed of a non-crosslinked acrylamide polymer obtained by radical polymerization under the condition of (D); (A) an amount of molybdenum added by the aforementioned polyoxyethylene macromonomer / The molar amount of the addition of the acrylate derivative monomer and/or the acrylamide derivative monomer is 1:10 to 1:250, and (B) the macro represented by the following formula (1) The molecular monomer is an acrylic acid derivative or a methacrylic acid derivative having a polyethylene glycol group of 8 to 200 repeating units, and the acrylate derivative monomer represented by the following formula (2) has a carbon number of 1 to The acrylic derivative or the methacrylic acid derivative of the alkyl group of 12, the acrylamide derivative monomer represented by the following formula (3) is a substituent having an alkyl group having 1 to 12 carbon atoms. The acrylamide derivative or the methacrylamide derivative, the (C) polymerization solvent is a water-alcohol mixed solvent, and the alcohol is selected from the group consisting of ethanol, dipropylene glycol, 1,3-butylene glycol, and isoprene glycol. Solvent composition of two or more kinds of (D) water-alcohol mixed solvents, the mass ratio at 20 ° C is water: alcohol = 90 to 10: 10 to 90, R ₁ represents an alkyl group having 1 to 3 carbon atoms, n is a number from 8 to 200; and 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 having 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 having an alkyl group having 1 to 12 carbon atoms.