JP2013112679A - Oil-in-water type emulsified skin cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an oil-in-water type emulsified skin cosmetic excellent in spreadability and compatibility with skin, and extremely superior in feeling of use without sticky feeling such as fresh and youthful feeling, penetrating feeling, emollient feeling or tension feeling.SOLUTION: This oil-in-water type emulsified skin cosmetic contains a following component (A) and (B). (A) An ester formed of a fatty acid mixture containing 16-18C fatty acids and pentaerythritol. (B) A thickener comprising microgel obtained by radically polymerizing dimethylacrylamide with 2-acrylamide-2-methylpropanesulfonic acid under the condition that microgel forms a single phase microemulsion or a fine W/O emulsion by a surfactant. The microgel is obtained by dissolving a water-soluble ethylenic unsaturated monomer in a dispersed phase in a composition wherein an organic solvent or an oil is used as a dispersion medium and water is used as the dispersed phase and radically polymerizing in the dispersed phase.

Description

  The present invention relates to a skin cosmetic excellent in use feeling. More particularly, the present invention relates to an oil-in-water emulsified skin cosmetic that has good spread and familiarity to the skin, is non-sticky, and is extremely excellent in use feeling such as freshness, penetrating feeling, emollient feeling, and stickiness.

  Conventionally, in skin cosmetics, polyhydric alcohols such as glycerin, 1,3-butylene glycol, and dipropylene glycol are blended as aqueous components to produce a moist, smooth, emollient feeling, etc. Furthermore, higher fatty acids such as stearic acid, palmitic acid, myristic acid, behenic acid; waxes such as petrolatum, carnauba wax, candelilla wax, ceresin, microcrystalline wax; lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol A technique has been adopted in which solid oils such as higher alcohols such as behenyl alcohol are blended and emulsified with an emulsifier to form an oil-in-water emulsified skin cosmetic.

  In order to suppress crystallization of these solid oils over time, hydrocarbon oils that are liquid at room temperature such as liquid paraffin and squalane that are compatible with the solid oils, cetyl palmitate, isopropyl isostearate, isodecyl pivalate In addition, attempts have been made to avoid crystal precipitation of solid oil by blending an ester oil having a relatively long carbon chain such as oleyl oleate with a carbon chain comparable to that of solid oil (for example, Non-Patent Document 1). reference).

However, the oil-in-water emulsified skin cosmetics prepared by the method as described above have emollient and sticky feelings when applied to the skin, but they are not well-suited to the spread and skin, are sticky, and are easy to use. The point was not satisfactory.
On the other hand, when no solid oil is blended, there is a problem in that there is no emollient feeling or stickiness, although it is excellent in terms of spreading and skin familiarity and no stickiness.

  In recent years, skin cosmetics using homopolymers or copolymers of acrylic acid and / or acrylamide skeleton and pentaerythritol ester, dipentaerythritol ester and / or tripentaerythritol ester have been proposed. However, although this skin cosmetic can give a good emollient feeling to the skin, it has not yet been sufficiently reduced in terms of stickiness after application (see, for example, Patent Document 1).

In skin cosmetics, conventionally, decamethylcyclopentasiloxane, dimethylpolysiloxane, methylphenylpolysiloxane, caprylylmethicone, methylhydrogenpolysiloxane, etc. are used to reduce the smoothness during application and the stickiness after application. Silicone rubber, silicone rubber such as highly polymerized dimethylpolysiloxane, amino-modified highly polymerized dimethylpolysiloxane, (dimethicone / vinyl dimethicone) cross polymer, (dimethicone / phenyl dimethicone) cross polymer, (vinyl dimethicone / lauryl dimethicone) cross polymer, (Lauryl dimethicone / polyglycerin-3) cross polymer, (lauryl polydimethylsiloxyethyl dimethicone / bisvinyl dimethicone) cross polymer, dimethicone cross polymer, etc. The use of the paste and the silicone elastomer are known dimensions silicone crosslinked product of various liquid oil, such as dimethicone and trioctanoin as a solvent. However, when blending these into oil-in-water emulsified skin cosmetics, compatibility with other oils in the oil phase, such as hydrocarbon oils, ester oils, waxes, etc. must be taken into account. In other words, the prescription composition is restricted (for example, see Patent Document 2 and Patent Document 3).
Furthermore, when oily components such as silicones, esters, and hydrocarbons are added to an aqueous base, it is necessary to emulsify, and an emulsifier is required, and stickiness derived from the emulsifier is often problematic. It was.

JP-T-2007-531776 JP 2009-102281 A JP 2009-126806 A

“Latest Cosmetic Science” (Revised Supplement II) edited by Japan Society of Engineers, Yakuji Nippo, published on July 10, 1992, p. 49

When manufacturing oil-in-water emulsified skin cosmetics by the above-mentioned technique, the present inventors have a bad feeling of spreading and skin, stickiness, freshness, and an active ingredient permeating into the skin ( Penetrating feeling), emollient feeling, inferior feeling to the result of repeated research,
(A) A composition comprising a fatty acid mixture containing a fatty acid having 16 to 18 carbon atoms and an ester of pentaerythritol and (B) an organic solvent or an oil component as a dispersion medium and water as a dispersed phase. A microgel obtained by dissolving an unsaturated monomer in a dispersed phase and radical polymerization in the dispersed phase, wherein the microgel forms a one-phase microemulsion or a fine W / O emulsion by a surfactant. If an oil-in-water emulsified skin cosmetic is prepared by blending a thickener made of microgel obtained by radical polymerization of dimethylacrylamide and 2-acrylamido-2-methylpropanesulfonic acid, Familiarity, non-stickiness, freshness, feeling that active ingredients penetrate into skin (penetration), emollient , Newly found that excellent oil-in-water emulsified skin cosmetic beams feeling is obtained, and have completed the present invention.

  The object of the present invention is that it has good spread and familiarity with the skin, is non-sticky, fresh, feels that the active ingredient penetrates into the skin (penetration feeling), emollient feeling, and feeling of elasticity. The object is to provide an oil-in-water emulsified skin cosmetic.

That is, this invention provides the oil-in-water type emulsified skin cosmetic characterized by containing the following component (A) and (B).
(A) An ester of a fatty acid mixture containing a fatty acid having 16 to 18 carbon atoms and pentaerythritol (B) In a composition having an organic solvent or oil as a dispersion medium and water as a dispersion phase, A microgel obtained by dissolving a saturated monomer in a dispersed phase and radical polymerization in the dispersed phase, wherein the microgel forms a one-phase microemulsion or a fine W / O emulsion by a surfactant. Thickener comprising a microgel obtained by radical polymerization of dimethylacrylamide and 2-acrylamido-2-methylpropanesulfonic acid

  Further, in the present invention, the content of the ester of the fatty acid mixture containing fatty acid having 16 to 18 carbon atoms and pentaerythritol is 0.5 with respect to the total amount of the oil-in-water emulsified skin cosmetic. The oil-in-water emulsified skin cosmetic described above, wherein the content of the thickener comprising the microgel of the component (B) is 0.1 to 2.0% by mass. Is to provide.

  The oil-in-water emulsified skin cosmetic of the present invention has good spread and familiarity to the skin, and is non-sticky, fresh, feeling that the active ingredient penetrates into the skin (penetration feeling), emollient feeling and elasticity. It is an oil-in-water emulsified skin cosmetic with an extremely excellent feeling of use.

  Hereinafter, the oil-in-water emulsified skin cosmetic of the present invention will be described in detail.

"(A) Esters of fatty acid mixtures containing fatty acids having 16 to 18 carbon atoms and pentaerythritol"
In the present invention, the component (A) fatty acid mixture containing a fatty acid having 16 to 18 carbon atoms and an ester of pentaerythritol functions as an oil in the present invention, and the oil-in-water emulsified skin cosmetic of the present invention It is a component which comprises the oil phase.
In the present invention, in addition to esters of fatty acid mixtures containing fatty acids having 16 to 18 carbon atoms and pentaerythritol, other oils such as hydrocarbon oils, silicone oils, waxes, fatty acid esters It is possible to produce skin cosmetics by blending higher alcohols and other oil components. Specific oils that can be blended will be described later.

  The ester of a fatty acid mixture containing a fatty acid having 16 to 18 carbon atoms and pentaerythritol used in the present invention has a hydroxyl group in its structure, and therefore has a water-holding function and has a moisturizing function for the skin. Excellent effect.

In the present invention, a fatty acid mixture containing a fatty acid having 16 to 18 carbon atoms is a saturated or unsaturated fatty acid in which the ester forming ester with pentaerythritol is a saturated or unsaturated fatty acid having 16 to 18 carbon atoms. It means a mixture containing a large amount of fatty acid having a chain or a branched chain.
The ester with pentaerythritol is preferably a monoester or a diester, more preferably 75 mol% or more of the ester is a diester.

  What is marketed as INCI name "Pentaerythrityl Distearate" can be used as a commercial item of the ester of a fatty acid mixture containing a fatty acid having 16 to 18 carbon atoms and pentaerythritol. Specific commercial product names include “Cutina PES (Cognis GmbH)”, “Dub DSPE (Stearinerie Dubois Fils)”, “Radiasurf 7175 (Oleon NV)”, and the like.

The blending amount of the ester of a fatty acid mixture containing a fatty acid having 16 to 18 carbon atoms and pentaerythritol is preferably 0.5 to 5.0% by mass based on the total amount of the oil-in-water emulsified skin cosmetic. More preferably, it is 1.0-3.0 mass%.
If it is less than 0.5% by mass, it is impossible to feel the moist and rich feeling during use and the emollient feeling after use, which are the effects of the present invention. On the other hand, even if it exceeds 5.0% by mass, the effect of the present invention is not enhanced, but rather stickiness is produced during use.

“(B) A microgel obtained by dissolving a water-soluble ethylenically unsaturated monomer in a dispersed phase in a composition having an organic solvent or oil as a dispersion medium and water as a dispersed phase, and radical polymerization in the dispersed phase. From the microgel obtained by radical polymerization of dimethylacrylamide and 2-acrylamido-2-methylpropanesulfonic acid under the conditions that the surfactant forms a one-phase microemulsion or a fine W / O emulsion with a surfactant. Thickener "
The thickener composed of the microgel of the component (B) used in the present invention is a polymer microgel produced by a polymerization method generally referred to as a reverse phase emulsion polymerization method for use as a thickener, A thickener made of a synthetic polymer obtained by a homogeneous polymerization system as disclosed in JP-A-2001-114641 is a thickener having a different polymerization method and mechanical properties. In order to blend a thickener composed of a synthetic polymer obtained by a homogeneous polymerization system disclosed in JP-A-2001-114641 into cosmetics, it must be pulverized into a powder state, Molecular gels may stand out and cause problems in appearance.
The details of (B) the thickener comprising the microgel used in the present invention are described in detail in JP-A No. 2004-43785, but the microgel is a fine particle of a synthetic polymer electrolyte produced by a reverse phase microemulsion polymerization method. Since the thickener consisting of can provide a high-viscosity solution that is visually uniform in appearance, there is no problem in appearance even when blended into cosmetics.

（Ｒ₁はＨまたはメチル基、Ｒ₂及びＲ₃はそれぞれ独立にメチル基、エチル基、プロピル基、イソプロピル基を表わす。）
また、イオン性モノマーは、一般式（III）に示すアニオン性アクリルアミド誘導体、又は、一般式（ＩＶ）に示すカチオン性アクリルアミド誘導体が好ましい。











一般式（III）

（Ｒ₄及びＲ₅はそれぞれ独立にＨ又はメチル基、Ｒ₆は炭素原子数１〜６の直鎖若しくは分岐のアルキル基、Ｘは金属イオン、ＮＨ₃、アミン化合物を表す。例えば、金属イオンはLi、Na、Kのアルカリ金属イオン、アミン化合物はトリエタノールアミン、トリイソプロパノールアミン等である。）
一般式（ＩＶ）

（Ｒ₇はＨ又はメチル基、Ｒ8はＨまたは炭素原子数１〜６の直鎖若しくは分岐のアルキル基、Ｒ₉は炭素原子数１〜６の直鎖若しくは分岐のアルキル基、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂はメチル基またはエチル基、Ｙは陰性カウンターイオンを表わし、例えば、Ｃｌ、Ｂｒ等のマイナスカウンターイオンである。）
特に好ましいジアルキルアクリルアミドは、ジメチルアクリルアミド、ジエチルアクリルアミドである。
特に好ましいイオン性アクリルアミド誘導体は、２−アクリルアミド２−メチルプロパンスルホン酸およびその塩である。
特に好ましいカチオン性アクリルアミド誘導体はＮ，Ｎ，−ジメチルアミノプロピルアクリルアミドメチルクロライドである。 The water-soluble ethylenically unsaturated monomer constituting the thickener composed of microgel is preferably a combination of a nonionic monomer and an ionic monomer (anionic monomer or cationic monomer).
The nonionic monomer is preferably a dialkylacrylamide represented by the following general formula (II).
Formula (II)

(R ₁ represents H or a methyl group, and R ₂ and R ₃ each independently represents a methyl group, an ethyl group, a propyl group, or an isopropyl group.)
The ionic monomer is preferably an anionic acrylamide derivative represented by the general formula (III) or a cationic acrylamide derivative represented by the general formula (IV).











General formula (III)

(R ₄ and R ₅ are each independently H or a methyl group, R ₆ is a linear or branched alkyl group having 1 to 6 carbon atoms, X is a metal ion, NH ₃ , or an amine compound. For example, a metal ion Are Li, Na, K alkali metal ions, and amine compounds are triethanolamine, triisopropanolamine, etc.)
Formula (IV)

(R ₇ is H or a methyl group, R 8 is H or a linear or branched alkyl group having 1 to 6 carbon atoms, R ₉ is a linear or branched alkyl group having 1 to 6 carbon atoms, R ₁₀ , R ₁₁ and R ₁₂ represent a methyl group or an ethyl group, and Y represents a negative counter ion, for example, a negative counter ion such as Cl or Br.)
Particularly preferred dialkylacrylamides are dimethylacrylamide and diethylacrylamide.
Particularly preferred ionic acrylamide derivatives are 2-acrylamido 2-methylpropane sulfonic acid and its salts.
A particularly preferred cationic acrylamide derivative is N, N, -dimethylaminopropylacrylamide methyl chloride.

The monomer composition ratio in the polymerization system of the nonionic monomer and the ionic monomer (the charge ratio of the polymerization system) is arbitrarily determined arbitrarily according to the monomer composition ratio of the target microgel. The monomer composition ratio of the microgel and the charging ratio to the polymerization system are almost the same. The charging ratio (molar ratio) of the polymerization system of the nonionic monomer and the ionic monomer is usually nonionic monomer: ionic monomer = 0.5: 9.5 to 9.5: 0.5, preferably 1. : 9 to 9: 1, more preferably 7: 3 to 9: 1. The optimum ratio is nonionic monomer: ionic monomer = 8: 2.
The above-mentioned water-soluble ethylenically unsaturated monomer is arbitrarily selected, and a thickener comprising a microgel used in the present invention is polymerized. A particularly preferred thickener is a binary copolymer microgel copolymerized from dimethylacrylamide and 2-acrylamido-2-methylpropanesulfonic acid as water-soluble ethylenically unsaturated monomers. In this case, there is no need for a crosslinking monomer, and a thickener that exhibits an excellent thickening effect and a feeling of use due to self-crosslinking can be obtained.

架橋性モノマーの使用量は、２−アクリルアミド−２−メチルプロパンスルホン酸またはその塩とジアルキルアクリルアミドの全モル数に対し0.0001〜2.0モル％の範囲で添加されることが好ましい。0.0001モル％未満で調製された増粘剤は架橋の効果が見られない場合がある。また、2モル％を超えて調製された場合、架橋密度が高すぎてミクロゲルが充分に膨潤出来ないために充分な増粘効果を発揮しない場合がある。 In addition, it is also preferable to use a crosslinking monomer, and it is also preferable to use a crosslinked N, N-dimethylacrylamide-2-acrylamido-2-methylpropanesulfonic acid sodium copolymer in the present invention. In that case, a crosslinking monomer represented by the general formula (V) is preferable, and methylenebisacrylamide is particularly preferable.
General formula (V)

The use amount of the crosslinkable monomer is preferably in the range of 0.0001 to 2.0 mol% with respect to the total number of moles of 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof and dialkylacrylamide. Thickeners prepared at less than 0.0001 mol% may not have a crosslinking effect. Moreover, when it exceeds 2 mol%, since a crosslinking density is too high and a microgel cannot fully swell, it may not exhibit sufficient thickening effect.

The molecular weight of the microgel used in the present invention is about 100,000 to 5,000,000 (average in terms of PEG: measured by GPC), and is adjusted by the viscosity required as a thickener.
The microgel constituting the present invention has all the following rheological properties (1) to (3). The thickener composed of the microgel is obtained by the production method by the polymerization method described above, and is preferably used as a thickener.
(1) The apparent viscosity of an aqueous dispersion of 0.5% (mass percentage) of the microgel is 10,000 mPa · s or more at a shear rate of 1.0 s ⁻¹ .
(2) The apparent viscosity of a 0.5% (percentage by mass) ethanol dispersion of the microgel is 5000 mPa · s or more at a shear rate of 1.0 s ⁻¹ .
(3) The dynamic elastic modulus of the microgel in a 0.5% (mass percentage) aqueous dispersion or ethanol dispersion is G ′> G ″ within a strain of 1% or less and a frequency of 0.01 to 10 Hz.
The apparent viscosity of the microgel water or ethanol dispersion is a viscosity at a measurement temperature of 25 ° C. and a shear rate of 1 s ⁻¹ using a cone plate rheometer (MCR-300 manufactured by Paar Rhysica).
The dynamic elastic modulus is the value of the storage elastic modulus (G ') and loss elastic modulus (G ") measured at a measurement temperature of 25 ° C and a strain of 1% or less in a frequency range of 0.01 to 10 Hz using the same measuring device. Means.
The microgel can be separated in a powder state after polymerization through a simple precipitation purification process. The microgel separated into a powder form easily disperses in water or ethanol or a mixed solvent of water / ethanol, swells quickly, and functions as a thickener.
In addition, by selecting a strongly acidic monomer (for example, a monomer containing a sulfonic acid residue) as an ionic monomer to be copolymerized with the microgel, an acidic preparation that cannot be thickened with a conventional carboxyvinyl polymer can be obtained. Thickening is also possible.

  The blending amount of the thickener comprising the microgel microgel used in the present invention is 0.1 to 2.0% by mass, preferably 0.2 to 1.5% by mass, based on the total amount of the oil-in-water emulsified skin cosmetic. It is. When it exceeds 2.0 mass%, a problem may arise in terms of stickiness or freshness. On the other hand, when the amount is less than 0.1% by mass, the feeling of use is inferior to the feeling of stickiness and may cause a problem in stability over time.

  In addition to the above essential components, the oil-in-water emulsified skin cosmetic of the present invention usually contains oil, water, emulsifier (surfactant), moisturizer, Other components can be appropriately blended within a range not impairing the effects of the present invention, and mixed by a conventional method. The amounts of oil, water, and emulsifier (surfactant) are appropriately determined according to the target product.

For example, hydrocarbon oils, silicone oils, waxes, fatty acid esters, higher alcohols, ultraviolet absorbers and the like are used as oil components constituting the oil phase.
Specifically, examples of the hydrocarbon oil include liquid paraffin, ozokerite, squalane, pristane, paraffin, ceresin, squalene, petrolatum, microcrystalline wax, polyethylene wax, and Fischer Tropus wax.
Examples of the silicone oil include linear polysiloxanes (for example, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.); cyclic polysiloxanes (for example, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, etc.), 3 Silicone resin forming a three-dimensional network structure, silicone rubber having an average molecular weight of 200,000 or more, various modified polysiloxanes (amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane, etc.) It is done.
Examples of waxes include beeswax, candelilla wax, carnauba wax, lanolin, liquid lanolin, jojoballow and the like.
Examples of fatty acid esters include myristyl myristate, cetyl palmitate, cholesteryl stearate, beeswax fatty acid 2-octyldodecyl, and the like.
Examples of the higher alcohol include hexyl alcohol, octyl alcohol, cetyl alcohol, stearyl alcohol, ceryl alcohol, behenyl alcohol, triacontyl alcohol, seraalkyl alcohol, and batyl alcohol.

Examples of the ultraviolet absorber include the following compounds.
(1) Benzoic acid-based ultraviolet absorbers For example, paraaminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester, N, N-dimethyl PABA ethyl ester, N, N-dimethyl PABA butyl ester, N, N-dimethyl PABA ethyl ester and the like.
(2) Anthranilic acid ultraviolet absorbers such as homomenthyl-N-acetylanthranilate.
(3) Salicylic acid ultraviolet absorbers such as amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate, and the like.
(4) Cinnamic acid UV absorbers For example, octyl cinnamate, ethyl-4-isopropyl cinnamate, methyl-2,5-diisopropyl cinnamate, ethyl-2,4-diisopropyl cinnamate, methyl-2,4- Diisopropyl cinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate, octyl-p-methoxycinnamate (2-ethylhexyl-p-methoxycinnamate), 2-ethoxy Ethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, glyceryl mono-2-ethylhexanoyl -Diparamethoxy Such as Nameto.
(5) Triazine-based ultraviolet absorber, for example, bisresorcinyl triazine. More specifically, bis {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) 1,3,5-triazine, 2,4,6-tris { 4- (2-ethylhexyloxycarbonyl) anilino} 1,3,5-triazine and the like.
(6) Other ultraviolet absorbers For example, 3- (4′-methylbenzylidene) -d, l-camphor, 3-benzylidene-d, l-camphor, 2-phenyl-5-methylbenzoxazole, 2,2 '-Hydroxy-5-methylphenylbenzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenylbenzotriazole), dianisoylmethane, 4-methoxy-4′-t-butyldibenzoylmethane, 5- (3,3-dimethyl-2-norbornylidene) -3-pentan-2-one, pyridazine derivatives such as dimorpholinopyridazinone.

  The blending amount of the oil component and the ultraviolet absorber constituting the oil phase is appropriately determined according to the target product.

  On the other hand, as water phase components of oil-in-water emulsified skin cosmetics with water, polyhydric alcohols, water-soluble polymers, lower alcohols, antioxidants, preservatives, organic or inorganic salts and their salts, various Examples include water-soluble drugs, plant extracts, and pigments. In addition, the compounding quantity of a water phase component is suitably determined according to the target product.

Specifically, examples of the polyhydric alcohol include polyethylene glycol, glycerin, diglycerin, 1,3-butylene glycol, erythritol, sorbitol, xylitol, maltitol, 1,2-pentanediol, hexylene glycol and the like. It is done.
Examples of the water-soluble polymer include carrageenan, pectin, mannan, curdlan, chondroitin sulfate, starch, glycogen, gum arabic, sodium hyaluronate, tragacanth gum, xanthan gum, mucoitin sulfate, hydroxyethyl guar gum, carboxymethyl guar gum, guar gum, dextran. , Keratosulfuric acid, locust bean gum, succinoglucan, chitin, chitosan, carboxymethylchitin, agar and the like.
Examples of the lower alcohol include ethanol.
Examples of the antioxidant include butylhydroxytoluene, σ-tocopherol, phytin and the like.
Examples of the preservative include benzoic acid, salicylic acid, sorbic acid, paraoxybenzoic acid alkyl ester, phenoxyethanol, hexachlorophene, and ε-polylysine.
Examples of organic or inorganic acids and salts thereof include citric acid, lactic acid, hexametaphosphoric acid and the like.
Examples of the various water-soluble drugs include salts of L-ascorbic acid and its derivatives, salts of tranexamic acid and its derivatives, salts of alkoxysalicylic acid and its derivatives, salts of glutathione and its derivatives, and the like.
L-ascorbic acid is generally referred to as vitamin C, and has a cell respiration effect, an enzyme activation effect, a collagen formation action by a strong reduction action, and a melanin reduction action. L-ascorbic acid derivatives include L-ascorbic acid monostearate, L-ascorbic acid monopalmitate, L-ascorbic acid monoalkyl esters such as L-ascorbic acid monooleate; L-ascorbic acid monophosphate, L- L-ascorbic acid monoesters such as ascorbic acid-2-sulfate; L-ascorbic acid dialkyl esters such as L-ascorbic acid distearate, L-ascorbic acid dipalmitate, L-ascorbic acid dioleate; L-ascorbic acid tristearate L-ascorbic acid trialkyl esters such as Late, L-ascorbic acid tripalmitate, L-ascorbic acid trioleate; L-ascorbic acid triesters such as L-ascorbic acid triphosphate; - such as L- ascorbic acid glucosides such as ascorbic acid 2-glucoside and the like. In this invention, it uses suitably in the form of each salt of L-ascorbic acid, L-ascorbic acid phosphate ester, L-ascorbic acid-2-sulfate ester, and L-ascorbic acid 2-glucoside.
Examples of the tranexamic acid derivatives include dimers of tranexamic acid (for example, trans-4- (trans-aminomethylcyclohexanecarbonyl) aminomethylcyclohexanecarboxylic acid, etc.), and esters of tranexamic acid and hydroquinone (for example, 4- (Trans-aminomethylcyclohexanecarboxylic acid 4′-hydroxyphenyl ester, etc.), ester form of tranexamic acid and gentisic acid (for example, 2- (trans-4-aminomethylcyclohexylcarbonyloxy) -5-hydroxybenzoic acid, etc. ), Amides of tranexamic acid (for example, trans-4-aminomethylcyclohexanecarboxylic acid methylamide, trans-4- (p-methoxybenzoyl) aminomethylcyclohexanecarboxylic acid, trans-4-guanidinome) In the present invention, it is preferably used in the form of a salt of tranexamic acid or a salt of tranexamic acid derivative.
Alkoxysalicylic acid is one in which the hydrogen atom at the 3-position, 4-position or 5-position of salicylic acid is substituted with an alkoxy group, and the alkoxy group as the substituent is preferably a methoxy group, an ethoxy group or a propoxy group. , An isopropoxy group, a butoxy group or an isobutoxy group, more preferably a methoxy group or an ethoxy group. Specific examples of compound names include 3-methoxysalicylic acid, 3-ethoxysalicylic acid, 4-methoxysalicylic acid, 4-ethoxysalicylic acid, 4-propoxysalicylic acid, 4-isopropoxysalicylic acid, 4-butoxysalicylic acid, 5-methoxysalicylic acid. , 5-ethoxysalicylic acid, 5-propoxysalicylic acid and the like. In this invention, it uses suitably in the form of each salt of alkoxy salicylic acid and its derivatives (ester etc.).
Although it does not specifically limit as a salt of the said chemical | medical agent, For example, salts, such as ammonium salt and an amino acid salt other than alkali metal salt or alkaline-earth metal salt like sodium salt, potassium salt, calcium salt, are mentioned.

In addition, as an optional component that can be blended in the present invention as an oil phase component or an aqueous phase component, the following components may be mentioned.
Examples of vitamin A derivatives include vitamin A, vitamin A palmitate, vitamin A acetate and the like.
Examples of vitamin B derivatives include vitamin B ₆ hydrochloride, vitamin B ₆ tripalmitate, vitamin B ₆ dioctanoate, vitamin B ₂ and derivatives thereof, vitamin B ₁₂ , vitamin B ₁₅ and derivatives thereof, and the like.
Examples of vitamin E derivatives include α-tocopherol, β-tocopherol, vitamin E acetate and the like.
Other vitamins such as vitamin D, vitamin H, pantothenic acid, panthetin; γ-oryzanol, allantoin, glycyrrhizic acid (salt), glycyrrhetinic acid, stearyl glycyrrhetinate, hinokitiol, bisabolol, eucalptone, thymol, inositol, psycho Saponins such as saponin, carrot saponin, loofah saponin, muclodisaponin, various drugs such as pantothenyl ethyl ether, arbutin, cephalanthin, borage, clara, kohone, orange, sage, yarrow, mallow, thyme, spruce, spruce, Extracts of plants such as birch, horsetail, loofah, maroonier, cypress, argon, arnica, lily, mugwort, peony, aloe, gardenia, cherry leaf, pigments such as β-carotene, etc. Can be blended.

Moreover, the emulsifier (surfactant) normally mix | blended with cosmetics can be used for this invention. Specific examples include the following emulsifiers (surfactants).
Hexaglyceryl monolaurate (HLB value 14.5), hexaglyceryl monomyristate (HLB value 11), hexaglyceryl monostearate (HLB value 9.0), hexaglyceryl monooleate (HLB value 9.0), monolaurin Decaglyceryl acid (HLB value 15.5), decaglyceryl monomyristate (HLB value 14.0), decaglyceryl monostearate (HLB value 12.0), decaglyceryl monoisostearate (HLB value 12.0), Polyglycerol fatty acid esters such as decaglyceryl monooleate (HLB value 12.0), decaglyceryl distearate (HLB value 9.5), decaglyceryl diisostearate (HLB value 10.0), and the like.
5 mole addition of polyoxyethylene monostearate (referred to as “POE (5)”, hereinafter the same) glyceryl (HLB value 9.5), POE (15) glyceryl monostearate (HLB value 13.5), monooleic acid Polyoxyethylene glycerin fatty acid esters such as POE (5) glyceryl (HLB value 9.5) and monooleic acid POE (15) glyceryl (HLB value 14.5).
Mono palm oil fatty acid POE (20) sorbitan (HLB value 16.9), monopalmitic acid POE (20) sorbitan (HLB value 15.6), monostearic acid POE (20) sorbitan (HLB value 14.9), monostearin Acid POE (6) sorbitan (HLB value 9.5), tristearic acid POE (20) sorbitan (HLB value 10.5), monoisostearic acid POE (20) sorbitan (HLB value 15.0), monooleic acid POE (20) Polyoxyethylene sorbitan fatty acids such as sorbitan (HLB value 15.0), monooleic acid POE (6) sorbitan (HLB value 10.0), trioleic acid POE (20) sorbitan (HLB value 11.0) Esters.
Monolauric acid POE (6) sorbite (HLB value 15.5), tetrastearic acid POE (60) sorbite (HLB value 13.0), tetraoleic acid POE (30) sorbite (HLB value 11.5), tetraoleic acid Polyoxyethylene sorbite fatty acid esters such as POE (40) sorbit (HLB value 12.5) and tetraoleic acid POE (60) sorbite (HLB value 14.0).
POE (10) lanolin (HLB value 12.0), POE (20) lanolin (HLB value 13.0), POE (30) lanolin (HLB value 15.0), POE (5) lanolin alcohol (HLB value 12. 5), POE (10) lanolin alcohol (HLB value 15.5), POE (20) lanolin alcohol (HLB value 16.0), POE (40) lanolin alcohol (HLB value 17.0), POE (20) sorbit Polyoxyethylene lanolin, lanolin alcohol, beeswax derivatives such as beeswax (HLB value 9.5).
POE (20) castor oil (HLB value 10.5), POE (40) castor oil (HLB value 12.5), POE (50) castor oil (HLB value 14.0), POE (60) castor oil (HLB) Value 14.0), POE (20) hydrogenated castor oil (HLB value 10.5), POE (30) hydrogenated castor oil (HLB value 11.0), POE (40) hydrogenated castor oil (HLB value 13.5) POE (60) hydrogenated castor oil (HLB value 14.0), POE (80) hydrogenated castor oil (HLB value 16.5), POE (40) hydrogenated castor oil (100) hydrogenated castor oil (HLB value 16.5) ) And other polyoxyethylene castor oils and hardened castor oils.
POE (5) phytosterol (HLB value 9.5), POE (10) phytosterol (HLB value 12.5), POE (20) phytosterol (HLB value 15.5), POE (30) phytosterol (HLB value 18.0) ), POE (25) phytostanol (HLB value 14.5), POE (30) cholestanol (HLB value 17.0), and other polyoxyethylene sterols and hydrogenated sterols.
POE (2) lauryl ether (HLB value 9.5), POE (4.2) lauryl ether (HLB value 11.5), POE (9) lauryl ether (HLB value 14.5), POE (5.5) Cetyl ether (HLB value 10.5), POE (7) cetyl ether (HLB value 11.5), POE (10) cetyl ether (HLB value 13.5), POE (15) cetyl ether (HLB value 15.5) ), POE (20) cetyl ether (HLB value 17.0), POE (23) cetyl ether (HLB value 18.0), POE (4) stearyl ether (HLB value 9.0), POE (20) stearyl ether (HLB value 18.0), POE (21) stearyl ether (HLB value 18.0), POE (7) oleyl ether (HLB value 10.5), POE 10) oleyl ether (HLB value 14.5), POE (15) oleyl ether (HLB value 16.0), POE (20) oleyl ether (HLB value 17.0), POE (50) oleyl ether (HLB value 18) 0.0), POE (10) behenyl ether (HLB value 10.0), POE (20) behenyl ether (HLB value 16.5), POE (30) behenyl ether (HLB value 18.0), POE (2) (C _12-15 ) alkyl ether (HLB value 9.0), POE (4) (C _12-15 ) alkyl ether (HLB value 10.5), POE (10) (C _12-15 ) alkyl ether (HLB 15.5), POE (5) secondary alkyl ether (HLB value 10.5), POE (7) secondary alkyl ether (HLB value 12.0), POE (9) alkyl Ether (HLB value 13.5), POE (12) polyoxyethylene alkyl ethers such as alkyl ether (HLB value 14.5).
1 mol addition of polyoxypropylene (hereinafter referred to as “POP (1)”, hereinafter the same) POP (4) cetyl ether (HLB value 9.5), POE (10) POP (4) cetyl ether (HLB value 10.5) , POE (20) POP (8) cetyl ether (HLB value 12.5), POE (20) POP (6) decyl tetradecyl ether (HLB value 11.0), POE (30) POP (6) decyl tetradecyl Polyoxyethylene polyoxypropylene alkyl ethers such as ether (HLB value 12.0).
Polyethylene glycol monolaurate 10 mol addition (hereinafter referred to as “PEG (10)”, hereinafter the same) (HLB value 12.5), PEG monostearate (10) (HLB value 11.0), PEG monostearate (25) (HLB value 15.0), PEG monostearate (40) (HLB value 17.5), PEG monostearate (45) (HLB value 18.0), PEG monostearate (55) (HLB value 18. 0), PEG 100 monostearate (HLB value 18.8), PEG monostearate 150 (HLB value 19), PEG monooleate (10) (HLB value 11.0), PEGyl distearate (HLB value 16.5) Polyethylene glycol fatty acid esters such as PEG diisostearate (HLB value 9.5).
PEG (8) glyceryl isostearate (HLB value 10.0), PEG (10) glyceryl isostearate (HLB value 10.0), PEG (15) glyceryl isostearate (HLB value 12.0), PEG isostearate (20 ) Glyceryl (HLB value 13.0), PEG isostearate (25) Glyceryl (HLB value 14.0), PEG glyceryl isostearate (30) (HLB value 15.0), PEG isyl stearate (40) glyceryl (HLB value) 15.0), polyoxyethylene glyceryl isostearates such as PEG (50) glyceryl isostearate (HLB value 16.0) and PEG (60) glyceryl isostearate (HLB value 16.0).
Polyoxyethylene cetyl ethers such as POE (2) cetyl ether (HLB value 5), POE (3) cetyl ether (HLB value 6), POE (5) cetyl ether (HLB value 8), and the like.
Polyoxyethylene oleyl ethers such as POE (3) oleyl ether (HLB value 6), POE (5) oleyl ether (HLB value 8), POE (6) oleyl ether (HLB value 8), and the like.
Polyoxyethylene isocetyl ethers such as POE (5) isocetyl ether (HLB value 8).
Polyoxyethylene isostearyl ethers such as POE (5) isostearyl ether (HLB value 8).
Polyoxyethylene octyldodecyl ethers such as POE (5) octyldodecyl ether (HLB value 7).
Polyoxyethylene behenyl ethers such as POE (5) behenyl ether (HLB value 7).
Polyoxyethylene decyl tetradecyl ethers such as POE (5) decyl tetradecyl ether (HLB value 6).
Polyoxyethylene cholesteryl ethers such as POE (5) cholesteryl ether (HLB value 7).
Polyoxyethylene / polyoxypropylene decyl ethers such as POP (2) POE (3) decyl ether (HLB value 7).
Sorbitan fatty acid esters such as sorbitan sesquioleate (HLB value 7) and sorbitan sesquiisostearate (HLB value 7).
Glyceryl stearate (HLB value 5), self-emulsifying glyceryl stearate (HLB value 5), self-emulsifying glyceryl stearate (HLB value 6), self-emulsifying glyceryl stearate (HLB value 7), glyceryl isostearate (HLB) Mono-fatty acid glyceryls such as value 6) and glyceryl diisostearate (HLB value 3).
Propylene glycol stearate (HLB value 4), propylene glycol laurate (HLB value 5), propylene glycol distearate (HLB value 2), propylene glycol dioleate (HLB value 2), propylene glycol dilaurate (HLB value 2), Propylene glycol fatty acid esters such as propylene glycol diisostearate (HLB value 2).
Glycol stearate (HLB value 4), glycol dilaurate (HLB value 2), glycol dioleate (HLB value 2), glycol distearate (HLB value 2), fatty acid (C _14-18 ) glycol (HLB value 2), etc. Ethylene glycol fatty acid esters.
PEG stearate (2) (HLB value 5), PEG stearate (3) (HLB value 7), PEG stearate (5) (HLB value 8), PEG monostearate (10) (HLB value 11.0) PEG monostearate PEG (25) (HLB value 15.0), PEG monostearate (PEG 40 monostearate) (HLB value 17.5), PEG monostearate (45) (HLB value 18. 0), PEG monostearate (55) (HLB value 18.0), PEG monostearate (100) (HLB value 18.8), PEG monostearate
(150) Polyethylene glycol monostearate such as (HLB value 19.0).
Monooleic acid polyethylene glycols such as oleic acid PEG (3) (HLB value 7).
Polyoxyethylene hydrogenated castor oils such as PEG (5) hydrogenated castor oil (HLB value 5), PEG (7) hydrogenated castor oil (HLB value 6), PEG (10) hydrogenated castor oil (HLB value 7), etc. .
Polyethylene glycol isostearates such as PEG (3) isostearate (HLB value 7).
Stearic acid POE (3) cetyl ether (HLB value 3), stearic acid POE (4) cetyl ether (HLB value 4), stearic acid POE (6) cetyl ether (HLB value 6), stearic acid POE (7) cetyl ether Stearic acid polyoxyethylene cetyl ethers such as (HLB value 7);
Stearic acid POE (4) stearyl ether (HLB value 4), stearic acid POE (6) stearyl ether (HLB value 5), stearic acid POE (9) stearyl ether (HLB value 6), stearic acid POE (7) stearyl ether Stearic acid polyoxyethylene stearyl ethers such as (HLB value 7), stearic acid POE (10) stearyl ether (HLB value 7), stearic acid POE (12) stearyl ether (HLB value 8);
Stearic acid POE (3) lauryl ether (HLB value 3), stearic acid POE (5) lauryl ether (HLB value 5), stearic acid POE (8) lauryl ether (HLB value 7), stearic acid POE (10) lauryl ether Stearic acid polyoxyethylene lauryl ethers such as (HLB value 8);
Isostearic acid POE (2) lauryl ether (HLB value 2), isostearic acid POE (5) lauryl ether (HLB value 5), isostearic acid POE (8) lauryl ether (HLB value 7), isostearic acid POE (8) lauryl ether Isostearic acid polyoxyethylene lauryl ethers such as (HLB value 7) and isostearic acid POE (10) lauryl ether (HLB value 8).
Dilauric acid PEG (2) (HLB value 4), dilauric acid PEG (3) (HLB value 5), dilauric acid PEG (4) (HLB value 5), dilauric acid PEG (6) (HLB value 5), dilauric acid Polyethylene glycol dilaurates such as PEG (8) (HLB value 8).
Distearic acid PEG (2) (HLB value 2), distearic acid PEG (3) (HLB value 3), distearic acid PEG (3) (HLB value 3), distearic acid PEG (3) (HLB value 3), distearic acid PEG (4) (HLB value 4), distearic acid PEG (6) (HLB value 5), distearic acid PEG (8) (HLB value 6), distearic acid PEG (12) (HLB value 8), distearic acid PEG ( Polyethylene glycol distearate such as HLB value 8).
Diisostearic acid PEG (2) (HLB value 3), diisostearic acid PEG (3) (HLB value 3), diisostearic acid PEG (4) (HLB value 4), diisostearic acid PEG (6) (HLB value 5), diisostearic acid Diisostearic polyethylene glycols such as PEG (8) (HLB value 6) and diisostearic acid PEG (12) (HLB value 8).
Dioleic acid PEG (2) (HLB value 3), Dioleic acid PEG (3) (HLB value 3), Dioleic acid PEG (4) (HLB value 4), Dioleic acid PEG (6) (HLB value 5), Dioleic acid Dioleic acid polyethylene glycols such as PEG (8) (HLB value 6) and dioleic acid PEG (12) (HLB value 8).
Polyoxyethylene sorbit sorbitan fatty acid such as PEG (4) sorbit tetraoleate (HLB value 3), PEG (3) sorbite tristearate (HLB value 3), PEG (4) sorbitan triisostearate (HLB value 3) Esters.
PEG (3) glyceryl triisostearate (HLB value 2), PEG (5) glyceryl triisostearate (HLB value 3), PEG (10) glyceryl triisostearate (HLB value 3), glyceryl triisostearate (20) Polyoxyethylene glyceryl triisostearate such as (HLB value 8).
Polyisoethylene glyceryl diisostearate such as PEG (10) glyceryl diisostearate (HLB value 7).
Polyoxyethylene glyceryl isostearates such as PEG (3) glyceryl isostearate (HLB value 6), PEG (5) glyceryl isostearate (HLB value 8), and PEG (6) glyceryl isostearate (HLB value 8).
PEG tristearate (3) glyceryl (HLB value 2), PEG tristearate (4) glyceryl (HLB value 2), PEG tristearate (5) glyceryl (HLB value 3), glyceryl tristearate (6) Polyoxyethylene glyceryl tristearates such as (HLB value 3), PEG (10) glyceryl tristearate (HLB value 5), PEG (20) tristearate (HLB value 8) and the like.
Polyoxyethylene glyceryl distearates such as PEG (4) glyceryl distearate (HLB value 4).
PEG trioleate (3) glyceryl (HLB value 2), PEG trioleate (5) glyceryl (HLB value 3), PEG trioleate (10) glyceryl (HLB value 5), glyceryl trioleate (20) Polyoxyethylene glyceryl trioleates such as (HLB value 8).
PEG (5) hydrogenated castor oil (HLB value 4), isostearic acid PEG (10) hydrogenated castor oil (HLB value 5), isostearic acid PEG (15) hydrogenated castor oil (HLB value 7), isostearic acid Polyoxyethylene hydrogenated castor oil isostearate such as PEG (20) hydrogenated castor oil (HLB value 8).
PEG (5) hydrogenated castor oil (HLB value 2), triisostearic acid PEG (10) hydrogenated castor oil (HLB value 4), triisostearic acid PEG (15) hydrogenated castor oil (HLB value 5) PEG (20) hydrogenated castor oil (HLB value 6), triisostearic acid PEG (30) hydrogenated castor oil (HLB value 7), triisostearic acid PEG (40) hydrogenated castor oil (HLB value 8) ) And the like, polyisoethylene stearic acid polyoxyethylene hydrogenated castor oil.
Lauric acid polyoxyethylene hydrogenated castor oil such as lauric acid PEG (20) hydrogenated castor oil (HLB value 8).
Polystearic acid PEG (3) trimethylolpropane (HLB value 2), tristearic acid PEG (5) trimethylolpropane (HLB value 3), tristearic acid PEG (10) trimethylolpropane (HLB value 5), etc. Oxyethylene tristearate trimethylolpropane.
Polyoxyethylene trimyristate trimethylolpropanes such as trimyristate PEG (3) trimethylolpropane (HLB value 2) and trimyristate PEG (5) trimethylolpropane (HLB value 3).
Polyoxyethylene distearate such as PEG (3) distearate (3) trimethylolpropane (HLB value 3), PEG (4) distearate (4) trimethylolpropane (HLB value 4), PEG (3) distearate (3) trimethylolpropane (HLB value 4) Acid trimethylolpropane.
Polyoxyethylene triisostearate trimethylolpropanes such as PEG (3) triisostearate (3) trimethylolpropane (HLB value 2) and PEG (20) triisostearate (HLB value 8).
Lauroylglutamate dihexyldecyl (HLB value 3), lauroylglutamate dioctyldodecyl (HLB value 3), stearoylglutamate dioctyldodecyl (HLB value 3), lauroylglutamate dioctyldodecyl (HLB value 3), lauroylglutamate dioctyldecyl ether ether POD HLB value 4), dioctyl lauroyl glutamate POE (5) dodecyl ether (HLB value 6), lauroyl glutamic acid POE (2) distearyl ether (HLB value 4), lauroyl glutamic acid POE (5) distearyl ether (HLB value 7), etc. N-acyl glutamates.
N-acyl neutral amino acid esters such as hexyldecyl myristoylmethylaminopropionate (HLB value 4).
Polyglyceryl stearate (2) (HLB value 6), polyglyceryl stearate (2) (HLB value 8), polyglyceryl distearate (2) (HLB value 4), polyglyceryl distearate (3) (HLB value 5), distearic acid Polyglyceryl (6) (HLB value 8), polyglyceryl tristearate (10) (HLB value 8), polyglyceryl diisostearate (2) (HLB value 4), polyglyceryl triisostearate (2) (HLB value 3), diisostearic acid Polyglyceryl (3) (HLB value 5), polyglyceryl diisostearate (6) (HLB value 8) polyglyceryl triisostearate (10) (HLB value 8), polyglyceryl oleate (2) (HLB value 8), polyglyceryl diisostearate ( 2) (HLB 4), polyglycerol fatty acid esters such as polyglyceryl diisostearate (3) (HLB value 5).
Silicone surfactants such as PEG (7) dimethicone (HLB value 5) and PEG (10) dimethicone (HLB value 6).

The oil-in-water emulsified skin cosmetic of the present invention can be preferably produced in a gel-like or cream-like product such as a moisturizing serum, anti-aging cosmetic liquid, whitening cosmetic liquid, moisturizing cream, anti-aging cream, whitening cream.
These products can be produced by a conventional method by mixing the essential components (A) and (B) of the present invention, water, and any blending components that are usually blended in cosmetics.

  Next, the present invention will be described in detail with reference to examples. The present invention is not limited only to the following examples. Unless otherwise specified, the amount is shown in mass%.

  First, the synthesis example of the microgel which comprises the thickener used for this invention is demonstrated. The microgel obtained in the synthesis example is a thickener composed of the microgel of component (B) used in the present invention.

Synthesis example 1
40 g of dimethylacrylamide (manufactured by Kojin) and 9 g of 2-acrylamide-2-methylpropanesulfonic acid (manufactured by Sigma) are dissolved in 250 g of ion-exchanged water and adjusted to pH = 7.0 with sodium hydroxide. To a 1000 ml three-necked flask equipped with a reflux apparatus, 250 g of n-hexane, 8.2 g of polyoxyethylene (3) oleyl ether (Emalex 503, manufactured by Nippon Emulsion) and polyoxyethylene (6) oleyl ether (Emalex 506, 16.4g (made in Japan Emulsion) is mixed and dissolved to replace N ₂ . An aqueous monomer solution is added to the three-necked flask and heated to 65 ° C. to 70 ° C. in an oil bath while stirring in an N ₂ atmosphere. After confirming that the system is in a translucent microemulsion state when the temperature of the system reaches 65 ° C. to 70 ° C., 2 g of ammonium persulfate is added to the polymerization system to start the polymerization. A microgel is produced by maintaining the polymerization system at 65 ° C. to 70 ° C. with stirring for 3 hours. After the polymerization is completed, acetone is added to the microgel suspension to precipitate the microgel, followed by washing with acetone three times to remove residual monomer and surfactant. The precipitate is filtered and dried under reduced pressure to obtain a dried white powdered microgel.

Synthesis example 2
35 g of dimethylacrylamide (manufactured by Kojin) and 17.5 g of 2-acrylamido-2-methylpropanesulfonic acid (manufactured by Sigma) are dissolved in 260 g of ion-exchanged water and adjusted to pH = 7.0 with sodium hydroxide. In a 1000 ml three-necked flask equipped with a reflux apparatus, 260 g of n-hexane, polyoxyethylene (3) oleyl ether (Emalex 503, manufactured by Nippon Emulsion) 8.7 g and polyoxyethylene (6) oleyl ether (Emalex 506, Japanese-made emulsion) 17.6g were mixed and dissolved into the N ₂ to replace. An aqueous monomer solution is added to the three-necked flask and heated to 65 ° C. to 70 ° C. in an oil bath while stirring in an N ₂ atmosphere. After confirming that the system is in a translucent microemulsion state when the temperature of the system reaches 65 ° C. to 70 ° C., 2 g of ammonium persulfate is added to the polymerization system to start the polymerization. A microgel is produced by maintaining the polymerization system at 65 ° C. to 70 ° C. with stirring for 3 hours. After the polymerization is completed, acetone is added to the microgel suspension to precipitate the microgel, followed by washing with acetone three times to remove residual monomer and surfactant. The precipitate is filtered and dried under reduced pressure to obtain a dried white powdered microgel.

Synthesis example 3
30 g of dimethylacrylamide (manufactured by Kojin) and 26.7 g of 2-acrylamide-2-methylpropanesulfonic acid (manufactured by Sigma) are dissolved in 280 g of ion-exchanged water, and the pH is adjusted to 7.0 with sodium hydroxide. To a 1000 ml three-necked flask equipped with a reflux apparatus, 280 g of n-hexane, 9.4 g of polyoxyethylene (3) oleyl ether (Emalex 503, manufactured by Nippon Emulsion) and polyoxyethylene (6) oleyl ether (Emalex 506, Japanese-made emulsion) 19g were mixed and dissolved into the N ₂ to replace. An aqueous monomer solution is added to the three-necked flask and heated to 65 ° C. to 70 ° C. in an oil bath while stirring in an N ₂ atmosphere. After confirming that the system is in a translucent microemulsion state when the temperature of the system reaches 65 ° C. to 70 ° C., 2 g of ammonium persulfate is added to the polymerization system to start the polymerization. A microgel is produced by maintaining the polymerization system at 65 ° C. to 70 ° C. with stirring for 3 hours. After the polymerization is completed, acetone is added to the microgel suspension to precipitate the microgel, followed by washing with acetone three times to remove residual monomer and surfactant. The precipitate is filtered and dried under reduced pressure to obtain a dried white powdered microgel.

Synthesis example 4
35 g of dimethylacrylamide (manufactured by Kojin), 17.5 g of 2-acrylamide-2-methylpropanesulfonic acid (manufactured by Sigma) and 7 mg of methylenebisacrylamide are dissolved in 260 g of ion-exchanged water and adjusted to pH = 7.0 with sodium hydroxide. In a 1000 ml three-necked flask equipped with a reflux apparatus, 260 g of n-hexane, polyoxyethylene (3) oleyl ether (Emalex 503, manufactured by Nippon Emulsion) 8.7 g and epolyoxyethylene (6) oleyl ether (Emalex 506) , manufactured by Nippon emulsion) 17.6g were mixed and dissolved into the N ₂ to replace. An aqueous monomer solution is added to the three-necked flask and heated to 65 ° C. to 70 ° C. in an oil bath while stirring in an N ₂ atmosphere. After confirming that the system is in a translucent microemulsion state when the temperature of the system reaches 65 ° C. to 70 ° C., 2 g of ammonium persulfate is added to the polymerization system to start the polymerization. A microgel is produced by maintaining the polymerization system at 65 ° C. to 70 ° C. with stirring for 3 hours. After the polymerization is completed, acetone is added to the microgel suspension to precipitate the microgel, followed by washing with acetone three times to remove residual monomer and surfactant. The precipitate is filtered and dried under reduced pressure to obtain a dried white powdered microgel.

Synthesis example 5
35 g of dimethylacrylamide (manufactured by Kojin), 17.5 g of 2-acrylamide-2-methylpropanesulfonic acid (manufactured by Sigma) and 70 mg of methylenebisacrylamide are dissolved in 260 g of ion-exchanged water and adjusted to pH = 7.0 with sodium hydroxide. In a 1000 ml three-necked flask equipped with a reflux apparatus, 260 g of n-hexane, polyoxyethylene (3) oleyl ether (Emalex 503, manufactured by Nippon Emulsion) 8.7 g and polyoxyethylene (6) oleyl ether (Emalex 506, Japanese-made emulsion) 17.6g were mixed and dissolved into the N ₂ to replace. An aqueous monomer solution is added to the three-necked flask and heated to 65 ° C. to 70 ° C. in an oil bath while stirring in an N ₂ atmosphere. After confirming that the system is in a translucent microemulsion state when the temperature of the system reaches 65 ° C. to 70 ° C., 2 g of ammonium persulfate is added to the polymerization system to start the polymerization. A microgel is produced by maintaining the polymerization system at 65 ° C. to 70 ° C. with stirring for 3 hours. After the polymerization is completed, acetone is added to the microgel suspension to precipitate the microgel, followed by washing with acetone three times to remove residual monomer and surfactant. The precipitate is filtered and dried under reduced pressure to obtain a dried white powdered microgel.

Synthesis Example 6
35 g of dimethylacrylamide (manufactured by Kojin) and 17.5 g of N, N-dimethylaminopropylacrylamide methyl chloride (manufactured by Kojin) are dissolved in 260 g of ion-exchanged water. In a 1000 ml three-necked flask equipped with a reflux apparatus, 260 g of n-hexane, polyoxyethylene (3) oleyl ether (Emalex 503, manufactured by Nippon Emulsion) 8.7 g and polyoxyethylene (6) oleyl ether (Emalex 506, Japanese-made emulsion) 17.6g were mixed and dissolved into the N ₂ to replace. An aqueous monomer solution is added to the three-necked flask and heated to 65 ° C. to 70 ° C. in an oil bath while stirring in an N ₂ atmosphere. After confirming that the system is in a translucent microemulsion state when the temperature of the system reaches 65 ° C. to 70 ° C., 2 g of ammonium persulfate is added to the polymerization system to start the polymerization. A microgel is produced by maintaining the polymerization system at 65 ° C. to 70 ° C. with stirring for 3 hours. After the polymerization is completed, acetone is added to the microgel suspension to precipitate the microgel, followed by washing with acetone three times to remove residual monomer and surfactant. The precipitate is filtered and dried under reduced pressure to obtain a dried white powdered microgel.

Synthesis example 7
35 g of dimethylacrylamide (manufactured by Kojin), 17.5 g of N, N-dimethylaminopropylacrylamide methyl chloride (manufactured by Kojin) and 7 mg of methylenebisacrylamide are dissolved in 260 g of ion-exchanged water. In a 1000 ml three-necked flask equipped with a reflux apparatus, 260 g of n-hexane, polyoxyethylene (3) oleyl ether (Emalex 503, manufactured by Nippon Emulsion) 8.7 g and polyoxyethylene (6) oleyl ether (Emalex 506, Japanese-made emulsion) 17.6g were mixed and dissolved into the N ₂ to replace. An aqueous monomer solution is added to the three-necked flask and heated to 65 ° C. to 70 ° C. in an oil bath while stirring in an N ₂ atmosphere. After confirming that the system is in a translucent microemulsion state when the temperature of the system reaches 65 ° C. to 70 ° C., 2 g of ammonium persulfate is added to the polymerization system to start the polymerization. A microgel is produced by maintaining the polymerization system at 65 ° C. to 70 ° C. with stirring for 3 hours. After the polymerization is completed, acetone is added to the microgel suspension to precipitate the microgel, followed by washing with acetone three times to remove residual monomer and surfactant. The precipitate is filtered and dried under reduced pressure to obtain a dried white powdered microgel.

The moisturizing cosmetic liquids (oil-in-water emulsified skin cosmetics) of Examples 1 to 9 and Comparative Examples 1 to 9 having the blending compositions described in “Table 1” and “Table 2” were produced by a conventional method.
About the obtained moisturizing serum (sample), the following test methods were used to give a feeling of use (prolongation to the skin, familiarity to the skin, stickiness, freshness, penetrating feeling, emollient feeling, stickiness) according to the following methods. evaluated.

[A feeling of use (spreading to the skin)]
An actual use test was conducted by a panel dedicated to women (10 persons), and the skin extension was evaluated according to the following evaluation criteria.
(Evaluation criteria)
A: All 10 persons judged that the spread was light and smooth.
○: 7 to 9 persons judged that the spread was light and smooth.
(Triangle | delta): Three to six persons judged that the spread was light and smooth.
X: 0 to 2 persons were judged to be light and smooth.

[Usage feeling (familiarity with skin)]
An actual use test was conducted by a panel dedicated to women (10 persons), and the familiarity with the skin was evaluated according to the following evaluation criteria.
(Evaluation criteria)
A: All 10 people determined that they were familiar with the skin.
○: Seven to nine people determined that they were familiar with the skin.
(Triangle | delta): Three to six persons determined with having familiarity with skin.
X: 0 to 2 persons determined that they were familiar with the skin.

[Usage feeling (stickiness)]
An actual use test was conducted by a panel dedicated to women (10 persons), and the stickiness was evaluated according to the following evaluation criteria.
(Evaluation criteria)
A: All 10 people judged that there was no stickiness and was moist.
○: 7 to 9 people judged that there was no stickiness and was moist.
(Triangle | delta): It determined that 3-6 persons did not have stickiness and were moist.
X: It was determined that 0 to 2 persons were not sticky and moist.

[Usage feeling (freshness)]
An actual use test was conducted by a panel dedicated to women (10 persons), and the freshness was evaluated according to the following evaluation criteria.
(Evaluation criteria)
(Double-circle): All 10 persons judged having freshness.
○: Seven to nine people determined that there was freshness.
(Triangle | delta): Three to six persons determined that there was freshness.
X: 0-2 persons judged having freshness.

[Usage feeling (penetration: active ingredient permeates the skin)]
An actual use test was conducted by a panel dedicated to women (10 persons), and the penetrance was evaluated according to the following evaluation criteria.
(Evaluation criteria)
(Double-circle): All 10 persons determined that there was a feeling of penetration.
○: Seven to nine people determined that there was a sense of penetration.
(Triangle | delta): Three to six persons determined that there was a penetrating feeling.
X: 0 to 2 persons determined that there was a sense of penetration.

[Usage feeling (emollient feeling)]
An actual use test was conducted by a panel dedicated to women (10 persons), and the emollient feeling was evaluated according to the following evaluation criteria.
(Evaluation criteria)
(Double-circle): All 10 persons determined that there was an emollient feeling.
○: Seven to nine people determined that there was an emollient feeling.
(Triangle | delta): Three to six persons determined with emollient feeling.
X: 0-2 persons judged having emollient feeling.

[A feeling of use (feel)]
An actual use test was conducted by a panel dedicated to women (10 persons), and the skin feel was evaluated according to the following evaluation criteria.
(Evaluation criteria)
(Double-circle): All 10 persons determined that there was a feeling of skin elasticity.
○: Seven to nine people determined that there was a feeling of skin stickiness.
(Triangle | delta): Three to six persons determined that there was a feeling of skin elasticity.
X: 0 to 2 persons determined that there was a feeling of skin stickiness.

（＊１）商品名：Cutina PES，BASF社製
（＊２）商品名：エルデュウPS-203，味の素ヘルシーサプライ株式会社製
（＊３）商品名：エルデュウPS-304，味の素ヘルシーサプライ社株式会製
（＊４）商品名：SIMULGEL EG，SEPIC社製
（＊５）商品名：SIMULGEL A，SEPIC社製
（＊６）商品名：SEPIGEL 305，SEPIC社製

(* 1) Product name: Cutina PES, manufactured by BASF (* 2) Product name: El Deu PS-203, manufactured by Ajinomoto Healthy Supply Co., Ltd. (* 3) Product name: El Deu PS-304, manufactured by Ajinomoto Healthy Supply Co., Ltd. (* 4) Product name: SIMULGEL EG, manufactured by SEPIC (* 5) Product name: SIMULGEL A, manufactured by SEPIC (* 6) Product name: SEPIGEL 305, manufactured by SEPIC

（＊１）商品名：Cutina PES，BASF社製
（＊２）商品名：エルデュウPS-203，味の素ヘルシーサプライ株式会社製
（＊３）商品名：エルデュウPS-304，味の素ヘルシーサプライ社株式会製
（＊４）商品名：SIMULGEL EG，SEPIC社製
（＊５）商品名：SIMULGEL A，SEPIC社製
（＊６）商品名：SEPIGEL 305，SEPIC社製

(* 1) Product name: Cutina PES, manufactured by BASF (* 2) Product name: El Deu PS-203, manufactured by Ajinomoto Healthy Supply Co., Ltd. (* 3) Product name: El Deu PS-304, manufactured by Ajinomoto Healthy Supply Co., Ltd. (* 4) Product name: SIMULGEL EG, manufactured by SEPIC (* 5) Product name: SIMULGEL A, manufactured by SEPIC (* 6) Product name: SEPIGEL 305, manufactured by SEPIC

  As is clear from the examples in “Table 1” and the comparative examples in “Table 2”, the moisturizing serums of Examples 1 to 9 containing the essential components of the present invention have excellent usability in all evaluation items. You can see that it has.

  Other examples of the oil-in-water emulsified skin cosmetic of the present invention are shown below.

Example 10 Whitening serum (compounding ingredients)
(1) Ion exchange water Residue (2) Sodium hexametaphosphate 0.1
(3) Sodium hyaluronate 0.1
(4) Tranexamic acid 2.0
(5) Titanium oxide 0.2
(6) Dipropylene glycol 3.0
(7) 1,3-butylene glycol 2.0
(8) Glycerin 3.0
(9) Component (B) Microgel of Synthesis Example 2 0.2
(10) Ethylparaben 0.1
(11) Rose apple leaf extract 0.1
(12) Apricot juice extract 0.1
(13) Sage extract 0.1
(14) Alkyl-modified carboxyvinyl polymer 0.05
(Product name: Pemulen TR-1, manufactured by Noveon Inc)
(15) Polyethylene glycol monostearate (POE120) 1.0
(16) Polyether-modified silicone 0.1
(Product name: KF-6017P, manufactured by Shin-Etsu Chemical Co., Ltd.)
(17) Pentaerythritol distearate 4.0
(Product name: Cutina PES, manufactured by BASF)
(18) α-olefin oligomer 1.0
(19) Isohexadecane 3.0
(20) Cetyl ethylhexanoate 1.0
(21) Octocrylene 0.1
(22) Perfume appropriate amount <Production method>
(15) to (22) were uniformly mixed and dissolved at 70 ° C. (oil phase). On the other hand, (1) to (14) were uniformly mixed and dissolved at 70 ° C. (aqueous phase). The mixture was emulsified with a homomixer while gradually adding the oil phase to the aqueous phase maintained at 70 ° C. When the emulsification was completed, the mixture was rapidly cooled to 40 ° C. or lower to obtain a desired whitening serum having a viscosity of 30000 mPa · s / 30 ° C. (BH type viscometer rotor No. 6, 10 rpm).
<Product properties>
The obtained whitening serum was evaluated in the same manner as in Examples 1 to 9, and was all excellent in use feeling (evaluation: A).

Example 11 Whitening cream (compounding ingredient)
(1) Ion exchange water Residue (2) Edetate 0.1
(3) Acetylated sodium hyaluronate 0.1
(4) Potassium 4-methoxysalicylate 1.0
(5) Silicic anhydride 0.2
(6) Dipropylene glycol 2.0
(7) 1,3-butylene glycol 3.0
(8) Glycerin 3.0
(9) Microgel of Synthesis Example 3 0.5
(10) Methylparaben 0.1
(11) Ethylparaben 0.2
(12) Atlantic hawthorn extract 0.1
(13) Lumpuyan extract 0.1
(14) Green tea extract 0.1
(15) POE (20) behenyl ether 1.2
(16) Behenyl alcohol 0.4
(17) Stearyl alcohol 0.2
(18) Isodecyl piperate 2.0
(19) Isododecane 1.0
(20) Pentaerythritol distearate 5.0
(Product name: Dub DSPE, Stearinerie Dubois Fils)
(21) Dimethylpolysiloxane 2 mPa · s 2.0
(22) Hydrogenated polyisobutene 3.0
(23) Perfume appropriate amount <Production method>
(15) to (23) were uniformly mixed and dissolved at 70 ° C. (oil phase). On the other hand, (1) to (14) were uniformly mixed and dissolved at 70 ° C. (aqueous phase). The mixture was emulsified with a homomixer while gradually adding the oil phase to the aqueous phase maintained at 70 ° C. When the emulsification was completed, the product was rapidly cooled to 40 ° C. or lower to obtain a desired whitening cream having a viscosity of 40,000 mPa · s / 30 ° C. (BH type viscometer rotor No. 6, 10 rpm).
<Product properties>
About the obtained whitening cream, when the same evaluation as Examples 1-9 was performed, it was what was excellent in all the feelings of use (evaluation: (double-circle)).

Example 12 Anti-aging serum (compounding ingredients)
(1) Ion exchange water Residue (2) Edetate 0.1
(3) Acetylated sodium hyaluronate 0.1
(4) Carnosine 3.5
(5) Erythritol 1.0
(6) Dipropylene glycol 2.0
(7) 1,3-butylene glycol 3.0
(8) Glycerin 5.0
(9) Microgel of Synthesis Example 4 0.15
(10) Methylparaben 0.1
(11) Phenoxyethanol 0.3
(12) Hydrolyzed yeast extract 0.1
(13) Shirobanaikouzorina leaf extract 0.1
(14) Citric acid appropriate amount (15) Self-emulsifying glyceryl monostearate 1.2
(16) POE (30) Phytosterol 0.9
(17) POE (60) hydrogenated castor oil 0.1
(18) Behenic acid 0.5
(19) Stearic acid 0.4
(20) Isononyl isononanoate 2.0
(21) Isododecane 1.0
(22) Pentaerythritol distearate 3.0
(Product name: Cutina PES, manufactured by BASF)
(23) Dimethylpolysiloxane 6 mPa · s 2.0
(24) Vitamin E acetate 0.1
(25) Perfume appropriate amount <Production method>
(15) to (25) were uniformly mixed and dissolved at 70 ° C. (oil phase). On the other hand, (1) to (14) were uniformly mixed and dissolved at 70 ° C. (aqueous phase). The mixture was emulsified with a homomixer while gradually adding the oil phase to the aqueous phase maintained at 70 ° C. When the emulsification was completed, the solution was rapidly cooled to 40 ° C. or lower to obtain a desired anti-aging cosmetic liquid having a viscosity of 35000 mPa · s (BH type viscometer rotor No. 6, 10 rpm).
<Product properties>
The obtained anti-aging cosmetic liquid was evaluated in the same manner as in Examples 1 to 9, and was excellent in all feelings of use (evaluation: A).

The oil-in-water emulsified skin cosmetic of the present invention is a skin cosmetic that has good spread and familiarity to the skin, is not sticky, and has an excellent feeling of use such as freshness, penetration, emollient, and stickiness. .
Therefore, it can be preferably used for gel-like or cream-like products such as anti-aging cosmetic liquid, whitening cosmetic liquid, anti-aging cream, and whitening cream.

That is, the present invention provides an oil-in-water emulsified skin cosmetic characterized by containing the following components (A), (B), and (C) .
(A) Pentaerythritol distearate (B) In a composition using an organic solvent or oil as a dispersion medium and water as a dispersion phase, water-soluble ethylenically unsaturated monomer is dissolved in the dispersion phase and radical polymerization is performed in the dispersion phase. Radical polymerization of dimethylacrylamide and 2-acrylamido-2-methylpropanesulfonic acid under the condition that the microgel forms a one-phase microemulsion or a fine W / O emulsion with a surfactant. Thickener made of microgel
(C) Emulsifier

Further, the present invention is to provide the oil-in-water emulsified skin cosmetic total amount, the content of distearate pentaerythritol said component (A) is 0.5 to 5.0 wt%, the component (B) The oil-in-water type emulsified skin cosmetic described above is characterized in that the content of the thickener comprising the microgel is 0.1 to 2.0% by mass.

Claims (2)

An oil-in-water emulsified skin cosmetic comprising the following components (A) and (B):
(A) An ester of a fatty acid mixture containing a fatty acid having 16 to 18 carbon atoms and pentaerythritol (B) In a composition having an organic solvent or oil as a dispersion medium and water as a dispersion phase, A microgel obtained by dissolving a saturated monomer in a dispersed phase and radical polymerization in the dispersed phase, wherein the microgel forms a one-phase microemulsion or a fine W / O emulsion by a surfactant. Thickener comprising a microgel obtained by radical polymerization of dimethylacrylamide and 2-acrylamido-2-methylpropanesulfonic acid   Content of ester of fatty acid mixture containing fatty acid having 16 to 18 carbon atoms and pentaerythritol is 0.5 to 5.0% by mass with respect to the total amount of oil-in-water emulsified skin cosmetic. The oil-in-water emulsified skin cosmetic according to claim 1, wherein the content of the thickener comprising the microgel of the component (B) is 0.1 to 2.0% by mass.