JP2009234917A - Oil-in-water emulsion composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oil-in-water emulsion composition containing a powdery component, which can sufficiently exert thickening effect of an associative thickener and is excellent in usability and stability. <P>SOLUTION: The oil-in-water emulsion composition comprises (a) a hydrophobically modified polyether urethane (the associative thickener) and (d) a thickening polysaccharide (e.g. succinoglycan, xanthan gum) in an outer phase (aqueous phase), and (b) a hydrophobic powder (e.g., hydrophobized titanium dioxide etc.) and (c) a dispersing agent (e.g., polyglycerin-modified silicone, acrylic silicone, polyoxyalkylene-modified silicone, etc.) in an inner phase. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an oil-in-water emulsion composition. More specifically, the present invention relates to an oil-in-water emulsified composition that has a feeling of elasticity, a smooth feeling of use, and excellent stability.

  Conventionally, as a cosmetic containing powder represented by makeup cosmetics, an oil-in-water emulsion composition is suitably applied to an emulsion foundation and the like because it has a fresh and refreshing feeling of use. In addition, an oil-in-water emulsified composition that improves water resistance and makeup has been developed by using a hydrophobized powder obtained by hydrophobizing the powder surface as a powder.

  However, in general, a system containing powder tends to be hard to thicken, has a poor feeling in use (no smoothness, etc.), has poor makeup, and has poor stability (= poor dispersibility and powder) There is a problem that the body agglomerates and settles and a color stripe appears.

  Therefore, it is conceivable to add a thickener to the oil-in-water emulsified composition containing powder in order to increase the viscosity. Conventionally, natural polymers such as casein, synthetic polymers such as acrylic acid polymers and carboxyvinyl polymers, clay minerals such as montmorillonite, and the like have been used as thickeners blended in cosmetics. However, these conventional thickeners have problems such as a slimy feeling peculiar to polymers, and when a clay mineral is blended, liquid separation is likely to occur due to temperature changes and the like.

  As a new thickener that solves the problems of the conventional thickeners, associative thickeners (eg, associative polyurethane) having a usability without a slimy feeling or sticky feeling have been proposed ( For example, see Patent Documents 1 and 2). However, when these associative thickeners coexist with the powder component, it is difficult to sufficiently exert the thickening effect, the use feeling is also poor (no smoothness, etc.), and the stability is poor (color fringes). Etc.).

JP 2000-63235 A JP 2000-239120 A

  In the oil-in-water emulsion composition containing the powder component, the present invention solves the above-mentioned conventional problems, and can sufficiently exhibit the thickening effect of the associative thickener, and is improved in usability and stability. An object is to provide an excellent oil-in-water emulsion composition.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive research. As a result, in an oil-in-water emulsion composition, an associative thickener and a thickening polysaccharide are blended in the outer phase (aqueous phase), and the inner phase ( By blending the powder component and dispersant in the oil phase), the thickening effect of the associative thickener can be fully demonstrated, usability (elasticity and smooth feel), and stability of the base The present inventors have found that an oil-in-water emulsion composition having excellent properties can be obtained, and have completed the present invention.

  That is, the present invention includes (a) a hydrophobically modified polyether urethane represented by the following formula (I), (b) a hydrophobic powder, and (c) a polyglycerin-modified silicone, an acrylic silicone, and a polyoxyalkylene-modified silicone. An oil-in-water emulsion composition containing one or more dispersants selected from (d) and a thickening polysaccharide is provided.

Wherein _{(I), R 1, R} 2 and R ₄ each independently represents a hydrocarbon group; R ₃ represents a hydrocarbon group which may have a urethane bond; R ₅ is a linear, Represents a branched chain or secondary hydrocarbon group; m is a number of 2 or more; h is a number of 1 or more; k and n are each independently a number of 0 to 1000. ]

  The present invention also provides the oil-in-water emulsion composition, wherein the component (d) is succinoglycan and / or xanthan gum.

In the present invention, the hydrophobic modified polyether urethane represented by the above formula (I) is one or more polyether polyols represented by R ₁ -[(O—R ₂ ) _k —OH] _m. And one or more polyisocyanates represented by R ₃ — (NCO) _{h + 1} , and one or more polyisocyanates represented by HO— (R ₄ —O) _n —R _5. The oil-in-water emulsion composition is a reaction product with an ether monoalcohol.

In the present invention, in the formula (I), R ₁ , R ₂ and R ₄ each independently represents an alkylene group having 2 to 4 carbon atoms or a phenylethylene group; R ₃ has a urethane bond R ₅ represents an alkyl group having 8 to 36 carbon atoms; m is a number of 2 or more; h is a number of 1 or more; , N each independently represents a number of 0 to 1000, and provides the oil-in-water emulsion composition.

  Moreover, this invention provides the said oil-in-water emulsion composition whose polyglycerin modified silicone of (c) component is the both-ends silicone-ized polyglycerin shown by following formula (II).

[In the formula (II), R ₆ represents a linear or branched alkyl group having 1 to 12 carbon atoms or a phenyl group; R ₇ represents an alkylene group having 2 to 11 carbon atoms; Q is a number from 1 to 11; q is a number from 1 to 11. ]

  The present invention also provides the oil-in-water emulsion composition, wherein the acrylic silicone as component (c) is a copolymer comprising a structural unit represented by the following formula (III).

[In the formula (III), R ₈ represents an alkyl group having 10 or more and less than 20 carbon atoms; a + b + c = 1, a, b and c are both numbers of 0.2 or more, and r is 5 to 100. Is an integer. ]
The present invention also provides the oil-in-water emulsion composition, wherein the polyoxyalkylene-modified silicone as component (c) is a copolymer represented by any of the following formulas (IV), (V), and (VI).

[In the formulas (IV) to (VI), R ₉ represents a methyl group or a phenyl group; R ₁₀ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; x is an integer of 1 to 5; y is an integer of 2 to 3; z, s, and t are, on average, the polyoxyalkylene-modified silicone contains 5 to 40% by mass of a polyoxyalkylene group in the molecule, and the polyoxyalkylene-modified silicone is A numerical value such that the molecular weight is 2000 or more is represented. ]

  Moreover, this invention provides the said oil-in-water type emulsion composition which contains 0.1-10 mass% of (a) component, and 0.1-50 mass% of (b) component.

  The oil-in-water emulsified composition of the present invention has an effect that it has elasticity, has a smooth feeling in use, and is excellent in the stability of the base (no color stripes appear).

  Hereinafter, the present invention will be described in detail.

  The component (a) used in the present invention is a hydrophobically modified polyether urethane represented by the following formula (I). The copolymer is an associative thickener. The associative thickener is a copolymer having a hydrophilic group as a skeleton and having a hydrophobic part at the end, and exhibits a thickening action by associating the hydrophobic parts of the copolymer in an aqueous medium. Such an associative thickener exhibits a thickening action as shown in FIG. 1, in which the hydrophobic portions of the copolymer are associated with each other in a water-soluble medium, and the hydrophilic portion has a loop shape or a bridge shape.

In the above formula (I), R ₁ , R ₂ and R ₄ each independently represent a hydrocarbon group. An alkylene group having 2 to 4 carbon atoms or a phenylethylene group is preferable.
R ₃ represents a hydrocarbon group which may have a urethane bond, and the hydrocarbon group is preferably an alkylene group having 1 to 10 carbon atoms.
R ₅ represents a straight chain, branched chain or secondary hydrocarbon group. Preferably, it is an alkyl group having 8 to 36 carbon atoms.
m is a number of 2 or more.
h is a number of 1 or more.
k and n are each independently a number of 0 to 1000.

The hydrophobically modified polyether urethane represented by the above formula (I) is, for example, R ₁ -[(O—R ₂ ) _k —OH] _m (where R ₁ , R ₂ , k, m are defined above). And one or more polyether polyols represented by: and R _3- (NCO) _{h + 1} (wherein R ₃ and h are as defined above) or One or more polyisocyanates represented by two or more polyisocyanates and HO— (R ₄ —O) _n —R ₅ (where R ₄ , R ₅ , and n are as defined above). A preferred example is a method obtained by reacting with an ether monoalcohol.

In this case, R _{1 to} R ₅ in formula (I) are R ₁ -[(O—R ₂ ) _k —OH] _m , R ₃ — (NCO) _{h + 1} , HO— (R ₄ —O) used. ) is determined by _n -R _5. The charge ratio of the above three members is not particularly limited, but the ratio of the hydroxyl group derived from polyether polyol and polyether monoalcohol to the isocyanate group derived from polyisocyanate is NCO / OH = 0.8: 1 to 1. .4: 1 is preferred.

The polyether polyol compound represented by the above formula R ₁ -[(O—R ₂ ) _k —OH] _m is an m-valent polyol containing an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, styrene oxide, or the like. It can be done by addition polymerization.

  Here, as the polyol, those having 2 to 8 valences are preferable. For example, dihydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol and neopentyl glycol; glycerin, trioxyisobutane, 1,2,3- Butanetriol, 1,2,3-pentatriol, 2-methyl-1,2,3-propanetriol, 2-methyl-2,3,4-butanetriol, 2-ethyl-1,2,3-butanetriol 2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-propyl-3,4,5-heptanetriol, 2,4-dimethyl-2,3,4-pentanetriol, pentamethylglycerin , Pentaglycerin, 1,2,4-butanetriol, 1,2,4-pentanetri , Trimethylol ethane, trimethylol propane and other trihydric alcohols; pentaerythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5 -Tetravalent alcohols such as pentanetetrol, 1,3,4,5-hexanetetrol; pentavalent alcohols such as adnit, arabit and xylit; hexavalent alcohols such as dipentaerythritol, sorbit, mannitol and exit; Examples include octahydric alcohols such as sucrose.

R ₂ is determined depending on the alkylene oxide, styrene oxide, etc. to be added, but it is particularly easily available, and in order to exert an excellent effect, alkylene oxide or styrene oxide having 2 to 4 carbon atoms is used. preferable.

The alkylene oxide, styrene oxide and the like to be added may be homopolymerization, two or more kinds of random polymerization, or block polymerization. The addition method may be a normal method. Moreover, the polymerization degree k is 0-1000, Preferably it is 1-500, More preferably, it is 10-200. The ratio of ethylene to total R ₂ is preferably 50 to 100 wt% of the total R _2.

The molecular weight of R ₁ -[(O—R ₂ ) _k —OH] _m is preferably from 500 to 100,000, particularly preferably from 1,000 to 50,000.

The polyisocyanate represented by the formula R ₃ — (NCO) _{h + 1} is not particularly limited as long as it has two or more isocyanate groups in the molecule. For example, aliphatic diisocyanate, aromatic diisocyanate, alicyclic diisocyanate, biphenyl diisocyanate, phenylmethane di-, tri-, and tetraisocyanate.

  Examples of the aliphatic diisocyanate include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dipropyl ether diisocyanate, 2,2-dimethylpentane diisocyanate, 3-methoxyhexane diisocyanate, Octamethylene diisocyanate, 2,2,4-trimethylpentane diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 3-butoxyhexane diisocyanate, 1,4-butylene glycol dipropyl ether diisocyanate, thiodihexyl diisocyanate, metaxylylene diisocyanate, paraxylylene Range isocyanine DOO, tetramethylxylylene diisocyanate, and the like.

  Examples of the aromatic diisocyanate include metaphenylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dimethylbenzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, tolidine diisocyanate, 1,4- Examples include naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, and 2,7-naphthalene diisocyanate.

  Examples of the alicyclic diisocyanate include hydrogenated xylylene diisocyanate and isophorone diisocyanate.

  Examples of the biphenyl diisocyanate include biphenyl diisocyanate, 3,3′-dimethylbiphenyl diisocyanate, and 3,3′-dimethoxybiphenyl diisocyanate.

  Examples of the diisocyanate of phenylmethane include diphenylmethane-4,4′-diisocyanate, 2,2′-dimethyldiphenylmethane-4,4′-diisocyanate, diphenyldimethylmethane-4,4′-diisocyanate, 2,5,2 ′. , 5′-tetramethyldiphenylmethane-4,4′-diisocyanate, cyclohexylbis (4-isothiontphenyl) methane, 3,3′-dimethoxydiphenylmethane-4,4′-diisocyanate, 4,4′-dimethoxydiphenylmethane 3,3′-diisocyanate, 4,4′-diethoxydiphenylmethane-3,3′-diisocyanate, 2,2′-dimethyl-5,5′-dimethoxydiphenylmethane-4,4′-diisocyanate, 3,3′- Dichlorodiphenyldimethyl Tan-4,4'-diisocyanate, benzophenone-3,3'-diisocyanate, and the like.

  Examples of the triisocyanate of phenylmethane include 1-methylbenzene-2,4,6-triisocyanate, 1,3,5-trimethylbenzene-2,4,6-triisocyanate, and 1,3,7-naphthalenetriisocyanate. Isocyanate, biphenyl-2,4,4′-triisocyanate, diphenylmethane-2,4,4′-triisocyanate, 3-methyldiphenylmethane-4,6,4′-triisocyanate, triphenylmethane-4,4 ′, 4 ″ -triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanate phenyl) Such as thiophosphate It is below.

  Moreover, you may use with the dimer and trimer (isocyanurate coupling | bonding) of these polyisocyanate compounds, and you may make it react with an amine and use it as a biuret.

Further, polyisocyanates having urethane bonds obtained by reacting these polyisocyanate compounds with polyols can also be used. As a polyol, the thing of 2-8 valence is preferable, and the above-mentioned polyol is preferable. Incidentally, R ₃ - (NCO) if the h + ₁ using trivalent or more polyisocyanates, polyisocyanate preferably has the urethane bond.

The polyether monoalcohol represented by the above formula HO— (R ₄ —O) _n —R ₅ is not particularly limited as long as it is a polyether of a linear, branched or secondary monohydric alcohol. Such a compound can be obtained by addition polymerization of alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, styrene oxide or the like to linear and branched chain or secondary monohydric alcohol.

  Here, the linear alcohol is represented by the following formula (VII).

R ₁₁ —OH (VII)

  Moreover, the branched chain alcohol here is represented by the following formula (VIII).

  The secondary alcohol is represented by the following formula (IX).

Therefore, R ₅ is a group obtained by removing the hydroxyl group in the above formulas (VII) to (IX). In the above formulas (VII) to (IX), R ₁₁ , R ₁₂ , R ₁₃ , R ₁₅ and R ₁₆ are hydrocarbon groups or fluorocarbon groups, for example, alkyl groups, alkenyl groups, alkylaryl groups, cycloalkyl groups. A cycloalkenyl group and the like.

  Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, isopentyl, neopentyl, tertiary pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl. , Tridecyl, isotridecyl, myristyl, palmityl, stearyl, isostearyl, icosyl, docosyl, tetracosyl, triacontyl, 2-octyldodecyl, 2-dodecylhexadecyl, 2-tetradecyloctadecyl, monomethyl branched-isostearyl and the like.

  Examples of the alkenyl group include vinyl, allyl, propenyl, isopropenyl, butenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, oleyl and the like.

  The alkylaryl group includes phenyl, toluyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonyl Examples include phenyl, α-naphthyl, β-naphthyl group and the like.

  Examples of the cycloalkyl group and cycloalkenyl group include a cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclohexenyl, methylcycloheptenyl group. Etc.

In the above formula (VIII), R ₁₄ is a hydrocarbon group or a fluorocarbon group, for example, an alkylene group, an alkenylene group, an alkylarylene group, a cycloalkylene group, a cycloalkenylene group or the like.

R ₅ is a hydrocarbon group or a fluorocarbon group, preferably an alkyl group, more preferably 8 to 36 carbon atoms, and particularly preferably 12 to 24 carbon atoms.

Further, the alkylene oxide, styrene oxide and the like to be added may be homopolymerization, two or more kinds of random polymerization, or block polymerization. The addition method may be a normal method. The degree of polymerization n is 0 to 1000, preferably 1 to 200, and more preferably 10 to 200. Further, the proportion of the ethylene group in R ₄ is preferably 50 to 100% by weight, more preferably 65 to 100% by weight of the total R _4. A sticky agent is obtained.

  As a method for producing the copolymer represented by the above formula (I), it can be obtained by reacting by heating at 80 to 90 ° C. for 1 to 3 hours, for example, in the same manner as in the reaction of an ordinary polyether and isocyanate. Can do.

In addition, polyether polyol (A) represented by R ₁ -[(O—R ₂ ) _k —OH] _m , polyisocyanate (B) represented by R ₃ — (NCO) _{h + 1} , and HO When the polyether monoalcohol (C) represented by — (R ₄ —O) _n —R ₅ is reacted, other than the copolymer having the structure of the formula (I) may be by-produced. For example, when diisocyanate is used, the main product is a CBACABC type copolymer represented by the formula (I). Copolymers such as-(A-B) _x- ABC type may be by-produced. In this case, the copolymer of the formula (I) can be used in the present invention in the form of a mixture containing the copolymer of the formula (I) without separating the copolymer of the formula (I).

  In the present invention, a commercially available product may be used as the component (a). As a commercial item, "Adecanol GT-700" (Asahi Denka Kogyo Co., Ltd. product) etc. are mentioned, for example.

  The blending amount of the component (a) is preferably 0.1 to 10% by mass in the composition of the present invention, more preferably 0.1 to 5% by mass, and particularly preferably 0.5 to 5% by mass. . If it is less than 0.1% by mass, the effect of adding the component (a) is not observed. On the other hand, if it exceeds 10% by mass, the viscosity becomes too high, and the efficiency of production of the composition decreases, or stickiness is caused in terms of usability. This is not preferable.

  The hydrophobic powder as the component (b) includes not only a hydrophobic powder itself but also a hydrophobized powder obtained by hydrophobizing the powder surface even if it is a hydrophilic powder or the like.

  Specific examples of the hydrophobic powder include polyamide resin powder (nylon powder), polyethylene powder, polymethyl methacrylate powder, polystyrene powder, copolymer resin powder of styrene and acrylic acid, benzoguanamine resin powder, polytetrafluoroethylene powder. Examples thereof include organic powders such as ethylene powder and cellulose powder, and silicone powders such as trimethylsilsesquioxane powder.

  Examples of the powder component of the hydrophobized powder include talc, kaolin, mica, sericite (sericite), muscovite, phlogopite, synthetic mica, safmica, biotite, lithia mica, permiculite, magnesium carbonate, calcium carbonate, Aluminum silicate, barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate (calcined gypsum), calcium phosphate, fluorapatite, hydroxyapatite, Ceramic powders, metal soaps (zinc myristate, calcium palmitate, aluminum stearate, etc.), inorganic powders such as boron nitride; inorganic white pigments such as titanium dioxide and zinc oxide; inorganics such as iron oxide (Bengara) and iron titanate Red pigment Inorganic brown pigments such as γ-iron oxide; Inorganic yellow pigments such as yellow iron oxide and ocher; Inorganic black pigments such as black iron oxide, carbon black, low-order titanium dioxide; Inorganic purple pigments such as mango violet and Baltic violet Pigments; inorganic green pigments such as chromium oxide, chromium hydroxide and cobalt titanate; inorganic blue pigments such as ultramarine and bitumen; titanium dioxide coated mica, titanium dioxide coated bismuth oxychloride, titanium dioxide coated talc, colored titanium dioxide Examples thereof include pearl pigments such as coated mica, bismuth oxychloride and fish scale foil; metal powder pigments such as aluminum powder and copper powder. In the present invention, those powder components obtained by hydrophobizing are used.

  The hydrophobizing treatment method may be any method as long as it can impart water repellency, and any method can be used. For example, a usual surface treatment method such as a gas phase method, a liquid phase method, an autoclave method, a mechanochemical method, etc. Can be used.

  For example, when a hydrophobizing agent is added to the raw material powder for treatment, it may be diluted with an appropriate solvent (dichloromethane, chloroform, hexane, ethanol, xylene, volatile silicone, etc.) or added directly. May be. For mixing and stirring the powder and the treatment agent, a ball mill, a hogersite ball mill, a vibrating ball mill, an attritor, a pot mill, a rod mill, a pan mill, a homomixer, a homodisper, a Henschel mixer, a nauter mixer, and the like can also be used. In addition to this, by utilizing the activity of the powder surface, a method of polymerizing cyclic organosiloxane on the powder surface at a low temperature of 100 ° C. or less by gas phase reaction (Japanese Patent Publication No. 1-54380), A method of adding a pendant group such as glycerol monoallyl ether to the Si—H portion of the silicone polymer (Japanese Patent Publication No. 1-54381) can also be used.

  Although it does not specifically limit as a hydrophobizing agent, Fatty acid dextrin processing powder, trimethylsiloxysilicic acid processing powder, fluorine-modified trimethylsiloxysilicic acid processing powder, methylphenylsiloxysilicic acid processing powder, fluorine-modified methylphenylsiloxysilicic acid processing powder Low viscosity to high viscosity oily polysiloxane treated powder such as dimethylpolysiloxane, diphenylpolysiloxane, methylphenylpolysiloxane, gum-like polysiloxane treated powder, methylhydrogenpolysiloxane treated powder, fluorine-modified methylhydrogenpolysiloxane treated powder , Methyltrichlorosilane, methyltrialkoxysilane, hexamethyldisilane, dimethyldichlorosilane, dimethyldialkoxysilane, trimethylchlorosilane, trimethylalkoxysilane, etc. Treatment powder with organic silyl compounds or their fluorine-substituted products, ethyltrichlorosilane, ethyltrialkoxysilane, propyltrichlorosilane, propyltrialkoxysilane, hexyltrichlorosilane, hexyltrialkoxysilane, long-chain alkyltrichlorosilane, long-chain alkyltri Examples thereof include treatment powders with organically modified silanes such as ethoxysilane or fluorine-substituted products thereof, amino-modified polysiloxane-treated powders, fluorine-modified polysiloxane-treated powders, and fluorinated alkyl phosphoric acid-treated powders.

  Hydrophobic powder has strong water repellency, and even when actually applied to an emulsion, it is resistant to water and sweat, and is most resistant to makeup, so it has excellent durability. Also, the emulsified particles are dense and have the longest stability.

  These hydrophobic powders may be used alone or in combination of two or more. Moreover, it should just be a hydrophobic powder applicable to a general cosmetics, and is not limited to the component of the said illustration.

  The amount of component (b) is preferably 1 to 40% by mass, more preferably 5 to 25% by mass, in the water-in-oil emulsion composition of the present invention. If the amount is too small, the concealability (covering power) is lowered, which is unsuitable as a makeup cosmetic. On the other hand, if the amount is too large, the powderiness tends to be remarkable and the stability tends to deteriorate. is there.

  Component (c) is one or more dispersants selected from polyglycerin-modified silicone, acrylic silicone, and polyoxyalkylene-modified silicone.

[Polyglycerin-modified silicone]
As the polyglycerin-modified silicone, a double-terminal silicone-modified polyglycerin represented by the following formula (II) is preferably used.

In the formula (II), R ₆ represents a linear or branched alkyl group having 1 to 12 carbon atoms or a phenyl group, R ₇ represents an alkylene group having 2 to 11 carbon atoms, and p is 10 to 10 120 is a number, and q is a number from 1 to 11.

  The copolymer represented by the above formula (II) can be produced, for example, by adding an isopropyl platinate chloroalcohol solution to a mixed solution of polyglyceryl diallyl ether and one-end hydrogenated dimethylpolysiloxane, and heating and reacting the solution. It can be obtained by adding an aqueous solution and carrying out superheat hydrolysis, followed by neutralization with an aqueous sodium bicarbonate solution, followed by purification and evaporation. However, it is not limited to this manufacturing method.

[Acrylic silicone]
As the acrylic silicone, a copolymer composed of a structural unit represented by the following formula (III) is preferably used.

In the formula (III), R ₈ represents an alkyl group having 8 or more and less than 20 carbon atoms, a + b + c = 1, a, b and c are both 0.2 or more, and r is 5 to 100. It is an integer.

R ₈ is preferably an isostearyl group having 18 carbon atoms or a 2-ethylhexyl group having 8 carbon atoms, particularly preferably an isostearyl group.

[Polyoxyalkylene-modified silicone]
As the polyoxyalkylene-modified silicone, a copolymer represented by any one of the following formulas (IV), (V), and (VI) is preferably used.

In the above formulas (IV) to (VI), each substituent has the following meaning.
R ₉ represents a methyl group or a phenyl group.
R ₁₀ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
x is an integer of 1-5.
y is an integer of 2-3.
z, s, and t are average numbers, and the polyoxyalkylene-modified silicone contains 5 to 40% by mass (= alkylene oxide modification rate) in the molecule, and the molecular weight of the polyoxyalkylene-modified silicone is 2000. The numerical value is as above.

  The amount of component (c) is not particularly limited as long as it is sufficient to disperse component (b) in the internal phase (oil phase) with good dispersibility. 1-10 mass% is preferable, More preferably, it is 0.1-5 mass%. If the amount is too large, the emulsion stability may be deteriorated.

  As the thickening polysaccharide of component (d), succinoglycan and / or xanthan gum is preferably used in the present invention.

  Succinoglycan is a kind of polysaccharide derived from microorganisms. More specifically, in addition to saccharide units derived from galactose and glucose, succinic acid and pyruvic acid, acetic acid as an optional component, or of these acids It means a polysaccharide derived from a microorganism containing a unit derived from a salt.

  More specifically, succinoglycan has an average molecular weight of about 1 galactose unit: 1, glucose unit: 7, succinic acid unit: 0.8, and pyruvic acid unit: 1, which may contain an optional acetic acid unit. 6 million water-soluble polymers represented by the following formula (X).

[In Formula (X), Gluc represents a glucose unit, and Galac represents a galactose unit. In addition, the indication in parentheses indicates the binding mode between sugar units. For example, (β1,4) represents a β1-4 bond. ]

  Examples of the microorganisms that supply the succinoglycan include bacteria belonging to the genus Pseudomonas, Rhizobium, Alkaligenes, or Agrobacterium. Among these bacteria, Agrobacterium tumefaciens I-736, a bacterium belonging to the genus Agrobacterium, was deposited with the Collection Organization of the Parties to Microbial Cultures (CNCM) on March 1, 1988 in accordance with the Budapest Treaty. Publicly available at ] Is particularly preferred as a source of succinoglycan.

  Succinoglycan can be produced by culturing these microorganisms in a medium. More specifically, carbon sources such as glucose, sucrose and starch hydrolysates; organic nitrogen sources such as casein, caseinate, vegetable powder, yeast extract and corn steep liquor (CSL); metal sulfates and phosphates It can be produced by culturing the above microorganisms in a medium containing inorganic salts such as carbonates and optional trace elements. However, it is not limited to these examples.

  In addition, succinoglycan can be blended as it is in the emulsified composition, and if necessary, degradation products such as acid degradation, alkali degradation, enzymatic degradation, and ultrasonic treatment can be blended in the same manner. .

  The amount of component (d) is not particularly limited as long as it is sufficient to disperse component (a) in the outer phase (aqueous phase) with good dispersibility, but it is usually 0 with respect to the total amount of the composition. 0.01 to 5% by mass is preferable, and 0.01 to 1% by mass is more preferable. If the amount is too large, stickiness may become worse, and there is a risk of sticking a sticky thread.

  By blending the components (c) and (d) in this way, the component (b) is blended in the inner phase (oil phase) and the component (a) in the outer phase (water phase), and each component is stably blended with good dispersibility. can do.

  The present invention is an oil-in-water emulsification having a feeling of elasticity, smooth use feeling, and excellent stability (= no color fringing) by combining and blending the above components (a) to (d). A composition is obtained.

  The oil blended in the inner phase (oil phase) is not particularly limited, and fats and oils, waxes, hydrocarbon oils, higher fatty acids, higher alcohols, synthetic ester oils, silicones and the like can be used. However, it is not limited to these examples.

  As fats and oils, avocado oil, camellia oil, evening primrose oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, sasanqua oil, castor oil, linseed oil , Safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnagiri oil, Japanese kiri oil, jojoba oil, germ oil, triglycerin, trioctanoic acid glycerin, triisopalmitic acid Liquid fats such as glycerin; cacao butter, palm oil, horse fat, hydrogenated palm oil, palm oil, beef tallow, sheep fat, hydrogenated beef tallow, palm kernel oil, pork fat, beef bone fat, owl kernel oil, hydrogenated oil, cow leg Examples thereof include solid fats and oils such as fat, mole, and hardened castor oil.

  The waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibota wax, whale wax, montan wax, nuka wax, lanolin, kapok wax, lanolin acetate, liquid lanolin, sugar cane wax, lanolin fatty acid isopropyl, lauryl hexyl, reduced lanolin, jojojo Examples include a wax, hard lanolin, shellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether, and the like.

  Examples of the hydrocarbon oil include oils such as liquid paraffin, ozokerite, squalene, pristane, paraffin, ceresin, squalene, petrolatum, and microcrystalline wax.

  Higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, 12-hydroxystearic acid, undecylenic acid, tolic acid, isostearic acid, linoleic acid, linolenic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA) and the like are exemplified.

  As higher alcohols, linear alcohols such as lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol; monostearyl glycerin ether (batyl alcohol), 2-decyltetradecinol, lanolin alcohol, Examples thereof include branched chain alcohols such as cholesterol, phytosterol, hexyldodecanol, isostearyl alcohol, and octyldodecanol.

Synthetic ester oils include isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyloctanoate, cetyl lactate, myristyl lactate Lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearylate, ethylene glycol di-2-ethylhexylate, dipentaerythritol fatty acid ester, N-alkylglycol monoisostearate, neopentyl glycol dicaprate, malic acid Diisostearyl, di-2-heptylundecanoic acid glycerin, tri-2-ethylhexyl trimethylolpropane, Trimethylolpropane phosphate, pentane erythritol tetra-2-ethylhexylate, glycerol 2-triethylhexylate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, glyceryl trimyristate, tri- 2-heptylundecanoic acid glyceride, castor oil fatty acid methyl ester, oleic oil, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamic acid-2-octyldecyl ester, adipic acid di- 2-heptylundecyl, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyl adipate Decyl, sebacic acid diisopropyl, 2-ethylhexyl succinate, ethyl acetate, butyl acetate, amyl acetate, triethyl citrate, crotamiton (C ₁₃ H ₁₇ NO) and the like are exemplified.

  Examples of silicone include chain polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane; cyclic polysiloxanes such as decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and tetramethyltetrahydrogenpolysiloxane; Examples thereof include silicone resin and silicone rubber forming a three-dimensional network structure.

  In the composition of the present invention, various components that are usually used in cosmetics, for example, a moisturizer, an ultraviolet absorber, a pH adjuster, an antioxidant, an antiseptic, an antibacterial agent, a drug, Plant extracts, fragrances, pigments and the like can be blended.

  Examples of the humectant include polyhydric alcohols such as glycerin, diethylene glycol, butylene glycol, and polyethylene glycol, amino acids, nucleic acids, proteins such as collagen and elastin, mucopolysaccharides such as hyaluronic acid and chondroitin sulfate, and the like.

  Examples of UV absorbers include benzoic acid UV absorbers such as paraaminobenzoic acid, anthranilic acid UV absorbers such as methyl anthranilate, salicylic acid UV absorbers such as octyl salicylate, phenyl salicylate and homomethyl salicylate, and paramethoxy cinnamon. Isopropyl acid, octyl paramethoxycinnamate, 2-ethylhexyl paramethoxycinnamate, glyceryl mono-2-ethylhexanoate diparamethoxycinnamate, [4-bis (trimethylsiloxy) methylsilyl-3-methylbutyl] -3 , 4,5, -trimethoxycinnamic acid ester, etc., cinnamic acid UV absorbers, urocanic acid, ethyl urocanate, 2-phenyl-5-methylbenzoxazole, 2- (2′-hydroxy-5 ′) -Methylphenyl) benzotriazole, 4-tert- Chill-4'-methoxy benzoyl methane, bis (Resorushiniru) triazine.

  Examples of the pH adjuster include lactic acid, citric acid, sodium citrate, glycolic acid, succinic acid, tartaric acid, dl-malic acid, potassium carbonate, sodium hydrogen carbonate, ammonium hydrogen carbonate and the like.

  Examples of the antioxidant include ascorbic acid, α-tocopherol, dibutylhydroxytoluene, butylhydroxyanisole and the like.

  As preservatives and antibacterial agents, paraoxybenzoic acid ester, phenoxyethanol, octoxyglycerin, benzoic acid, salicylic acid, carboxylic acid, sorbic acid, parachlormethcresol, hexachlorophene, benzalkonium chloride, chlorhexidine chloride, trichlorocarbanilide, A photosensitive element etc. are mentioned.

  The oil-in-water emulsion composition of the present invention can be widely applied to cosmetics, pharmaceuticals, and quasi drugs that are applied to the outer skin. The product form is also arbitrary, and examples include emulsion products such as emulsification foundations and sunscreen emulsions, and cream-like products such as skin creams.

  The oil-in-water emulsified composition of the present invention is obtained by a conventional method such as preparing an oil phase and an aqueous phase in advance and emulsifying by mixing and stirring while gradually adding the oil phase to the aqueous phase thus prepared. However, it is not limited to these exemplary manufacturing methods.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited thereto. Unless otherwise specified, all the amounts are mass%.

  First, the evaluation method used in the present invention will be described.

[Evaluation of usability during application]
Each sample (composition) of each example and comparative example was used by a female panel (40 persons), and usability evaluation (elasticity and smoothness) at the time of application was evaluated based on the following evaluation criteria. .
(Evaluation)
◎: More than 80% of subjects answered that they had elasticity when applied and had a smooth feeling when used. ○: More than 50% and less than 80% of subjects had elasticity when applied and had a smooth feeling when used. △: 30% or more and less than 50% of subjects answered that they had a feeling of elasticity when applied and had a smooth feel when used. ×: Less than 30% of subjects showed a feeling of elasticity when applied and was smooth. Answer that it is a feeling of use

[Stability evaluation]
A female panel (40 persons) visually observed the color fringe state of each sample (composition) of each example and comparative example, and comprehensively evaluated the results of evaluation based on the following evaluation criteria.
(Evaluation)
○: No color stripes were observed in the sample (composition). Δ: No color stripes were observed in the sample (composition). X: Color stripes were observed in the sample (composition).

In this example, the following compounds were used as the components shown below.
Both-end silicone polyglyceryl ^{(* 1)} [component (c)]: compound represented by the above formula (II) (wherein R ₆ = C ₄ H ₉ , R ₇ = C ₃ H ₆ , p = 60, q = 3) was used.
Acrylic silicone ^{(* 2)} [Component (c)]: A compound represented by the above formula (III) (wherein R ₈ = isostearyl group, molecular weight 12,000) was used.
POE-modified methylpolysiloxane ^{(* 3)} [component (c)]: compound represented by the above formula (IV) (wherein R ₉ = CH ₃ , R ₁₀ = H, x = 3, y = 2, EO-modified) 20% by mass, molecular weight 6,000).
EO-PO block copolymer ^{(* 4)} : EO / PO = 200 mol / 40 mol.
Hydrophobically modified polyether urethane ^{(* 5)} [component (a)]: copolymer represented by the above formula (I) (wherein R ₁ , R ₂ and R ₄ are an ethylene group, R ₃ = hexamethylene group, R ₅ = 2-dodecyldodecyl group, h = 1, m = 2, k = 120, n = 20).

Example 1
In ion-exchanged water, 10% by mass of 1,3-butylene glycol and 1% by mass of hydrophobically modified polyether urethane ^{(* 5)} were added (adjusted so that the total amount was 100% by mass) to prepare Test Solution 1.

  On the other hand, for comparison, for comparison, 10 mass% of 1,3-butylene glycol and 1 mass% of agar are added to ion-exchanged water (adjusted so that the total amount becomes 100 mass%). (Control test solution) was prepared.

  These test solutions 1 and 2 are put in a container, and as shown in FIG. 2, a 20 mm diameter needle is inserted 2 cm by a rheometer (manufactured by Rheotech Co., Ltd .; FUDOH rheometer NRM-3002D), and then for 10 seconds. The state of stopping and restoring the base was graphed by time and stress.

  As a result, the result shown in FIG. 3 (A) was obtained with the test solution 1, and the result shown in FIG. 3 (B) was obtained with the test solution 2. As is clear from this result, the hydrophobically modified polyether urethane used in the present invention has a shape memory property, and a shape recovery effect with time against stress was confirmed. On the other hand, with agar, the shape collapsed over time with respect to the stress, and the shape could not be recovered.

  That is, if the function of the component (a) used in the present invention can be sufficiently exerted, when used in an external preparation for skin such as makeup cosmetics, it is possible to obtain a feeling of use having a feeling of elasticity over a long period of time.

(Example 2)
With the formulation shown in Table 1 below, an oil-in-water emulsion composition was produced by the following production method.
(Manufacturing method)
(1) to (12) were mixed and cracked and crushed with a bead mill (oil phase). On the other hand, (13) to (20) were mixed and dissolved (aqueous phase). The oil phase was emulsified with a homomixer while gradually adding the oil phase to the aqueous phase.

  About the obtained composition (sample), usability and stability were evaluated by the said test method. The results are shown in Table 1.

  As is clear from the results shown in Table 1, in Samples 1 to 3 and 5 containing the components (a) to (d), there is a composition having elasticity, smooth use feeling, and excellent stability. Obtained. On the other hand, the effect of the present invention could not be obtained in a system in which the component (c) of the present invention was not blended or a system in which the component (d) was not blended (Samples 4 and 6).

(Example 3)
With the formulation shown in Table 2 below, an oil-in-water emulsion composition was produced by the following production method.
(Manufacturing method)
(1) to (6) were mixed and decomposed and crushed with a bead mill (oil phase). On the other hand, (7) to (18) were mixed and dissolved (aqueous phase). The oil phase was emulsified with a homomixer while gradually adding the oil phase to the aqueous phase.

  About the obtained composition (sample), usability and stability were evaluated by the said test method. The results are shown in Table 2.

  As is clear from the results shown in Table 2, the effect of the present invention could not be obtained when a powder component that was not hydrophobized was blended (Samples 7 to 9).

  Below, the formulation example of this invention is shown further.

(Example 4: Suncut oil-in-water emulsion)
(Mixed component) (mass%)
Oil phase component (1) Hydrophobized titanium dioxide 7.5
(2) Acrylic silicone ^{(* 2)} 1.5
(3) POE-modified methylpolysiloxane ^{(* 3)} 1
(4) Decamethylcyclopentasiloxane 10
(5) Octyl paramethoxycinnamate 5
Aqueous component (6) PEG-60 hydrogenated castor oil 2
(7) Dynamite glycerin 6
(8) Succinoglycan 0.3
(9) Carboxymethylcellulose 0.3
(10) Ethanol 5
(11) Hydrophobic modified polyether urethane ^{(* 5)} 1
(12) Residual ion exchange water (Production method)
(1) to (5) were mixed and decomposed and crushed with a bead mill (oil phase). On the other hand, (6) to (12) were mixed and dissolved (aqueous phase). The oil phase was emulsified with a homomixer while gradually adding the oil phase to the aqueous phase.

(Example 5: Oil-in-water emulsion)
(Mixed component) (mass%)
Oil phase component (1) Hydrophobized fine particle titanium dioxide 5
(2) Hydrophobized zinc oxide 5
(3) Acrylic silicone ^{(* 2)} 2
(4) POE-modified methylpolysiloxane ^{(* 3)} 1
(5) Decamethylcyclopentasiloxane 10
(6) Octyl paramethoxycinnamate 5
Aqueous component (7) PEG-60 hydrogenated castor oil 2
(8) Dynamite glycerin 6
(9) Xanthan gum 0.3
(10) Carboxymethylcellulose 0.3
(11) Ethanol 5
(12) Hydrophobic modified polyether urethane ^{(* 5)} 0.5
(13) Residual ion exchange water (Production method)
(1) to (6) were mixed and decomposed and crushed with a bead mill (oil phase). On the other hand, (7) to (13) were mixed and dissolved (aqueous phase). The oil phase was emulsified with a homomixer while gradually adding the oil phase to the aqueous phase.

(Example 6: UV protection whitening serum)
(Mixed component) (mass%)
Oil phase component (1) Hydrophobized fine particle titanium dioxide 5
(2) Acrylic silicone ^{(* 2)} 1
(3) Isostearic acid 1
(4) Decamethylcyclopentasiloxane 10
(5) Octyl paramethoxycinnamate 5
Aqueous component (6) PEG-60 hydrogenated castor oil 2
(7) Dynamite glycerin 6
(8) Succinoglycan 0.3
(9) Carboxymethylcellulose 0.3
(10) Ethanol 6
(11) Citric acid appropriate amount (12) Sodium citrate appropriate amount (13) Ascorbic acid glycoside 2
(14) Caustic potash (15) Hydrophobically modified polyether urethane ^{(* 5)} 0.5
(16) Residual ion-exchanged water (Production method)
(1) to (5) were mixed and decomposed and crushed with a bead mill (oil phase). On the other hand, (6) to (16) were mixed and dissolved (aqueous phase). The oil phase was emulsified with a homomixer while gradually adding the oil phase to the aqueous phase.

It is explanatory drawing of the hydrophobic modified polyether urethane (associative thickener) used for this invention. FIG. 3 is an explanatory diagram showing an experimental method in Example 1. It is a graph which shows the experimental result in Example 1, (A) in the figure is a graph which shows the test result at the time of using the hydrophobic modified polyether urethane (associative thickener) used for this invention, ( B) is a graph showing test results when agar is used.

Claims (8)

(A) Hydrophobically modified polyether urethane represented by the following formula (I), (b) hydrophobic powder, and (c) one selected from polyglycerin modified silicone, acrylic silicone, and polyoxyalkylene modified silicone Alternatively, an oil-in-water emulsion composition containing two or more dispersants and (d) a thickening polysaccharide.
Wherein _{(I), R 1, R} 2 and R ₄ each independently represents a hydrocarbon group; R ₃ represents a hydrocarbon group which may have a urethane bond; R ₅ is a linear, Represents a branched chain or secondary hydrocarbon group; m is a number of 2 or more; h is a number of 1 or more; k and n are each independently a number of 0 to 1000. ]   The oil-in-water emulsion composition according to claim 1, wherein component (d) is succinoglycan and / or xanthan gum. The hydrophobic modified polyether urethane represented by the above formula (I) is one or more polyether polyols represented by R ₁ -[(O—R ₂ ) _k —OH] _m , and R ₃ — (NCO) one or more polyisocyanates represented by _{h + 1} and one or more polyether monoalcohols represented by HO— (R ₄ —O) _n —R ₅ The oil-in-water emulsion composition according to claim 1 or 2, which is a reaction product. In the above formula (I), R ₁ , R ₂ and R ₄ each independently represents an alkylene group having 2 to 4 carbon atoms or a phenylethylene group; R ₃ is a carbon which may have a urethane bond. R 1 represents an alkylene group having 1 to 10 atoms; R ₅ represents an alkyl group having 8 to 36 carbon atoms; m is a number of 2 or more; h is a number of 1 or more; The oil-in-water emulsion composition according to claim 1, wherein the oil-in-water emulsion composition has a number of 0 to 1000. The oil-in-water emulsion composition according to any one of claims 1 to 4, wherein the polyglycerin-modified silicone as the component (c) is a both-ends-siliconized polyglycerin represented by the following formula (II).
[In the formula (II), R ₆ represents a linear or branched alkyl group having 1 to 12 carbon atoms or a phenyl group; R ₇ represents an alkylene group having 2 to 11 carbon atoms; Q is a number from 1 to 11; q is a number from 1 to 11. ] (C) The oil-in-water emulsion composition of any one of Claims 1-4 whose acrylic silicone of a component is a copolymer which consists of a structural unit shown by following formula (III).
[In the formula (III), R ₈ represents an alkyl group having 10 or more and less than 20 carbon atoms; a + b + c = 1, a, b and c are both numbers of 0.2 or more, and r is 5 to 100. Is an integer. ] The oil-in-water type according to any one of claims 1 to 4, wherein the polyoxyalkylene-modified silicone as the component (c) is a copolymer represented by any one of the following formulas (IV), (V), and (VI): Emulsified composition.


[In the formulas (IV) to (VI), R ₉ represents a methyl group or a phenyl group; R ₁₀ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; x is an integer of 1 to 5; y is an integer of 2 to 3; z, s, and t are, on average, the polyoxyalkylene-modified silicone contains 5 to 40% by mass of a polyoxyalkylene group in the molecule, and the polyoxyalkylene-modified silicone is A numerical value such that the molecular weight is 2000 or more is represented. ]   The oil-in-water emulsion composition according to any one of claims 1 to 7, comprising 0.1 to 10% by mass of component (a) and 0.1 to 50% by mass of component (b).