JP6434220B2 - Emulsified makeup cosmetics - Google Patents

Description

  The present invention relates to an emulsified makeup cosmetic, and more particularly to an emulsified makeup cosmetic that has improved stickiness after finishing and the hardness of a cosmetic film, and is excellent in long-lasting makeup.

  In general, emulsified cosmetics contain water, so they give a refreshing feeling when applied to the skin, and they spread well on the skin, making it easier to obtain a uniform finish without unevenness. It has the characteristics such as. In addition, in makeup cosmetics, along with the beauty of color development, the sustainability of makeup effects is an essential function. Conventionally, techniques for enhancing the cosmetic durability of emulsified cosmetics include a technique of blending a hydrophobized powder with an oil-soluble resin (see Patent Document 1) and a silicone polymer having a specific three-dimensional crosslinked structure. A technique for blending a paste-like composition and a polymer emulsion (see Patent Document 2) is known.

Japanese Patent No. 2657219 JP 2005-314372 A

  However, the technique of Patent Document 1 has a problem that depending on the type of the oil-soluble resin, there is a stickiness after finishing, or the skin feels strong due to the hardness of the resin film. Further, the technique of Patent Document 2 is not satisfactory in terms of the flexibility of the decorative film and the twist of the decorative film in a minute portion over time. Accordingly, it is an object of the present invention to solve the problems such as stickiness after finishing of the emulsified makeup cosmetic, the hardness of the cosmetic film, and the twisting over time, and to provide a cosmetic with excellent usability. To do.

  As a result of diligent investigation in view of such circumstances, the film characteristics of the new composite resin emulsion are focused, and this is combined with a partially crosslinked organopolysiloxane polymer and a hydrophobized powder, It has been found that the use of a cosmetic can improve the stickiness after finishing and the hardness of the cosmetic film, and can realize a cosmetic that has a long-lasting makeup, and in particular, has no twist, leading to the completion of the present invention. It was.

That is, the present invention provides [1] the following components (A) to (C):
(A) The following steps (1) to (4);
(1) A polymerization monomer that contains an ester group-containing (meth) acrylic acid monomer, and a polymer obtained by polymerizing the monomer has a glass transition temperature of 95 ° C. or higher and 105 ° C. or lower. Prepolymer containing an isocyanate group and a carboxyl group by reacting polypropylene glycol, dimethylolpropionic acid and an aliphatic or alicyclic polyvalent isocyanate in the presence of a functional monomer (component (b)) Producing (component (a)) and obtaining a mixture of component (a) and component (b),
(2) The carboxyl group contained in the component (a) in the mixture of the component (a) and the component (b) obtained in (1) is neutralized with an equivalent amount of triethanolamine, and (a) A step of obtaining a neutralized product of the component and a mixed solution of the component (b),
(3) A step of emulsifying and dispersing the mixture of the neutralized product of component (a) and component (b) obtained in (2) in an aqueous medium to obtain an emulsion,
(4) It is obtained by polymerizing the component (b) in the emulsion obtained in (3) and sequentially performing each step of obtaining a composite resin emulsion. In step (1), as polypropylene glycol, Two types of polypropylene glycol having a number average molecular weight of 1000 and polypropylene glycol having a number average molecular weight of 2000 are used in a ratio of 94: 6 to 92: 8 (mass ratio), and the components (a) and (b) The ratio of (a) component: (b) component (pure mass ratio) = 50: 50-60: 40 composite resin emulsion component (B) partially crosslinked organopolysiloxane polymer component (C) lipophilic The present invention relates to an emulsified makeup cosmetic characterized by blending a powder with a modified powder.

[2] The compounding amount of the component (A) is 0.05 to 5% by mass in terms of solid content, the compounding amount of the component (B) is 0.1 to 5% by mass, and the compounding amount of the component (C) is It is 1-20 mass%, Cosmetics as described in said [1] characterized by the above-mentioned.

[3] The partially crosslinked organopolysiloxane polymer of component (B) is a partially crosslinked methylpolysiloxane, partially crosslinked methylphenylpolysiloxane, partially crosslinked polyether-modified silicone, or partially crosslinked alkyl-modified silicone. The cosmetic according to [1] or [2], wherein the cosmetic is selected from partially crosslinked alkyl / polyether co-modified silicone and partially crosslinked fluorine-modified silicone.

  The emulsified makeup cosmetic of the present invention has excellent usability, having no stickiness after finishing, flexibility of the cosmetic film, and long-lasting makeup.

  Component (A) used in the present invention is a composite polymer emulsion in which a urethane polymer and an acrylic polymer are blended. This composite resin emulsion comprises a urethane prepolymer (a) containing an isocyanate group and a carboxyl group (hereinafter sometimes referred to as “component (a)”) and a specific polymerizable monomer (b) (hereinafter referred to as “ An aqueous emulsion obtained by emulsifying and dispersing a mixed solution with (b) component ”in some cases in an aqueous medium and polymerizing the component (b) in the emulsion.

The component (A) can be obtained by sequentially performing the following steps (1) to (4).
(1) A polymerization monomer that contains an ester group-containing (meth) acrylic acid monomer, and a polymer obtained by polymerizing the monomer has a glass transition temperature of 95 ° C. or higher and 105 ° C. or lower. Prepolymer containing an isocyanate group and a carboxyl group by reacting polypropylene glycol, dimethylolpropionic acid and an aliphatic or alicyclic polyvalent isocyanate in the presence of a functional monomer (component (b)) Producing (component (a)) and obtaining a mixture of component (a) and component (b),
(2) The carboxyl group contained in the component (a) in the mixture obtained in (1) is neutralized using an equivalent amount of triethanolamine, and the neutralized product of the component (a) and the component (b) Obtaining a mixture of
(3) A step of emulsifying and dispersing the mixed liquid obtained in (2) in an aqueous medium to obtain an emulsion.
(4) A step of polymerizing the component (b) in the emulsion obtained in (3) to obtain a composite resin emulsion.

  Each step will be described below. First, the carboxyl group-containing urethane prepolymer of component (a) obtained in step (1) is a urethane prepolymer containing an isocyanate group and a carboxyl group, and includes polypropylene glycol, dimethylolpropionic acid, aliphatic or It is a polymer obtained by reacting an alicyclic polyvalent isocyanate.

  As polypropylene glycol, two kinds of polypropylene glycol (PPG1000) having a number average molecular weight of about 1000 and polypropylene glycol (PPG2000) having a number average molecular weight of about 2000 are used in a ratio of PPG1000: PPG2000 = 94: 6 to 92: 8 (mass ratio). To do.

  Aliphatic or alicyclic polyvalent isocyanate compounds are those having at least two isocyanate groups in one molecule. Specific examples thereof include dicyclohexylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 1, Examples include 3-cyclohexylene diisocyanate and 1,4-cyclohexylene diisocyanate.

  The acid value of the component (a) is preferably 15 mgKOH / g or more, and more preferably 20 mgKOH / g or more. If it is less than 15 mgKOH / g, the dispersion state in the aqueous solvent may be deteriorated. On the other hand, the upper limit is preferably 70 mgKOH / g, and more preferably 60 mgKOH / g or less. What is necessary is just to adjust the usage-amount of a dimethylol propionic acid so that the acid value of (a) component formed by superposition | polymerization may become said range.

  A desirable use ratio of dimethylolpropionic acid is preferably 30 mol% or more and more preferably 50 mol% or more in the total of polypropylene glycol and dimethylolpropionic acid. On the other hand, it is preferably 90 mol% or less, and more preferably 80 mol% or less. By setting it within this range, the above acid value range can be satisfied.

  On the other hand, the use ratio of polypropylene glycol and dimethylolpropionic acid and the aliphatic or alicyclic polyvalent isocyanate compound is an equivalent ratio, and polypropylene glycol and dimethylolpropionic acid: polyvalent isocyanate compound = 1: 1.2 to 2 is preferable, and 1: 1.5 to 1.9 is more preferable. Thus, by reacting the diol component polypropylene glycol and dimethylolpropionic acid with a stoichiometric excess of the aliphatic or alicyclic polyvalent isocyanate compound, the component (a) Isocyanate groups are introduced.

  The urethane formation reaction for producing the component (a) is carried out in the presence of the component (b). The reaction system is diluted by the component (b), and the reaction can be performed uniformly.

  The polymerizable monomer as the component (b) is a monomer having a polymerizable double bond containing an ester group-containing (meth) acrylic acid monomer, and is particularly reactive with an isocyanate group. Preferred is a polymerizable monomer having no active hydrogen group.

  Examples of such a component (b), particularly a polymerizable monomer containing no active hydrogen group, are (meth) acrylic acid alkyl esters having 1 to 24 carbon atoms, ester group-containing vinyl monomers, styrene. Derivatives, vinyl ether monomers and the like.

  Examples of the (meth) acrylic acid alkyl ester having 1 to 24 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, ( (Meth) butyl acrylate, (meth) acrylate isobutyl, (meth) acrylate s-butyl, (meth) acrylate t-butyl, (meth) acrylate pentyl, (meth) acrylate s-pentyl, (meth) 1-ethylpropyl acrylate, 2-methylbutyl (meth) acrylate, isopentyl (meth) acrylate, t-pentyl (meth) acrylate, 3-methylbutyl (meth) acrylate, neopentyl (meth) acrylate, (meta ) Hexyl acrylate, 2-methylpentyl (meth) acrylate, 4-methylpentyl (meth) acrylate Ruthel, 2-ethylbutyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, 2-heptyl (meth) acrylate, 3-heptyl (meth) acrylate, Octyl (meth) acrylate, 2-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, (3,3,5-acrylic acid) Trimethylhexyl, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, eicosyl (meth) acrylate, (meth) acrylic acid Docosyl, Tetracosyl (meth) acrylate, Methylsic (meth) acrylate Hexyl, (meth) acrylic acid isobornyl (meth) norbornyl acrylate, (meth) acrylate, benzyl (meth) phenethyl acrylate are exemplified. Among these, (meth) acrylic acid alkyl esters having 1 to 24 carbon atoms, particularly (meth) acrylic acid alkyl esters having 1 to 8 carbon atoms are preferable. “(Meth) acryl” means “acryl or methacryl”.

  Specific examples of the ester group-containing vinyl monomer include hydrophobic vinyl monomers such as vinyl acetate, diethyl maleate, dibutyl maleate, vinyl (meth) acrylate, fluoroalkyl esters of (meth) acrylic acid, radical polymerization Examples thereof include unsaturated group-containing macromonomers such as an unsaturated group-containing silicon macromonomer.

  Examples of the styrene derivative include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene and the like. Specific examples of the vinyl ether monomer include vinyl methyl ether and vinyl cyclohexyl ether.

  Only one type of these (b) components may be used, or a plurality of types may be mixed and used. In the case of consisting of one kind, the homopolymer thereof, and in the case of comprising a plurality of kinds, the glass transition temperature of the copolymer in the composition ratio is 95 ° C. or more and 105 ° C. or less. If it is less than 95 ° C., the coating film strength may be insufficient, resulting in twisting, or the drying speed may be slow and color transfer may occur. On the other hand, when the temperature exceeds 105 ° C., the minimum film-forming temperature increases, and a uniform film may not be formed.

In addition, when it is a copolymer, the calculation method of the glass transition temperature is based on following formula (1). Here, Tg is the glass transition temperature (K) of the copolymer, Tga, Tgb, Tgc, etc. are the glass transition temperatures (K) of the homopolymers of the respective monomers a, b, c, etc. Wa, Wb, Wc, etc. indicate the weight fraction of each monomer a, b, c in the copolymer.
1 / Tg = (Wa / Tga) + (Wb / Tgb) + (Wc / Tgc) + (1)
The glass transition temperature of each homopolymer is described in POLYMER HANDBOOK (Polymer Handbook) and the like.

  In the presence of component (b), urethanization reaction of polypropylene glycol, dimethylolpropionic acid, aliphatic or alicyclic polyvalent isocyanate produces component (a). The urethanization reaction may be performed at about 50 to 100 ° C. for about 0.5 to 20 hours. Thereby, (a) component which contains an isocyanate group in a carboxyl group and the terminal can be obtained.

  (A) As a catalyst used for manufacture of a component, the catalyst generally used for a urethanation reaction can be used. Specific examples include dibutyltin dilaurate.

  The number average molecular weight of the component (a) is preferably 800 to 10,000, more preferably 1000 to 9000. When the number average molecular weight is less than 800, the resulting film becomes hard, and problems such as a feeling of stickiness may occur when used as a cosmetic. On the other hand, when it is more than 10,000, the viscosity of the prepolymer itself becomes high, and gelation may occur or a stable emulsion may not be obtained.

  After the urethanization reaction, a mixture of the produced component (a) and component (b) is obtained. The mixing ratio of the component (a) and the component (b) in the mixed solution is (a) :( b) = 50: 50 to 60:40 in terms of a pure weight ratio. When the proportion of the component (b) is larger than this, the decorative film becomes hard and it becomes easy to feel the burden of the decorative film. On the other hand, if the amount of the component (b) is small, the cosmetic film is too soft, so that it tends to cause twisting and the makeup lasting is worsened.

  In step (2), the carboxyl group contained in component (a) in the mixture of component (a) and component (b) obtained in step (1) above is neutralized using an equivalent amount of triethanolamine. Thus, a neutralized product of the component (a) and a mixed solution of the component (b) are obtained. Thus, the dispersibility in the aqueous medium of (a) component can be improved by neutralizing the carboxyl group which (a) component contains.

  Next, in step (3), the neutralized product of component (a) and the mixed solution of component (b) obtained in step (2) are emulsified and dispersed in an aqueous medium to obtain an emulsion. As a method of adding the aqueous medium to the mixture of the neutralized product of component (a) and component (b), a method of dropping and dispersing the aqueous medium in the mixed solution, and dropping and dispersing the mixed solution in the aqueous medium Either method may be used. Examples of the aqueous medium include water and a mixed solution of water and an organic solvent compatible with water such as methanol and ethanol. Among these, water is preferable from the environmental aspect. The temperature during emulsification dispersion is preferably 0 ° C. or higher, more preferably 10 ° C. or higher. On the other hand, 80 degrees C or less is preferable and 60 degrees C or less is more preferable. If the temperature is too high, component (a) may be denatured.

  Further, in step (4), component (b) in the emulsion obtained in step (3) is polymerized to obtain a composite resin emulsion. The polymerization reaction during the polymerization of the component (b) can be performed by a general polymerization method according to the component (b), for example, by adding a radical polymerization initiator to the mixed solution. it can.

  As the radical polymerization initiator, a conventional radical polymerization initiator may be used. For example, azo initiators such as azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyanovaleric acid, sodium persulfate Persulfate initiators such as potassium persulfate and ammonium persulfate, t-butyl hydroperoxide, dilauroyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, etc. Organic peroxide initiators can be used. A redox polymerization initiator in which an organic peroxide initiator or persulfate initiator is combined with a reducing agent such as ascorbic acid, Rongalite or metal sulfite is also preferably used. The amount of the radical polymerization initiator used may be about 0.1 to 5% by mass, preferably about 0.5 to 2% by mass with respect to the polymerizable monomer (b).

  The polymerization of the component (b) is preferably performed at a polymerization temperature of 10 to 80 ° C, and more preferably 30 to 60 ° C. The polymerization is usually almost completed by maintaining the temperature at about 40 to 90 ° C. for about 30 minutes to 3 hours after the end of heat generation. Thereby, a component (A) composite resin emulsion is obtained. This composite resin is considered to have a structure in which a urethane polymer is a core and an acrylic polymer is a shell.

  The minimum film-forming temperature of the component (A) composite resin emulsion is preferably + 20 ° C. or less, and more preferably + 15 ° C. or less. If it exceeds + 20 ° C., defects such as cracks are likely to occur in the resulting film. On the other hand, the minimum film forming temperature is preferably −10 ° C. or higher, and more preferably 0 ° C. or higher. If it is less than -10 degreeC, the water resistance of the film obtained may deteriorate.

  The solid content concentration of the component (A) composite resin emulsion thus obtained is not particularly limited, but is preferably 20 to 50% by mass. In addition, this component (A) composite resin emulsion can be manufactured according to the manufacturing method as described in Unexamined-Japanese-Patent No. 2007-001969.

  The compounding amount of the component (A) in the present invention is preferably 0.05 to 5% by mass, more preferably 0.1 to 2.5% by mass in terms of solid content. If it is such a range, it will be excellent in the stickiness and hardness of the finished decorative film, and the long-lasting makeup.

  The partially crosslinked organopolysiloxane polymer of component (B) used in the present invention is not particularly limited, and a partially crosslinked organopolysiloxane polymer used in ordinary cosmetics can be arbitrarily used. For example, partially cross-linked methylpolysiloxane such as (dimethicone / vinyl dimethicone) crosspolymer, partially cross-linked methylphenylpolysiloxane such as (dimethicone / phenyldimethicone) crosspolymer, dimethicone / (PEG-10 / 15)) crosspolymer, etc. Partially cross-linked polyether-modified silicone, partially cross-linked alkyl-modified silicone such as (vinyl dimethicone / lauryl dimethicone) cross-polymer, partially cross-linked alkyl-polyether co-modified silicone such as PEG-15 lauryl dimethicone cross-polymer, trifluoropropyl dimethicone / Trifluoropropyldivinyldimethicone) Partially cross-linked fluorine-modified silicones such as cross-polymers and the like can be mentioned, and one or more can be used.

  When the partially crosslinked organopolysiloxane polymer of component (B) is swollen with an oil agent, it is more uniformly dispersed, and more stickiness and an effect of improving the hardness of the decorative film are obtained. Further, the partially crosslinked organopolysiloxane polymer of component (B) is often marketed as a mixture with an oil agent, and in the present invention, this commercially available product can also be used. Component (B) is commercially available in the form of a mixture. As a mixture of partially crosslinked methylpolysiloxane and cyclic silicone, KSG-15 (5% solids), partially crosslinked methylpolysiloxane and dimethylpolysiloxane are mixed. KSG-16 (solid content 20-30%) as a mixture, KSG-18 (solid content 10-20%) as a mixture of partially crosslinked methylphenylpolysiloxane and phenyltrimethicone, partially crosslinked polyether-modified silicone and dimethyl KSG-210 (solid content 20-30%) as a mixture with polysiloxane, KSG-41 (solid content 25-35%), KSG-42 (solid content 20- 20%) as a mixture of partially crosslinked alkyl-modified silicone and oil agent 30%), KSG-43 (solid content 25-35%) and KSG-44 (solid content 25-35%), KSG-310 (solid content: 25-35%), KSG-320 (solid content: 20-30%), KSG-330 (solid content: 15-25%) as a mixture of a cross-linked alkyl / polyether co-modified silicone and an oil agent ), KSG-340 (solid content 25-35%) and KSG-340 (solid content 25-35%) (manufactured by Shin-Etsu Chemical Co., Ltd.). The partially crosslinked fluorine-modified silicone is used as a mixture with a cyclic fluorine-containing silicone such as a fluoroalkyl group-containing cyclic organopolysiloxane. For example, KSG-51 (solid content: 15 to 25%: manufactured by Shin-Etsu Chemical Co., Ltd.) is there.

  Although the compounding quantity of the component (B) in this invention is not restrictive, 0.1 to 5.0% is preferable in cosmetics whole quantity. If it is this range, what was excellent from the viewpoint of the stickiness and hardness of the finished decorative film will be obtained.

  The lipophilic powder of component (C) used in the present invention is not particularly limited, and any powder that has been subjected to a lipophilic surface treatment for powders used in ordinary cosmetics can be used arbitrarily. Can do. The powder used for the component (C) can be any powder used for normal cosmetics, and is in the form of plates, spindles, needles, etc., fumes, fine particles, pigment grades, etc. It is not particularly limited by the particle structure such as diameter, porous, non-porous, etc., and examples thereof include inorganic powders, glitter powders, organic powders, pigment powders, composite powders and the like. Specifically, conch, ultramarine, bengara, yellow iron oxide, black iron oxide, titanium oxide, zinc oxide, anhydrous silicic acid, aluminum oxide, cerium oxide, magnesium oxide, zirconium oxide, magnesium carbonate, calcium carbonate, chromium oxide, Inorganic powders such as chromium hydroxide, carbon black, aluminum silicate, magnesium silicate, magnesium aluminum silicate, mica, synthetic mica, synthetic sericite, sericite, talc, kaolin, silicon carbide, barium sulfate, boron nitride , Bismuth oxychloride, titanium mica, iron oxide treated mica, iron oxide treated mica titanium, organic pigment treated mica titanium, silicon dioxide / titanium oxide coated mica, titanium oxide treated glass powder, iron oxide titanium oxide treated glass powder, aluminum powder, etc. Glitter powders, magnesium stearate, Organic powders such as zinc thetaate, N-acyl lysine, nylon, pigment powders such as organic tar pigments, organic pigment lake pigments, fine titanium oxide coated mica titanium, fine zinc oxide coated mica titanium, barium sulfate coating Examples include composite powders such as mica titanium, titanium oxide-containing silicon dioxide, and zinc oxide-containing silicon dioxide, and anhydrous silicic acid. One or more of these can be used. Moreover, you may use the composite powder which compounded 2 or more types of these powder.

  Further, the treatment agent used for the lipophilic treatment is not particularly limited as long as it imparts hydrophobicity or lipophilicity to the powder. Examples of such treatment agents include fluorine compounds, silicone compounds, N-lauroyl-L-lysine, metal soaps, hydrocarbons, higher fatty acids, higher alcohols, esters, waxes, waxes, phospholipids, surfactants. Etc., and composite processing combining these.

  The lipophilic treatment on the powder can be carried out by mixing, heating, baking, gas phase polymerization method, etc. according to a conventional method, and it is sufficient to treat with one or more kinds of treatment agents. Although there is no restriction | limiting in particular as a processing amount of the lipophilic processing agent with respect to, About 0.05 to 15% in processed powder is preferable.

  Although the compounding quantity of the component (C) in this invention is not restrictive, it is preferable that it is 1-20 mass% in the cosmetics whole quantity from a viewpoint of the hardness of the finished cosmetic film and the long-lasting makeup.

  The present invention is an emulsified makeup cosmetic, which may be any of an oil-in-water type, a water-in-oil type, a water-in-oil-in-water type, etc., but has a non-sticky makeup film and a long-lasting makeup effect. The oil-in-water type is preferable because it can be remarkably exhibited.

  As components constituting the aqueous phase, in addition to water, polyhydric alcohols such as 1,3-butylene glycol, dipropylene glycol, glycerin, propylene glycol, and polypropylene glycol or polymers thereof, sugars such as sorbitol, maltitol, and glucose Aqueous components such as alcohol and lower alcohol can be used. The water is not particularly limited, and examples thereof include normal water, purified water, hot spring water, deep water, lavender water, rose water, orange flower water and other steam-derived distilled water, and one or more of them are used. be able to. As a compounding quantity of an aqueous component, it is preferable that it is 5-95% in cosmetics whole quantity from a viewpoint of ensuring the compounding property of a component (A) and making it easy to exhibit an effect.

The oil agent constituting the oil phase may be any solid, semi-solid or liquid oil generally used in cosmetics, including those acting as a solvent for the component (B), and may be animal oil, vegetable oil, mineral oil or synthetic oil. There are hydrocarbons, fats and oils, waxes, esters, fatty acids, higher alcohols, silicone oils, fluorine oils, etc., which can be used.
Examples of the hydrocarbon oil include liquid paraffin, ozokerite, squalane, squalene, pristane, paraffin, isoparaffin, ceresin, petrolatum, microcrystalline wax, and the like, and one kind or two or more kinds can be used.
Liquid oils include linseed oil, camellia oil, macadamia nut oil, corn oil, mink oil, olive oil, avocado oil, sasanqua oil, castor oil, safflower oil, kyounin oil, cinnamon oil, jojoba oil, grape oil, sunflower oil, Almond oil, rapeseed oil, sesame oil, wheat germ oil, rice germ oil, rice bran oil, cottonseed oil, soybean oil, peanut oil, teaseed oil, evening primrose oil, egg yolk oil, cow leg fat, liver oil, triglycerin, glyceryl trioctanoate And glycerin triisopalmitate, and the like, and one kind or two or more kinds can be used. Examples of the solid fat include cacao butter, palm oil, palm oil, palm kernel oil, beef tallow, sheep fat, lard, horse fat, hardened oil, hardened castor oil, owl and shea butter.
Examples of the waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibota wax, whale wax, montan wax, nuka wax, lanolin, reduced lanolin, hard lanolin, kapok wax, sugar cane wax, jojoba wax, shellac wax and the like.
Examples of ester oils include octanoic esters such as cetyl octanoate, lauric esters such as hexyl laurate, myristate esters such as isopropyl myristate and octyldodecyl myristate, palmitate esters such as octyl palmitate, and isocetyl stearate. Stearic acid ester, isostearic acid ester such as isopropyl isostearate, isopalmitic acid ester such as octyl isopalmitate, oleic acid ester such as isodecyl oleate, adipic acid diester such as diisopropyl adipate, sebacic acid such as diethyl sebacate A diester, diisostearyl malate, etc. are mentioned, 1 type, or 2 or more types can be used.
Examples of the silicone oil include dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and the like, and one kind or two or more kinds can be used.
Although the compounding quantity of an oil-based component changes with dosage forms, 3-75% is preferable in cosmetics whole quantity, and 5-50% is more preferable.

  In the present invention, in addition to the above-described components, surfactants, moisturizing components, water-soluble polymers, ultraviolet absorbers, pH, and the like are usually added to cosmetics as long as the effects of the present invention are not impaired. A regulator, an antioxidant, a metal chelating agent, an antiseptic, a powder other than the component (C), a fragrance, various drugs, and the like can be arbitrarily blended within a range not impeding the effects of the present invention, and the production The method is usually a method for producing a cosmetic, and is not particularly limited.

  The emulsified makeup cosmetic of the present invention can be applied to foundations, foundations, BB creams, concealers, eye colors and the like. Moreover, the form of the emulsified makeup cosmetic of the present invention can be carried out as a commonly used dosage form such as a solid, gel, cream or liquid.

  The following examples further illustrate the present invention. In addition, these do not limit this invention at all.

Production Example 1
In a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, 19.7 parts by weight of methyl methacrylate and 0.8 part by weight of n-butyl acrylate, which are polymerizable monomers (b), are used as a reaction solvent. Polypropylene glycol (7.7 parts by weight of number average molecular weight 1000 (* 1) and 0.6 parts by weight of number average molecular weight 2000 (* 2)) and 2.0 parts by weight of dimethylolpropionic acid were added, and the internal temperature Then, 10.2 parts by weight of isophorone diisocyanate was added, and the mixture was heated to 90 ° C. and reacted at this temperature for 5 hours to obtain a urethane prepolymer (a) containing an isocyanate group and a carboxyl group.
While maintaining the obtained urethane prepolymer (a) solution at 50 ° C., 2.3 parts by weight of triethanolamine was added to neutralize the carboxyl groups in the urethane prepolymer (a). Subsequently, 56.6 parts by weight of purified water was added dropwise to this solution at 50 ° C. over 15 minutes to obtain a milky white transparent dispersion.
Thereafter, this dispersion was kept at 50 ° C., and at this temperature, 0.15 part by weight of a 7% by weight aqueous solution of t-butyl hydroperoxide and 0.05 part by weight of an aqueous 1% by weight ascorbic acid were used as a radical polymerization catalyst. Was added to initiate polymerization of the polymerizable monomer (b). After completion of heat generation, the composite resin emulsion 1 was obtained by further heating to 70 ° C. and maintaining for 3 hours.
(In the composite resin emulsion 1, the glass transition temperature of the copolymer obtained by polymerizing the component (b) is about 95 ° C., and the mixing ratio of the urethane prepolymer (a) and the polymerizable monomer (b) is 50:50. .)
* 1: Polypropylene glycol, diol type, 1000 (hydroxyl value: 111 mgKOH / g, manufactured by Wako Pure Chemical Industries, Ltd.)
* 2: Polypropylene glycol, diol type, 2000 (manufactured by Wako Pure Chemical Industries, Ltd., hydroxyl value: 56 mgKOH / g)

Production Example 2
Into a four-necked flask equipped with a thermometer, a stirrer and a reflux condenser, 20.2 parts by weight of methyl methacrylate as a polymerizable monomer (b) and 0.2 part by weight of n-butyl acrylate were added, and Polypropylene glycol (7.2 parts by weight of the above * 1, 0.58 parts by weight of the above * 2) and 2.6 parts by weight of dimethylolpropionic acid were added to bring the internal temperature to 50 ° C. Then, isophorone diisocyanate was added to 10.1 parts. Part by weight was added and the mixture was heated to 90 ° C. and reacted at this temperature for 5 hours to obtain a urethane prepolymer (a) containing an isocyanate group and a carboxyl group.
While maintaining the obtained urethane prepolymer (a) solution at 50 ° C., 2.8 parts by weight of triethanolamine was added to neutralize all the carboxyl groups in the urethane prepolymer (a). Next, 56.3 parts by weight of an aqueous medium was added dropwise to the solution at 50 ° C. over 15 minutes to obtain a milky white transparent dispersion.
Thereafter, this dispersion was kept at 50 ° C., and at this temperature, 0.14 parts by weight of a 7% by weight aqueous solution of t-butyl hydroperoxide as a radical polymerization catalyst and 0.06 parts by weight of an aqueous 1% by weight ascorbic acid solution were obtained. Was added to initiate polymerization of the polymerizable monomer (b). After completion of heat generation, the composite resin emulsion 2 was obtained by further heating to 70 ° C. and maintaining for 3 hours.
(In the composite resin emulsion 2, the glass transition temperature of the copolymer obtained by polymerizing the component (b) is about 102 ° C., and the mixing ratio of the urethane prepolymer (a) and the polymerizable monomer (b) is 50:50. .)

Production Example 3
To a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, 19.6 parts by weight of methyl methacrylate as the polymerizable monomer (b) and 0.8 part by weight of n-butyl acrylate were added, and Polypropylene glycol (8.7 parts by weight of the above * 1 and 0.6 parts by weight of the above * 2) and 2.3 parts by weight of dimethylolpropionic acid were added to an internal temperature of 50 ° C., and then 8.9% of isophorone diisocyanate was added. Part by weight was added and the mixture was heated to 90 ° C. and reacted at this temperature for 5 hours to obtain a urethane prepolymer (a) containing an isocyanate group and a carboxyl group.
While maintaining the obtained urethane prepolymer (a) solution at 50 ° C., 2.6 parts by weight of triethanolamine was added to neutralize all the carboxyl groups in the urethane prepolymer (a). Next, 56.5 parts by weight of an aqueous medium was added dropwise to this solution at 50 ° C. over 15 minutes to obtain a milky white transparent dispersion.
Thereafter, this dispersion was kept at 50 ° C., and at this temperature, 0.07 part by weight of a 7% by weight aqueous solution of t-butyl hydroperoxide as a radical polymerization catalyst and 0.02 part by weight of an aqueous 1% by weight ascorbic acid solution were obtained. Was added to initiate polymerization of the polymerizable monomer (b). After completion of heat generation, the composite resin emulsion 3 was obtained by further heating to 70 ° C. and maintaining for 3 hours.
(In the composite resin emulsion 3, the glass transition temperature of the copolymer obtained by polymerizing the component (b) is about 95 ° C., and the mixing ratio of the urethane prepolymer (a) and the polymerizable monomer (b) is 50:50. .)

Production Example 4
To a four-necked flask equipped with a thermometer, a stirrer and a reflux condenser, 14.8 parts by weight of methyl methacrylate as the polymerizable monomer (b) and 0.6 part by weight of n-butyl acrylate were added, and Polypropylene glycol (9.8 parts by weight of the above * 1 and 0.7 parts by weight of the above * 2) and 2.6 parts by weight of dimethylolpropionic acid were added to an internal temperature of 50 ° C. Then, isophorone diisocyanate was added to 10.1 parts. Part by weight was added and the mixture was heated to 90 ° C. and reacted at this temperature for 5 hours to obtain a urethane prepolymer (a) containing an isocyanate group and a carboxyl group.
While maintaining the obtained urethane prepolymer (a) solution at 50 ° C., 2.9 parts by weight of triethanolamine was added to neutralize all the carboxyl groups in the urethane prepolymer (a). Next, 53.2 parts by weight of an aqueous medium was added dropwise to the solution at 50 ° C. over 15 minutes to obtain a milky white transparent dispersion.
Thereafter, this dispersion was kept at 50 ° C., and at this temperature, 0.11 part by weight of a 7% by weight aqueous solution of t-butyl hydroperoxide as a radical polymerization catalyst and 0.04 part by weight of an aqueous 1% by weight ascorbic acid solution were obtained. Was added to initiate polymerization of the polymerizable monomer (b). After completion of the heat generation, the composite resin emulsion 4 was obtained by further heating to 70 ° C. and maintaining for 3 hours.
(In the composite resin emulsion 4, the glass transition temperature of the copolymer obtained by polymerizing the component (b) is about 95 ° C., and the mixing ratio of the urethane prepolymer (a) and the polymerizable monomer (b) is 60:40. .)

Examples 1 to 3 and Comparative Examples 1 to 5; oil-in-water type liquid foundation Liquid foundations were prepared by the composition shown in Table 1 and the following production method, and <i> no stickiness after finishing, <b>> The flexibility of the cosmetic film, <c> The evaluation of makeup retention. The results are also shown in Table 1.

* 1: Phospholipid (PC purity 70%) 3% treatment * 2: Mass ratio of component (a): component (b) = 50: 50, theoretical Tg of component (b) 95 ° C., solid content 40%
* 3: YODOSOL GH800F (manufactured by Akzo Nobel, solid content 45%)
* 4: DYNAMX (manufactured by Akzo Nobel, polyurethane-14: acrylate copolymer mass ratio = 70:30 mixed ethanol aqueous solution, solid content 28%)
* 5: Rikabond SU-U0609-SS (manufactured by Chuo Rika Kogyo Co., Ltd., (a) component: mass ratio of component (b) = 50: 50, (b) component theoretical Tg 6 ° C., solid content 30%)

(Production method)
A. Ingredients (1) to (7) are uniformly mixed and dissolved.
B. Components (8) to (14) are uniformly dispersed and added to A with stirring.
C. Ingredients (19) to (22) are uniformly dissolved by heating.
D. Ingredients (15) to (18) are uniformly heated and dissolved, and added to C with stirring.
E. What was cooled with stirring is added to B with stirring.
F. Components (23) to (27) were added to E with stirring to obtain an oil-in-water liquid foundation.

(Evaluation method)
Test items <i> No stickiness after finishing, <b> Flexibility of the cosmetic film (no feeling of skin burden), <c> Make-up lasting (no wrinkle), each sample was used by 20 specialist panels Each panel gave a rating based on the following evaluation criteria in 7 levels and given a score. The average value was calculated from the scores of all the panel members, and was determined in 4 levels according to the following criteria.
(Evaluation criteria)
(Score): (Evaluation)
6: very good 5: good 4: slightly good 3: normal 2: slightly bad 1: bad 0: very bad (judgment criteria)
(Average score): (Judgment)
5.0 or more: ◎ (very good)
3.5 or more and less than 5.0: ○ (good)
1.5 or more and less than 3.5: △ (Normal)
Less than 1.5: × (defect)

  From the results shown in Table 1, the liquid foundations of Examples 1 to 3 of the present invention are less sticky after finishing, the flexibility of the cosmetic film, and the longevity of the makeup (no twist) compared to those of Comparative Examples 1 to 5. Was good and excellent. On the other hand, Comparative Example 1 in which the component (A) composite resin emulsion was not blended did not exhibit the effect of suppressing twisting over time, and the alkyl acrylate copolymer was used instead of the composite resin emulsion of component (A). Comparative Example 2 using a polymer emulsion polymer, Comparative Example 3 using a urethane / acrylic mixed polymer instead of the composite resin emulsion of component (A), and (b) of component (A) instead of the composite resin emulsion of component (A) In Comparative Example 4 using the composite resin emulsion having a low theoretical Tg, the stickiness and the hardness of the decorative film have not been improved, and the twist has not been improved. In Comparative Example 5 in which the partially crosslinked organopolysiloxane polymer of component (B) was not blended, the stickiness and the hardness of the decorative film could not be suppressed.

Examples 4 to 6 and Comparative Examples 6 to 10: Water-in-oil bases Bases were prepared according to the composition shown in Table 2 and the following production method, and <i> no stickiness after finishing, <b> We evaluated the softness of the cosmetic film and <c> makeup retention. The results are also shown in Table 2.

(Production method)
A. Components (1) to (12) are uniformly dispersed.
B. Components (13) to (20) were mixed uniformly and added to A with stirring to obtain a water-in-oil base.

  From the results of Table 2, the bases of Examples 4 to 6 of the present invention are less sticky after finishing, softness of the cosmetic film, and long lasting (no twist) compared to those of Comparative Examples 6 to 10. It was good and an excellent effect was obtained. On the other hand, Comparative Example 6 in which the component (A) composite resin emulsion was not blended did not exhibit the effect of suppressing twisting with time, and the alkyl acrylate copolymer was used instead of the composite resin emulsion of component (A). Comparative Example 7 using a polymer emulsion polymer, Comparative Example 8 using a urethane / acrylic mixed polymer instead of the composite resin emulsion of component (A), and (b) of component (A) instead of the composite resin emulsion of component (A) In Comparative Example 9 using the composite resin emulsion having a low theoretical Tg, the stickiness and the hardness of the decorative film could not be improved, and the twist was not improved. In Comparative Example 10 in which the partially crosslinked organopolysiloxane polymer of the component (B) was not blended, the stickiness and the hardness of the decorative film could not be suppressed.

Example 7 BB cream A BB cream was prepared by the following composition and production method.
(Ingredient) (%)
(1) Silicone-treated fine particle zinc oxide * 6 8.0
(2) Phospholipid-treated titanium oxide * 1 6.0
(3) Silicone-treated Bengala * 7 0.12
(4) Silicone-treated yellow iron oxide * 7 0.6
(5) Silicone-treated black iron oxide * 7 0.06
(6) Lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone 2.0
(7) Cyclopentasiloxane 20.0
(8) Mineral oil 1.4
(9) (PEG-15 / Lauryl Dimethicone) Cross Polymer 0.6
(10) Ethylhexyl methoxycinnamate 5.0
(11) Diethylaminohydroxybenzoyl hexyl benzoate 1.0
(12) Bisethylhexyloxyphenol methoxyphenyltriazine 0.5
(13) Neopentyl glycol dicaprate 3.0
(14) Methyl paraoxybenzoate Appropriate amount (15) Ethanol 3.0
(16) 1,3-butylene glycol 3.0
(17) Remaining amount of purified water (18) Sodium chloride 0.1
(19) Composite resin emulsion of Production Example 2 * 8 0.5
* 7: Treatment with 3% of dimethylpolysiloxane (20cs) * 8: Mass ratio of component (a): component (b) = 50: 50, theory of component (b) Tg 102 ° C., solid content 40%

(Production method)
A. Ingredients (10) to (13) are heated and uniformly mixed and dissolved.
B. Components (1) to (9) are uniformly dispersed and mixed with A while stirring.
C. Ingredients (14) to (19) were uniformly mixed and added to B with stirring to obtain a BB cream.

  The BB cream of Example 7 obtained as described above had very good finish, no stickiness after finishing, flexibility of the cosmetic film, and long lasting makeup.

Example 8 Liquid Eye Color A liquid eye color was prepared by the following composition and production method.
(Ingredient) (%)
(1) Composite resin emulsion of Production Example 4 * 9 8.0
(2) Dipropylene glycol 8.0
(3) 1,3-butylene glycol 8.0
(4) Preservative appropriate amount (5) pH adjuster appropriate amount (6) remaining amount of purified water (7) agar 0.5
(8) Stearoyl methyl taurine Na 0.5
(9) Glycerin fatty acid ester 0.6
(10) Behenyl alcohol 0.8
(11) Triethylhexanoin 1.4
(12) (Vinyl Dimethicone / Lauryl Dimethicone) Cross Polymer 0.6
(13) Octyl palmitate 1.0
(14) Mineral oil 1.5
(15) 1,3-butylene glycol 5.0
(16) Lecithin 1.0
(17) Octyl silylation treatment Bengala * 10 0.2
(18) Octyl silylation-treated yellow iron oxide * 10 0.5
(19) Octyl silylation-treated iron oxide coated mica titanium * 10 1.0
(20) Octyl silylation-treated mica titanium * 10 3.0
* 9: Mass ratio of component (a): component (b) = 60: 40, theoretical Tg of component (b) Tg 95 ° C., solid content 40%
* 10: Treatment with 2% triethoxycaprylylsilane

(Production method)
A. Ingredients (2) to (8) are uniformly heated and dissolved.
B. Ingredients (9) to (14) are uniformly dissolved by heating and added to A with stirring.
C. After cooling with stirring, the uniformly dispersed components (15) to (20) and component (1) were added to obtain a liquid eye color.

  The liquid eye color of Example 8 obtained as described above was excellent in the non-stickiness after finishing, the flexibility of the decorative film, and the longevity of the makeup.

Claims (3)

The following components (A) to (C):
(A) The following steps (1) to (4);
(1) A polymerization monomer that contains an ester group-containing (meth) acrylic acid monomer, and a polymer obtained by polymerizing the monomer has a glass transition temperature of 95 ° C. or higher and 105 ° C. or lower. Prepolymer containing an isocyanate group and a carboxyl group by reacting polypropylene glycol, dimethylolpropionic acid and an aliphatic or alicyclic polyvalent isocyanate in the presence of a functional monomer (component (b)) Producing (component (a)) and obtaining a mixture of component (a) and component (b),
(2) The carboxyl group contained in the component (a) in the mixture of the component (a) and the component (b) obtained in (1) is neutralized with an equivalent amount of triethanolamine, and (a) A step of obtaining a neutralized product of the component and a mixed solution of the component (b),
(3) A step of emulsifying and dispersing the mixture of the neutralized product of component (a) and component (b) obtained in (2) in an aqueous medium to obtain an emulsion,
(4) It is obtained by polymerizing the component (b) in the emulsion obtained in (3) and sequentially performing each step of obtaining a composite resin emulsion. In step (1), as polypropylene glycol, Two types of polypropylene glycol having a number average molecular weight of 1000 and polypropylene glycol having a number average molecular weight of 2000 are used in a ratio of 94: 6 to 92: 8 (mass ratio), and the components (a) and (b) The ratio of (a) component: (b) component (pure mass ratio) = 50: 50-60: 40 composite resin emulsion component (B) partially crosslinked organopolysiloxane polymer component (C) lipophilic An emulsified makeup cosmetic characterized by comprising a powdered powder. The compounding amount of the component (A) is 0.05 to 5% by mass in terms of solid content, the compounding amount of the component (B) is 0.1 to 5% by mass, and the compounding amount of the component (C) is 1 to 20% by mass. The cosmetic material according to claim 1, wherein the cosmetic material is a cosmetic material. The partially crosslinked organopolysiloxane polymer of component (B) is partially crosslinked methylpolysiloxane, partially crosslinked methylphenylpolysiloxane, partially crosslinked polyether modified silicone, partially crosslinked alkyl modified silicone, partially crosslinked alkyl 3. The cosmetic according to claim 1, wherein the cosmetic is selected from polyether co-modified silicone and partially cross-linked fluorine-modified silicone.