JP2015193551A - Cosmetic for eyelashes - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cosmetic for eyelashes which is excellent in curling effect and in prolonged effect of curling over time, while giving resilient, elastic feeling without impairing the eyelashes' original texture because of flexibility of cosmetic film, and further is excellent in glossy feeling of cosmetic film.SOLUTION: The cosmetic for eyelashes comprises: film-forming emulsion polymer in which urethane-based polymers and acryl-based polymers are blended in a specific ratio and which has specific glass transition temperature; a gelatinizer; and oil-soluble resin.

Description

  The present invention relates to cosmetics for wrinkles, and more specifically, while having excellent curling effect and long-lasting curling effect, the decorative film is flexible, so that it has a flexible elasticity without impairing the original texture of wrinkles. Further, the present invention relates to a vaginal cosmetic that is excellent in the gloss of the decorative film.

Cosmetics for eyelids have a cosmetic effect that attractively creates the impression of the eyes by curling the eyelids (curling effect) to make the eye circumference larger and more three-dimensional. Since the makeup film easily breaks down due to frequent blinking, not only the makeup effect immediately after, but also the curl sustaining effect that keeps the finish unchanged over time is regarded as an important factor. More recently, from the viewpoint of cosmetic expression that a natural and uncomfortable finish is preferred, and from the viewpoint of reducing the burden, makeup films that evoke the natural suppleness of elasticity and healthy habits. New added value, such as the glossiness of, has been demanded.
Conventional salmon cosmetics are mainly composed of solid oily components such as wax, film forming agents such as resins and synthetic polymers, and powders, in order to provide functionality that meets consumer demands. Various compounding studies have been conducted.

  For example, by using a (meth) acrylic acid / (meth) acrylic acid alkyl copolymer emulsion, nonionic surfactant, non-volatile liquid oil, and wax together, the curl-keep effect, good elongation, adhesion, resistance Techniques for cosmetics that are excellent in sebum and friction resistance and have good storage stability (see Patent Document 1) have been studied. Also, the combined use of aqueous phase, fatty phase, structurant and polyurethane / poly (meth) acrylate graft copolymer has the effect of lengthening wrinkles, film homogeneity, flexibility, improved separability, long Techniques for cosmetic compositions having the advantage of banding (see Patent Document 2) have been studied.

JP 2005-263701 A JP 2007-45827 A

  However, the technique of Patent Document 1 is excellent in the curl effect and the curl sustaining effect, but the film is hard, and the natural supple feeling of elasticity is lost, and further, a sufficient glossy feeling cannot be obtained, which is unnatural. There was a tendency to be finished. In addition, the technique of Patent Document 2 is excellent in flexibility, so that a natural finish that maintains a supple feeling of elasticity is obtained, but the strength of the decorative film is not sufficient, and the curling effect and the curling effect are persistent. It was inferior. Therefore, while being excellent in curling effect and curling sustaining effect over time, it has a flexible elasticity without sacrificing the original texture of the bag because of the softness of the decorative film, and also excellent in the gloss of the decorative film A vaginal cosmetic was desired.

  As a result of intensive research to solve the above problems, the present inventor has made a film-forming property having a specific glass transition temperature, in which a urethane polymer and an acrylic polymer are blended at a specific ratio, with respect to cosmetics for vases. Focusing on the emulsion polymer creating a flexible film, combining with a gelling agent and an oil-soluble resin, the cosmetic film is flexible while being excellent in curling effect and curling effect over time The present inventors have found that a vaginal cosmetic that has a supple elasticity without sacrificing the original texture of the wrinkle and that is also excellent in the gloss of the decorative film can be obtained.

That is, the present invention includes 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 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) 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 to 60:40 composite resin emulsion (B) gelling agent (C) cosmetics containing oil-soluble resin A fee is provided.

  The present invention has a curling effect and a long-lasting curling effect, but has a flexible elasticity without sacrificing the original texture due to the softness of the decorative film. Is also related to excellent vaginal cosmetics.

Hereinafter, the present invention will be described in detail.
The component (A) used in the present invention is in the form of a polymer emulsion in which a urethane polymer and an acrylic polymer are blended, and this composite resin emulsion is a urethane prepolymer containing an isocyanate group and a carboxyl group (a ) (Hereinafter sometimes referred to as “component (a)”) and a specific polymerizable monomer (b) (hereinafter sometimes referred to as “component (b)”) in an aqueous medium. An aqueous emulsion obtained by emulsifying and dispersing and polymerizing the component (b) in the emulsion (hereinafter referred to as “acryl urethane composite emulsion polymer”). After drying, a flexible film having excellent strength is obtained. Therefore, the decorative film of the present invention can exhibit the effect of making the curl effect and the curl lasting effect compatible with the supple elasticity.

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.
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.

  The aliphatic or alicyclic polyvalent isocyanate compound has 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 bulk bleeding, 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.

  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 a polo drop that is partially lost tends to occur. On the other hand, if the amount of the component (b) is small, the decorative film is too soft, so that bleeding tends to occur.

  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.

  Furthermore, in the step (4), the component (b) in the emulsion obtained in the step (3) is polymerized to obtain a core-shell type polymer 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 solid content concentration of the component (A) acrylic urethane composite emulsion polymer used in the present invention is not particularly limited, but is 20 to 50% by mass (hereinafter simply referred to as “%”), and the content in the present invention is In terms of solid content, it is preferably 1 to 30%, more preferably 2 to 20%. If it is within this range, the decorative film is flexible, so it has excellent flexibility and glossiness of the decorative film. Can be obtained. The preferred content of the component (A) in the oil-in-water type having the aqueous component as the main component and the aqueous component as the outer layer is 4 to 30%, more preferably 8 to 20%, and in the oil having the oil component as the outer layer. The preferable content of the component (A) in the water mold is 1 to 20%, and further 2 to 10%.

  The component (B) gelling agent used in the present invention ensures appropriate usability as a vaginal cosmetic by preventing dripping and blurring, and has an appropriate film thickness that can function as a decorative film. It has a role of attaching to the ridge. If it is normally used for cosmetics, it can be used without being specifically limited. Examples of the oil gelling agent that gels the oil component include wax, metal soap, organically modified clay mineral, and anhydrous silicic acid. Specifically, paraffin wax, ceresin wax, microcrystalline wax, hydrogenated microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, ethylene / propylene copolymer, candelilla wax, carnauba wax, beeswax, mole, gay wax, jiro, Waxes such as montan wax, stearyl-modified methylpolysiloxane, behenyl-modified methylpolysiloxane, metal soaps such as aluminum stearate and magnesium stearate, dextrin fatty acid esters such as dextrin palmitate, sucrose palmitate, starch palmitic acid Esters, polysaccharide fatty acid esters such as fructooligosaccharide stearates, dioctadecyldimethylammonium salts Sex montmorillonite, organically modified clay minerals such as dihexadecyldimethylammonium salt-modified montmorillonite, a porous or fumed silicic anhydride, silicic acids such as dimethylsilyl silica, and 12-hydroxystearic acid. Among them, vaginal cosmetics containing waxes not only increase the viscosity of the cosmetic liquid and make it suitable for application, but also contribute to improving the strength of the formed cosmetic film. It is preferable at the point from which the thing excellent in the sustained effect is obtained. Commercially available products include EPS wax (manufactured by Nippon Natural Products), PERFORMALENE 655, PERFORMALENE 500 (manufactured by New Phase Technology), PM-WAX82 (manufactured by Nikko Rica), multi-wax W-445 (manufactured by SONNEBORN), NC -1630 Candelilla wax (manufactured by Celerica Noda), refined candelilla wax SR-3, high melting point candelilla wax FR100, refined candelilla wax MD-21, refined carnauba wax No. 1 (produced by Nippon Natural Products), WHITE Examples include BEES WAX (manufactured by Miki Chemical Co., Ltd.), BEES WAX S (manufactured by Croda), and the like.

  Examples of the gelling agent for the aqueous component include an aqueous alkaline thickened polymer emulsion. Aqueous alkali thickening polymer emulsion is a system in which polymer fine particles are stably dispersed in an aqueous solvent. A liquid obtained by polymerizing a monomer emulsified with a surfactant or a milky sap that exists in nature. Under neutrality, it is a milky white emulsion, which is thickened by neutralization with an alkaline agent and imparts viscosity to the cosmetic. An aqueous dispersion prepared by adjusting an aqueous alkali-thickened polymer emulsion to 0.3% in terms of solid content has an increase in viscosity when neutralized with triethanolamine as an alkali agent to adjust the pH to 7.5. Compared to the viscosity before neutralization with 100% or more. In the present invention, the viscosity is a value measured with a B-type viscometer, for example, a single cylindrical rotational viscometer vistron VS-A1 (manufactured by Shibaura System Co., Ltd.).

  Specific examples include a polymer emulsion containing a copolymer of acrylic acid and an alkyl acrylate ester as a polymer component, a polymer emulsion containing a copolymer of acrylic acid and an alkyl methacrylate ester as a polymer component, acrylic acid and an alkyl acrylate ester. And a polymer emulsion containing a copolymer of methacrylic acid alkyl ester as a polymer, a polymer emulsion containing a copolymer of acrylic acid, methacrylic acid and alkyl acrylate as a polymer, acrylic acid, alkyl acrylate and polyethylene acrylate A polymer emulsion comprising a copolymer of glycol ester, a copolymer of acrylic acid, alkyl methacrylate and acrylic acid (polyoxyethylene monoalkyl ether) ester Polymer emulsion containing polymer, polymer emulsion containing acrylic acid, methacrylic acid alkyl ester and methacrylic acid (polyoxyethylene monoalkyl ether) ester copolymer, acrylic acid alkyl ester and methacrylic acid (polyoxyethylene mono) Examples include polymer emulsions containing a copolymer of alkyl ether) ester as a polymer, and polymer emulsions containing a copolymer of acrylic acid, alkyl acrylate ester and itaconic acid (polyoxyethylene monoalkyl ether) ester as a polymer. . Of these, the alkyl group of alkyl acrylate or alkyl methacrylate may be one type having 1 to 12 carbon atoms or two or more types. Above all, if the monomer constituting the polymer is a polymer having acrylic acid, it not only increases the viscosity of the cosmetic liquid and makes it suitable for coating, but also contributes to improving the strength of the cosmetic film. This is preferable in terms of achieving both elasticity. Examples of commercially available products include Primal ASE-60 (solid content 28%) (manufactured by Polymer Latex), SALCARE SC81 (solid content 30%) (manufactured by Ciba Specialty Chemicals), ACULYN22 (solid content 30%), ACULYN28 ( Solid content 20%), ACULYN33A (solid content 28%) (both manufactured by Rohm & Haas) and the like.

  The component (B) in this invention can be used 1 type or in combination of 2 or more types. The content of the component (B) varies depending on the type and shape of the gelling agent and is not particularly limited, but is preferably 0.1 to 25% in the total cosmetic. If it is this range, the usability | use_condition is excellent and the cosmetics for glazing which were excellent in the point of making it adhere to a wrinkle with the film thickness sufficient to exhibit the function of a decorative film are obtained. In addition, when the component (B) is a wax, the structure of the wax easily collapses due to friction during application, so that the spread is good, the uniformity of the decorative film is excellent, and the strength of the decorative film after formation is high. Since it contributes to the improvement, it is possible to obtain a vaginal cosmetic that is excellent in curling effect and curling effect over time. When component (B) is a wax, it is preferably contained in the total cosmetics in an amount of 3 to 25%, more preferably 5 to 15%.

  The oil-soluble resin of component (C) used in the present invention is not particularly limited and can be used as long as it is usually used in cosmetics. Examples thereof include terpene resins such as candelilla resin, hydrogenated pentaerythrityl rosinate, hydrogenated glyceryl abietate, silicone resin, vinyl acetate resin, polyvinyl isobutyl ether, polyisobutylene, and the like. Among them, silicone resins such as polymethylsilsesquioxane such as trimethylsiloxysilicic acid, acrylic-silicone graft copolymer, and trimethylsilsesquioxane have excellent curling effect and curl sustaining effect due to their excellent hardness. Is preferably used because it can improve glossiness by enhancing the smoothness of the decorative film. As these commercial products, KF7312J (solid content 50% decamethylcyclopentasiloxane solution, manufactured by Shin-Etsu Chemical Co., Ltd.), KF-9021 (50% decamethylcyclopentasiloxane solution, Shin-Etsu) is trimethylsiloxysilicic acid. Chemical Industry Co., Ltd.), BY11-018 (30% decamethylcyclopentasiloxane solution, Toray Dow Corning Silicone Co., Ltd.), alkyl acrylate / dimethicone) copolymer KP541 (solid content 60% , Solvent: isopropanol), KP545 (solid content 30%, solvent: decamethylcyclopentasiloxane), KP575 (solid content 30%, solvent: decamethylcyclopentasiloxane) which is a copolymer of (acrylates / ethylhexyl acrylate / dimethicone methacrylate) (Shin-Etsu Chemical Co., Ltd.) SILFORM FLEXIBLE RESIN (manufactured by Momentive Performance Materials Japan), which is a polymethylsilsesquioxane, and the like.

The content of the component (C) in the present invention is preferably 0.5 to 15%, more preferably 1 to 10% as a solid content concentration. Within this range, the curl effect and the curl sustaining effect are dramatically improved. These oil-soluble resins can be used alone or in combination of two or more, and can also be used by dissolving in other low-viscosity oils.

  In addition to the components described above, the vaginal cosmetics of the present invention are components that are usually used in cosmetics, emulsion polymers, oily components, powder components, surfactants, as long as the effects of the present invention are not hindered. An aqueous component, an ultraviolet absorber, a moisturizer, an anti-fading agent, an antioxidant, an antifoaming agent, a cosmetic component, an antiseptic, a fragrance and the like can be appropriately contained.

  Examples of emulsion polymers other than component (A) and component (B) include, for example, alkyl acrylate copolymer emulsion, alkyl acrylate copolymer emulsion, alkyl methacrylate copolymer emulsion, alkyl methacrylate copolymer emulsion, acrylic acid / alkyl acrylate copolymer emulsion. , Acrylic acid / alkyl methacrylate copolymer emulsion, methacrylic acid / alkyl acrylate copolymer emulsion, methacrylic acid / alkyl methacrylate copolymer emulsion, organopolysiloxane polymer emulsion, polyvinyl acetate polymer emulsion, etc. Two or more types can be used.

  Oily components other than the above essential components include hydrocarbons, fats and oils, waxes, hardened oils, regardless of the origin, such as animal oils, vegetable oils, synthetic oils, and solid oils, semisolid oils, liquid oils, etc. , Ester oils, fatty acids, higher alcohols, silicone oils, fluorinated oils, lanolin derivatives, oily gelling agents, oil-soluble resins, volatile oils, etc., one or two of these More than seeds can be used. Specifically, hydrocarbons such as liquid paraffin, squalane, petrolatum, oils such as olive oil, castor oil, mink oil, macadamian nut oil, jojoba oil, cetyl isooctanoate, isopropyl myristate, isopropyl palmitate, Octyldodecyl myristate, glyceryl trioctanoate, polyglyceryl diisostearate, diglyceryl triisostearate, glyceryl tribehenate, diisostearyl malate, neopentyl glycol dioctanoate, cholesterol fatty acid ester, N-lauroyl-L-glutamate di (cholesteryl Esters such as behenyl octyldodecyl), stearyl alcohol, cetyl alcohol, lauryl alcohol, oleyl alcohol, isostearyl alcohol, behenyl alcohol Higher alcohols such as alcohol, silicones such as methylphenyl polysiloxane and fluorine-modified organopolysiloxane, fluorine oils such as perfluorodecane, perfluorooctane and perfluoropolyether, lanolin, lanolin acetate, lanolin fatty acid isopropyl Volatile oils such as lanolin derivatives such as lanolin alcohol, hydrocarbon oils such as light liquid isoparaffin and isododecane, silicones such as decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, methyltrimethicone, and low polymerization degree dimethylpolysiloxane Etc.

  The powder component is not particularly limited by the shape of a plate, spindle, needle, etc., particle size, particle structure such as porous, non-porous, etc., inorganic powders, glitter powders, organic Examples thereof include powders, pigment powders, and composite powders. Specifically, carbon black, conch, ultramarine, bengara, yellow iron oxide, black iron oxide, titanium oxide, zinc oxide, aluminum oxide, cerium oxide, magnesium oxide, zirconium oxide, magnesium carbonate, calcium carbonate, chromium oxide, water Inorganic powders such as chromium oxide, 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 coated mica, iron oxide coated mica titanium, silicic anhydride coated mica titanium, organic pigment treated mica titanium, titanium oxide coated glass powder, titanium oxide / iron oxide coated glass powder, titanium oxide / anhydrous Silica coated glass powder, aluminum powder, etc. Glitter powders, organic powders such as magnesium stearate, zinc stearate, N-acyl lysine, nylon, pigment powders such as organic tar pigments, lake pigments of organic pigments, fine titanium oxide coated mica titanium, Fine powder zinc oxide coated mica titanium, barium sulfate coated mica titanium, titanium oxide-containing silicon dioxide, zinc oxide-containing silicon dioxide, etc., polyethylene terephthalate / aluminum / epoxy laminated powder, polyethylene terephthalate / polyolefin laminated film powder, polyethylene terephthalate / Examples thereof include polymethyl methacrylate laminated film powders, and one or more of them can be used. These powders may be used alone or in combination of two or more, and are known using fluorine compounds, silicone oils, metal soaps, waxes, surfactants, oils and fats, hydrocarbons, etc. It may be subjected to a surface treatment by a method.

  As the surfactant, any surfactant that is generally used in cosmetics can be used. Nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, etc. Is mentioned. For example, glycerin fatty acid ester and its alkylene glycol adduct, polyglycerin fatty acid ester and its alkylene glycol adduct, sorbitan fatty acid ester and its alkylene glycol adduct, sucrose fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyalkylene alkyl co-modified Examples thereof include organopolysiloxane, polyether-modified organopolysiloxane, and lecithin.

  The aqueous component may be any component that is soluble in water, for example, lower alcohols such as ethyl alcohol and butyl alcohol, glycols such as propylene glycol, 1,3-butylene glycol, dipropylene glycol, and polyethylene glycol. Glycerols such as glycerin, diglycerin and polyglycerin, and plant extracts such as aloe vera, witch hazel, hamamelis, cucumber, lemon, lavender and rose. Examples of water-soluble polymers include guar gum, sodium chondroitin sulfate, sodium hyaluronate, gum arabic, sodium alginate, carrageenan and other semi-synthetic compounds such as methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, carboxyvinyl polymer, Synthetic compounds such as alkyl-added carboxyvinyl polymer and sodium polyacrylate can be mentioned. Other moisturizing agents such as protein, mucopolysaccharide, collagen, elastin, keratin and the like can also be contained.

  Examples of ultraviolet absorbers include benzophenone-based, PABA-based, cinnamic acid-based, salicylic acid-based, 4-tert-butyl-4'-methoxydibenzoylmethane, and oxybenzone. Examples of humectants include protein, mucopolysaccharide, and collagen. , Elastin, keratin, etc., antioxidants such as α-tocopherol, ascorbic acid, etc., cosmetic ingredients such as vitamins, anti-inflammatory agents, herbal medicines, etc., antiseptics such as paraoxybenzoic acid esters, phenoxyethanol, 1 , 2-pentanediol and the like.

  Examples of the cosmetics for wrinkles of the present invention include mascara, mascara base coat, mascara top coat, and the like, and can be used in any of aqueous, oil-in-water, and water-in-oil types.

Hereinafter, the present invention will be described in more detail with reference to examples. Note that these do not limit the present invention.
(Composite resin emulsion)
[Production Example 1]: Composite resin emulsion 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]: Composite resin emulsion 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 raising the temperature 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]: Composite resin emulsion 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 raising the temperature 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]: Composite resin emulsion 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 heat generation, the composite resin emulsion 4 was obtained by further raising the temperature 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. .)

(Cosmetic for salmon)
Examples 1 to 8 and Comparative Examples 1 to 4: Oil-in-water mascara cosmetic (cream)
A mascara cosmetic with the formulation shown in Table 1 below was prepared, a. Curl effect, b. Curling effect, c. Supple elasticity, d. The gloss of the decorative film was evaluated by the following evaluation method. The results are also shown in Table 1.

* 1: Pine Crystal KE-311 (Arakawa Chemical Industries)
* 2: 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%)
* 3: YODOSOL GH810F (solid content 45%) (manufactured by Akzo Nobel)
* 4: DYNAMX (manufactured by Akzo Nobel, polyurethane-14: acrylate copolymer mass ratio = 70:30 mixed ethanol aqueous solution, solid content 28%)

(Production method)
A. Components (1) to (8) are heated and dissolved at 100 ° C.
B. Components (9) to (19) are heated and mixed at 90 ° C.
C. Add B to A and emulsify.
D. C was filled into a container to obtain a mascara cosmetic.

(Evaluation method)
About the following item, the use test by 20 expert panels was done about each sample. Each sample was applied at the time of wrinkle once, and each panel member immediately after application for a, c, d, and for b, the condition of the cosmetic film after normal life for 8 hours after application, the following absolute evaluation criteria The evaluation was made in 7 stages, given a score, the average value was calculated from the total score of all the panel members, and judged according to the following criteria.
<Evaluation item>
a. Curl effect b. Curling effect c. Supple elasticity d. Glossy makeup film

<Absolute evaluation criteria>
(Score): (Evaluation)
6: Very good 5: Good 4: Somewhat good 3: Normal 2: Somewhat bad 1: Bad 0: Very bad
<Criteria>
(Judgment): (Average score)
◎: More than 4.5 points: Very good ○: More than 3.5 points and less than 4.5 points: Good △: More than 1 point and less than 3.5 points: Slightly poor ×: Less than 1 point: Bad

As is apparent from the results in Table 1, the mascara cosmetics of Examples 1 to 8 of the present invention are superior in curling effect and curling sustaining effect over time, compared to the mascara cosmetics of Comparative Examples 1 to 4, Since the decorative film is flexible, it has a supple elasticity without impairing the original texture of the bag, and also has an excellent gloss feeling of the decorative film.
On the other hand, in Comparative Example 1 using the acrylic part of the acrylic urethane composite emulsion polymer of component (A) having a theoretical Tg of 6 ° C., the coating strength of the acrylic part is insufficient and the decorative film is too soft. For this reason, the curling effect was low immediately after coating, and a satisfactory curling effect was not obtained. In Comparative Example 2 in which an alkyl acrylate copolymer emulsion polymer was used in place of the acrylic urethane composite emulsion polymer of component (A), the decorative film was hard and brittle, so there was no supple elasticity and not only the curling effect. In addition, the satisfactory glossiness of the decorative film was not obtained. In Comparative Example 3 in which a urethane / acrylic mixed polymer was used instead of the acrylic urethane composite emulsion polymer of component (A), the cosmetic film was too soft, so that the curl effect and the curl sustaining effect were not sufficient, and the acrylic was hard Reflecting the characteristics, we were not able to obtain a satisfactory supple elasticity.
Since Comparative Example 4 which does not contain the gelling agent of component (B) cannot be applied in a wrinkle shape with a sufficient thickness for the decorative film to function, the curling effect, the curling effect, the supple elasticity, and the makeup In all respects of film gloss, satisfactory results were not obtained.

Examples 9 to 16 and Comparative Examples 5 to 8: Water-in-oil type mascara cosmetic (gel)
A mascara cosmetic with the formulation shown in Table 2 below was prepared: a. Curl effect, b. Curling effect, c. Supple elasticity, d. The gloss of the decorative film was evaluated by the following evaluation method. The results are also shown in Table 2.

* 5: Leopard KL (Chiba Flour Mills)
* 6: BENTONE 38V BC (Made by Elementis)
* 7: SILFORM FLEXIBLE RESIN (made by Momentive Performance Materials Japan)
* 8: KF-7312J (manufactured by Shin-Etsu Chemical Co., Ltd.)

(Production method)
A. Components (1) to (14) are heated and dissolved at 100 ° C.
B. Components (15) to (23) are heated and mixed at 90 ° C.
C. Cool to room temperature, add B to A and emulsify.
D. C was filled into a container to obtain a mascara cosmetic.

(Evaluation method)
About the following item, the use test by 20 expert panels was done about each sample. Each sample was applied at the time of wrinkle once, and each panel member immediately after application for a, c, d, and for b, the condition of the cosmetic film after normal life for 8 hours after application, the following absolute evaluation criteria The evaluation was made in 7 stages, given a score, the average value was calculated from the total score of all the panel members, and judged according to the following criteria.
<Evaluation item>
a. Curl effect b. Curling effect c. Supple elasticity d. Glossy makeup film

<Absolute evaluation criteria>
(Score): (Evaluation)
6: Very good 5: Good 4: Somewhat good 3: Normal 2: Somewhat bad 1: Bad 0: Very bad
<Criteria>
(Judgment): (Average score)
◎: More than 4.5 points: Very good ○: More than 3.5 points and less than 4.5 points: Good △: More than 1 point and less than 3.5 points: Slightly poor ×: Less than 1 point: Bad

As is apparent from the results in Table 2, the mascara cosmetics of Examples 9 to 16 of the present invention are superior in curling effect and curl sustaining effect over time, as compared to the mascara cosmetics of Comparative Examples 5 to 8. Since the decorative film is flexible, it has a supple elasticity without impairing the original texture of the bag, and also has an excellent gloss feeling of the decorative film.
On the other hand, in Comparative Example 5 using the acrylic part of the acrylic urethane composite emulsion polymer of component (A) having a theoretical Tg of 35 ° C., the coating strength of the acrylic part is insufficient and the decorative film is too soft. For this reason, the curling effect was low immediately after coating, and a satisfactory curling effect was not obtained. In Comparative Example 6 in which the alkyl acrylate copolymer emulsion polymer was used instead of the acrylic urethane composite emulsion polymer of component (A), the decorative film was hard and brittle, so there was no supple elasticity and not only the curling effect. In addition, the satisfactory glossiness of the decorative film was not obtained. In Comparative Example 7 in which a urethane / acrylic mixed polymer was used instead of the acrylic urethane composite emulsion polymer of component (A), the cosmetic film was too soft, so that the curl effect and the curl sustaining effect were not sufficient, and the acrylic was hard Reflecting the characteristics, we were not able to obtain a satisfactory supple elasticity.
Since Comparative Example 8 which does not contain the gelling agent of component (B) cannot be applied in a wrinkle shape with sufficient thickness for the decorative film to exhibit its function, the curl effect, the curl lasting effect, the supple elasticity, the makeup In all respects of film gloss, satisfactory results were not obtained.

Example 17: Water-in-oil mascara cosmetic (liquid)
(Ingredient) (%)
(1) Acrylic-silicone graft copolymer * 9 15
(2) Trimethylsiloxysilicate solution * 8 10
(3) Vaseline 5
(4) Carnauba wax 10
(5) Microcrystalline wax * 10 5
(6) Dextrin fatty acid ester * 11 2
(7) Decamethylcyclopentasiloxane Residual amount (8) Organically modified bentonite * 12 3
(9) Talc 10
(10) Polypropylene fiber * 13 2
(11) Haze-like silicic acid * 14 3
(12) Methyl paraoxybenzoate 0.1
(13) Phenoxyethanol 0.1
(14) Lecithin 0.2
(15) Composite resin emulsion 2 of Production Example 2 1

* 9: KP-545 (manufactured by Shin-Etsu Chemical Co., Ltd.) (solid content 30%, solvent: decamethylcyclopentasiloxane)
* 10: MULTIWAX W-835 MYCROCRYSTALLINEWAX (manufactured by SONNEBORN)
* 11: Leopard TL2 (Chiba Flour Mills)
* 12: BENTONE 27V (manufactured by ELEMENTIS)
* 13: 6T, 3mm
* 14: AEROSIL 200 (Nippon Aerosil Co., Ltd.)

(Manufacturing method)
A. Ingredients (1) to (7) are heated and mixed at about 110 ° C. to be uniform.
B. Ingredients (8) to (15) are added to A and mixed uniformly.
C. B was filled in a container to obtain an oily mascara cosmetic.

The mascara cosmetics obtained as described above are excellent in curling effect and long-lasting curling effect, but have a flexible elasticity without sacrificing the original texture of the skin due to the flexible makeup film. Furthermore, the gloss of the decorative film was excellent.

Example 18: Water-in-oil mascara base cosmetic (gel)
(Ingredient) (%)
(1) Hydrogenated rosin acid pentaerythrityl * 15 1
(2) Light liquid isoparaffin 30
(3) Hydrogenated ester gum * 1 2
(4) Fischer-Tropsch wax (melting point 80-84 ° C.) 15
(5) Polyethylene terephthalate powder * 16 5
(6) Lauroyl lysine 3
(7) Ethyl paraoxybenzoate 1
(8) Purified water remaining amount (9) Nylon fiber * 17 0.5
(10) Titanium / titanium oxide sintered product * 18 10
(11) Bengala-coated mica titanium 1
(12) Sodium hyaluronate 0.1
(13) Trehalose 0.1
(14) 1,3-butylene glycol 3
(15) Alkyl acrylate / vinyl acetate copolymer emulsion * 19 5
(16) Composite resin emulsion 3 2 of Production Example 3

* 15: Ester gum HP (Arakawa Industrial Co., Ltd.)
* 16: Snow Reef P (Oken)
* 17: 3T, 1 mm, untreated * 18: TILACK D (Ako Kasei Co., Ltd.)
* 19: Vinizole 2140L (solid content 43%) (manufactured by Daido Kasei Kogyo Co., Ltd.)

(Manufacturing method)
A. Components (1) to (7) are heated and dissolved at 100 ° C. and cooled to room temperature.
B. Components (8) to (16) are added and emulsified.
C. B was filled in a container to obtain a water-in-oil mascara base cosmetic.

The mascara base cosmetic obtained as described above is excellent in curling effect and long-lasting curling effect, but has a flexible makeup film, so it has a flexible elasticity without damaging the original texture. In addition, the gloss of the decorative film was excellent.

Example 19: Oil-in-water mascara topcoat cosmetic (gel)
(Ingredient) (%)
(1) Carnauba wax 2
(2) Candelilla wax 2
(3) Beeswax 8
(4) Iron oxide 5
(5) Titanium oxide coated glass flakes * 20 3
(6) Silicone resin powder * 21 5
(7) Alkali thickening polymer emulsion * 22 2
(8) Purified water remaining amount (9) Carbon black 1
(10) Ethanol 10
(11) 1,3-butylene glycol 5
(12) Polyoxyethylene cetyl ether 0.5
(13) Triethanolamine 2
(14) Alkyl acrylate copolymer emulsion * 35
(15) Alkyl acrylate copolymer emulsion * 23 5
(16) Composite resin emulsion 4 of Production Example 4 15

* 20: Metashine 1080 (manufactured by Nippon Sheet Glass Co., Ltd.) (dimethylpolysiloxane treatment)
* 21: Tospearl 150KA (manufactured by GE Toshiba Silicone)
* 22: ACULYN 33A (solid content 28%) (Rohm & Haas)
* 23: Binizole 1086WP (solid content 40%) (Daido Kasei Kogyo Co., Ltd.)

(Production method)
A. Ingredients (1) to (6) are uniformly dissolved by heating to 90 ° C.
B. Ingredients (7)-(16) are mixed uniformly and heated to 90.
C. A is added to B and emulsified.
D. C was filled into a container to obtain a mascara top coat cosmetic.

The mascara topcoat cosmetic obtained as described above is excellent in curling effect and curling effect over time, but it has a flexible makeup film, so it has a flexible elasticity without damaging the original texture. Further, the gloss of the decorative film was excellent.

Claims (3)

The following components (A) and (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 core-shell type polymer 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 component (a) in the mixed solution ( b) Composite resin core-shell type polymer emulsion (B) gelling agent (C) oil-solubility in which the ratio with the component is (a) component: (b) component (pure mass ratio) = 50: 50-60: 40 Cosmetics for vases containing resin. The vaginal cosmetic according to claim 1, wherein the component (B) is a wax. The vaginal cosmetic according to claim 1 or 2, wherein the component (C) is a silicone resin.