JP6434218B2 - Eyeliner cosmetics - Google Patents

Description

  The present invention spreads smoothly during use, there is no bleeding or partial polo drop off of the cosmetic film, it is excellent in the drying speed of the cosmetic film, and the cosmetic film is flexible, so there is no sense of incongruity in the makeup part, Furthermore, it is related with the eyeliner cosmetics excellent in the glossiness of the cosmetic film.

  Eyeliner cosmetics are applied to the eyes and are widely used for the purpose of enhancing the impression of the eyes by emphasizing the outlines of the eyes. It is necessary to be excellent. On the other hand, since the use site is a narrow range that is limited to the eye, it is required to spread smoothly during use, to be easily applied, and to be excellent in usability. Further, since the eyeliner cosmetic is used in a delicate place near the eyes, it is important not to feel uncomfortable in the makeup part. Furthermore, after application, it needs to be dried quickly to prevent color transfer to other parts, and it does not bleed even when it comes into contact with tears, sweat, sebum, etc. It is desired to have makeup sustainability that is not lost.

  Therefore, various studies have been made to solve these problems. For example, a technique (see Patent Document 1) that produces a smooth feeling of use and a long-lasting cosmetic effect by using a specific silicone-based spherical powder, a plate-like powder, and an aqueous emulsion in combination has been studied. In addition, the combination of glitter pigments, carbon black, plant-derived polysaccharides, volatile alcohols, and alkyl acrylate copolymer emulsions provides a smooth drawing comfort, vivid color, and excellent liquid resistance. A liner technique (see Patent Document 2) is disclosed. On the other hand, Patent Document 3 discloses an aqueous emulsion composition for cosmetics containing an aqueous emulsion of a specific urethane composite resin.

JP-A-11-302126 JP 2007-153744 A JP 2007-001969 A

  However, the technique of Patent Document 1 has the drawbacks that the adhesiveness is poor, a sufficient glossiness cannot be obtained, and the cosmetic film is hard, so that the cosmetic part is uncomfortable. Further, the liquid eyeliner described in Patent Document 2 is excellent in smoothness, glossiness and long-lasting makeup. However, it takes time and effort to remove the makeup film because the makeup film falls in the form of flakes, and the glitter pigment. There is a problem that the gloss becomes unnatural due to the use of. Further, when the aqueous emulsion disclosed in Patent Document 3 is used for an eyeliner cosmetic, a cosmetic film having a soft and uncomfortable feeling can be obtained. However, since the cosmetic film is too soft, it cannot be fixed to the use site and cannot be fixed. However, there are drawbacks such as a polo drop that is partially lost, and a slow drying speed and color transfer to other parts of the basket. As described above, in the prior art, it is actually difficult to realize eyeliner cosmetics having the required quality.

  The present invention has good usability, and after application, it dries quickly and suppresses color transfer, and has a certain coating strength while being flexible, and a decorative film with high followability and adhesion is formed. Therefore, an object of the present invention is to provide an eyeliner cosmetic that does not feel uncomfortable, has excellent makeup sustainability, and has a good gloss.

  As a result of intensive studies to solve the above problems, the present inventor has combined a film-forming emulsion polymer containing a polymer having a specific structure with an alkali thickening emulsion polymer, an alkali agent and silicic anhydride. It spreads smoothly during use, dries quickly after application, and forms a decorative film with softness, high adhesion and constant coating strength. The present inventors have found that an eyeliner cosmetic that is suppressed, has no discomfort in color transfer and a makeup site, and has an excellent gloss feel, and has completed the present invention.

That is, the present invention provides the following components (A) to (D);
(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: 50-60: 40 composite resin emulsion (B) alkali thickening emulsion polymer (C) alkali agent (D) anhydrous It is an eyeliner cosmetic containing silicic acid.

  The eyeliner cosmetic of the present invention smoothly spreads and has a good feeling of use and has a fast drying speed after application, and therefore, color transfer to portions other than the application site is suppressed. In addition, the formed decorative film has high flexibility and adhesion, and has sufficient coating strength, so there is no bleeding or partial missing polo, excellent makeup sustainability, and no uncomfortable feeling at the makeup site. Furthermore, it is also excellent in glossiness.

  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 and bleeding may occur, 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.

各単独重合体のガラス転移温度は、ＰＯＬＹＭＥＲ ＨＡＮＤＢＯＯＫ（ポリマーハンドブック）等に記載されている。 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.

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 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.

  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.

  1-40 mass% is preferable in conversion of solid content, and, as for the compounding quantity of the component (A) in the eyeliner cosmetics of this invention, More preferably, it is 5-30 mass%. If it is such a range, since a makeup | decoration film | membrane will become a flexible thing, there is no sense of incongruity in a makeup part and the thing excellent in the glossiness is obtained.

  The component (B) alkali-thickened emulsion polymer is an emulsion in which polymer particles are dispersed and stabilized in water. Before the alkali is added, it is a milky white emulsion, but it is thickened by adding an alkali to neutralize it. Is. In the present invention, the alkali thickening type refers to the viscosity of a polymer emulsion diluted with water to a concentration of 0.3% by mass in terms of solid content and triethanolamine added as alkali until pH is 7.5. However, the viscosity is 100 times or more compared to the viscosity before adding the alkali. Here, the viscosity is a value measured with a single cylinder type rotational viscometer bistron VS-A1 manufactured by Shibaura System.

  Specific examples of the component (B) alkali-thickened emulsion polymer include poly (meth) acrylic acid emulsion polymer, polymer emulsion containing a copolymer of acrylic acid and alkyl acrylate, and acrylic acid and alkyl methacrylate. Polymer emulsion containing a copolymer of an ester copolymer, polymer emulsion containing a copolymer of acrylic acid, alkyl acrylate ester and alkyl methacrylate ester, copolymer of acrylic acid, methacrylic acid and alkyl acrylate ester Polymer emulsion containing polymer as a polymer component, polymer emulsion containing acrylic acid, alkyl acrylate ester and polyethylene glycol acrylate copolymer as polymer component, acrylic acid, methacrylic acid polymer A polymer emulsion comprising a copolymer of a kill ester and an acrylic acid (polyoxyethylene monoalkyl ether) ester as a polymer component, and a copolymer of acrylic acid, an alkyl methacrylate and a methacrylic acid (polyoxyethylene monoalkyl ether) ester Polymer emulsion containing polymer, polymer emulsion containing acrylic acid alkyl ester and methacrylic acid (polyoxyethylene monoalkyl ether) ester copolymer, acrylic acid, acrylic acid alkyl ester and itaconic acid (polyoxyethylene monoalkyl ester) Examples thereof include polymer emulsions having a copolymer of an alkyl ether) ester as a polymer component. The alkyl group of the alkyl acrylate or alkyl methacrylate may be one type having 1 to 12 carbon atoms or two or more types.

  Since the component (B) alkali-thickened emulsion polymer is of the alkali-thickened type as described above, it is preferable that it contains essentially acrylic acid or methacrylic acid as a monomer constituting the polymer. When acrylic acid or methacrylic acid is contained in the constituent monomer of the polymer, the carboxyl group is neutralized by alkali, the structure of the polymer in water changes, and the viscosity increases. Specifically, (meth) acrylic acid emulsion polymer, polymer emulsion containing a copolymer of acrylic acid and alkyl acrylate ester as a polymer, polymer emulsion containing a copolymer of acrylic acid and methacrylic acid alkyl ester as a polymer Etc. are preferably used.

  Commercially available components (B) alkali thickened emulsion polymers include “Primal ASE-60” (solid content 28%) (manufactured by Polymer Latex), “SALCARE SC81” (solid content 30%) (Ciba Specialty Chemicals) ), “ACULYN22” (solid content 30%), “ACULYN28” (solid content 20%), “ACULYN33A” (solid content 28%) (all manufactured by Rohm & Haas), etc. Accordingly, one or two or more kinds can be used in appropriate combination.

  The amount of component (B) in the eyeliner cosmetic of the present invention is preferably 0.1 to 4% by mass, more preferably 0.5 to 2% by mass in terms of solid content. Within such a range, it is possible to produce the smoothness of spreading by imparting an appropriate viscosity to the cosmetics, and also to prevent blurring of the cosmetic film and partially missing polo drops and gloss of the cosmetic film. An excellent feeling can be obtained.

  The component (C) alkaline agent used in the present invention is used as a neutralizing agent for the component (B). As such an alkali agent, any one can be used as long as it is usually used in cosmetics, for example, an inorganic alkali such as sodium hydroxide or potassium hydroxide, or a basic such as L-arginine. Organic alkalis such as amino acids, triethanolamine, ammonia, aminomethylpropanol and the like can be mentioned.

  The compounding amount of component (C) in the eyeliner cosmetic of the present invention is an amount sufficient to neutralize component (B), and varies depending on the combination of components (B) and (C).

The component (D) silicic anhydride used in the present invention can be used without particular limitation as long as it is usually blended in cosmetics, but if the average particle size is in the range of 1 to 10 μm, the cosmetic film It is suitable because it is excellent in the effect of preventing bleeding and increasing the drying speed of the decorative film to prevent color transfer to areas other than the makeup site. The average particle diameter can be measured by a known apparatus or method such as a laser diffraction particle diameter distribution measuring apparatus. In addition, it is preferable to use a material having a specific surface area of 100 to 1000 m ² / g because the effect of increasing the drying speed of the decorative film and preventing the color transfer to the part other than the makeup part is similarly achieved. Any shape such as a plate shape, a spindle shape, a needle shape, or a spherical shape can be used. Examples of such commercially available silicic acid products include Silicia 250, 350, 550 (manufactured by Fuji Silysia Chemical Co., Ltd.), SUNSPHERE H-31, H-51 (manufactured by AGC S-Tech, Inc.), and NIPSIL E-220. (Manufactured by Tosoh Silica). In addition, silicic acid is subjected to a surface treatment by a known method using a fluorine compound, a silicone-based oil agent, a metal soap, a wax, a surfactant, a fat, a hydrocarbon, etc., as long as the effects of the present invention are not impaired. Also good.

  It is preferable that the compounding quantity of the component (D) silicic acid anhydride in the eyeliner cosmetics of this invention is 0.1-7 mass%, More preferably, it is 0.5-5 mass%. If it is this range, what was excellent in the effect which prevents the smearing of a decorative film, speeds up the drying speed of a decorative film, and prevents the color transfer to those other than a makeup part will be obtained.

  In addition to the components described above, the eyeliner cosmetic of the present invention is a component usually used in cosmetics, for example, a powder component other than component (D), an oily component, component (A) and component (B). Other emulsion polymers, surfactants for powder dispersion and feel adjustment, aqueous components as moisturizers, UV absorbers, moisturizers, antifading agents, antioxidants, antifoaming agents, cosmetic ingredients, preservatives, fragrances, etc. Can be appropriately blended within a range not impairing the effects of the present invention.

  The powder component other than the component (D) is not particularly limited as long as it is used in cosmetics, such as a plate shape, a spindle shape, a needle shape, a particle diameter, a porous shape, a nonporous shape, and the like. It is not particularly limited by the particle structure and the like, and examples thereof include inorganic powders, glitter powders, organic 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 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, bentonite, smectite, boron nitride Powders, bismuth oxychloride, titanium mica, iron oxide coated mica, iron oxide coated mica titanium, anhydrous silica coated mica titanium, organic pigment-treated mica titanium, titanium oxide coated glass powder, titanium oxide / iron oxide coated glass powder, Titanium oxide and anhydrous silica coated glass Powders such as aluminum powder, organic powders such as magnesium stearate, zinc stearate, N-acyl lysine and nylon, pigment powders such as organic tar pigments and lake pigments of organic pigments, fine particles Titanium oxide coated mica titanium, fine particle 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 powder Examples thereof include a film powder, a polyethylene terephthalate / polymethyl methacrylate laminated film powder, and the like, 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.

  Oily components include hydrocarbons, oils and fats, waxes, hardened oils, ester oils, regardless of the origin, such as animal oils, vegetable oils, synthetic oils, and solid oils, semisolid oils, liquid oils, etc. , Fatty acids, higher alcohols, silicone oils, fluorine oils, lanolin derivatives, oily gelling agents, oil-soluble resins, volatile oils and the like. Specifically, hydrocarbons such as liquid paraffin, squalane, petrolatum, paraffin wax, ceresin wax, microcrystalline wax, ethylene propylene copolymer, montan wax, fisher trops wax, molasses, olive oil, castor oil, mink oil, macadamia Oils such as peanut oil, beeswax, carnauba wax, candelilla wax, waxes such as gay wax, jojoba oil, cetyl isooctanoate, isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, glyceryl trioctanoate, diisostearate Polyglyceryl acid, diglyceryl triisostearate, glyceryl tribehenate, diisostearyl malate, neopentyl glycol dioctanoate, cholesterol fat Acid esters, esters such as N-lauroyl-L-glutamate di (cholesteryl, behenyl, octyldodecyl), stearyl alcohol, cetyl alcohol, lauryl alcohol, oleyl alcohol, isostearyl alcohol, behenyl alcohol and other higher alcohols, methylphenyl poly Silicones such as siloxane and fluorine-modified organopolysiloxane, fluorinated oils such as perfluorodecane, perfluorooctane and perfluoropolyether, lanolin, lanolin acetate, lanolin fatty acid isopropyl, lanolin derivatives such as lanolin alcohol, dextrin octoate , Dextrin laurate, dextrin palmitate, dextrin myristate, dextrin stearate, dextrin behenate, coconut oil Fatty acid dextrin, (palmitic acid / octanoic acid) dextrin, sucrose fatty acid ester, starch fatty acid ester, 12-hydroxystearic acid, calcium stearate and other oily gelling agents, hydrogenated rosin acid pentaerythrityl, specific alkyl acrylate Volatilization of oil-soluble resins such as methylpolysiloxane esters, hydrocarbon oils such as light liquid isoparaffin and isododecane, silicones such as decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, methyltrimethicone, and low polymerization degree dimethylpolysiloxane Oily agents and the like.

  Examples of emulsion polymers other than components (A) and (B) include, for example, alkyl acrylate copolymer emulsions, alkyl acrylate copolymer emulsions, alkyl methacrylate copolymer emulsions, alkyl methacrylate copolymer emulsions, acrylic acid / alkyl acrylate copolymer emulsions, 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., one or two of these More than seeds can be used.

  As the surfactant to be blended for the purpose of powder dispersion and feel adjustment, any surfactant that is generally used in cosmetics can be used. Nonionic surfactants and anionic surfactants can be used. , Cationic surfactants, amphoteric surfactants and the like. 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 dosage form of the eyeliner cosmetic of the present invention include aqueous, oil-in-water and water-in-oil types containing an aqueous component.

  Hereinafter, the present invention will be described in more detail with reference to examples. Note that these do not limit the present invention.

Production Example 1
In a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, 7.1 parts by weight of methyl methacrylate and 13.4 parts 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 temperature was further raised to 70 ° C. and maintained for 3 hours to obtain the desired composite resin emulsion.
(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 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
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
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. .)

Examples 1-7 and Comparative Examples 1-3: Aqueous eyeliner cosmetics (liquid)
1. Prepare eyeliner cosmetics with the formulation shown in Table 1 below: a. Makeup (no polo removal), b. Make-up (no smearing), c. Drying speed, d. The flexibility of the cosmetic film, e. The gloss of the decorative film was evaluated by the following evaluation method. The results are also shown in Table 1.

* 1: Composite resin emulsion of Production Example 1 ((a) component: (b) component mass ratio = 50: 50, (b) component theoretical Tg 95 ° C., solid content 40%)
* 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: DYNAMX (manufactured by Akzo Nobel, polyurethane-14: acrylate copolymer mass ratio = 70:30, mixed ethanol aqueous solution, solid content 28%)
* 4: YODOSOL GH800F (solid content 45%) (manufactured by Akzo Nobel)
* 5: Primal ASE-60 (solid content 28%) (manufactured by Polymer Latex)
* 6: NIPSIL E-220 (manufactured by Tosoh Silica) (average particle size 1.5 μm, specific surface area 220 m ² / g)

(Production method)
A. Components (1) to (11) are mixed uniformly, and components (12) to (15) are added and mixed uniformly.
B. A was filled into a container to obtain an eyeliner cosmetic.

(Evaluation method)
The following items were used by 20 specialist panels. Each sample was applied at the time of wrinkle once, and each panel person at the time of application and immediately after application for c to e, and for a and b, the state of the cosmetic film after normal life about 8 hours after application, The following absolute evaluation criteria were evaluated in 7 levels, given a score, the average value was calculated from the total score of all the panels, and judged according to the following criteria.
<Evaluation item>
a. Has makeup (no polo removal)
b. Makeup (no smearing)
c. Drying speed d. Cosmetic film flexibility e. Glossiness of the decorative 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 eyeliner cosmetics of Examples 1 to 7 of the present invention have a smearing of the cosmetic film and a partially missing polo drop compared to the eyeliner cosmetics of Comparative Examples 1 to 3. In addition, the cosmetic film was excellent in the drying rate, and the decorative film was flexible, so that the makeup site did not feel uncomfortable and the gloss of the decorative film was excellent.
On the other hand, in Comparative Example 1 using the composite resin emulsion having a low theoretical Tg of the component (b), the acrylic film is insufficient in coating strength, and the decorative film becomes soft, causing bleeding, and drying. Since the speed was remarkably reduced, satisfactory results were not obtained in that the color transferred to other than the makeup part. In Comparative Example 2 in which a urethane / acrylic mixed polymer was used instead of the composite resin emulsion of component (A), it was originally an aqueous polymer, so the cosmetic film was poor in water resistance, and bleeding with sweat and sebum was observed. It was. Moreover, in the comparative example 3 which used the alkyl acrylate copolymer emulsion polymer instead of the composite resin emulsion of a component (A), the makeup | decoration film was hard and lacked in the softness | flexibility, and the polo drop | off | missing partially missing was seen.

Example 8: Water-based eyeliner cosmetic (liquid)
(Ingredient) (%)
(1) Polyoxyethylene alkyl (12-15) ether phosphoric acid 3.5
(2) Glycerin 2
(3) Purified water remaining amount (4) L-arginine 0.4
(5) Phenoxyethanol 0.5
(6) Dipropylene glycol 7
(7) 1,2-pentanediol 1
(8) Composite resin emulsion * 7 5
(9) Alkyl acrylate copolymer emulsion polymer * 8 1
(10) Titanium black 0.3
(11) Bengala * 9 1
(12) Titanium mica * 10 10
(13) Silicic anhydride * 11 2
(14) Silylated silica anhydride * 12 0.1
(15) Olive oil 0.1
(16) Polyvinyl acetate emulsion polymer * 13 0.1
(17) Methylsiloxane network polymer * 14 1
(18) Fragrance 0.3
* 7: Composite resin emulsion of Production Example 2 (mass ratio 50:50 of component (a) and component (b), theoretical Tg of component (b) 102 ° C., solid content 40%))
* 8: ACURYN 33A (solid content 28%) (Rohm and Haas Japan)
* 9: 2% perfluoroalkyl phosphate treatment * 10: FLAMENCO RED (manufactured by BASF) dimethylpolysiloxane 2% treatment * 11: Silicia 550 (manufactured by Fuji Silysia) (average particle size 3.85 μm, specific surface area 470 m) ² / g)
* 12: AEROSIL R972 (manufactured by Nippon Aerosil Co., Ltd.) (average particle size 16 nm, specific surface area 110 m ² / g)
* 13: Vinibrand GV-5651 (manufactured by Nissin Chemical Industry Co., Ltd.)
* 14: TOPSPEARL 2000B (Momentive Performance Materials Japan GK)

(Production method)
A. Components (1) to (9) are mixed uniformly, and components (10) to (18) are mixed uniformly.
B. A was filled into a container to obtain an eyeliner cosmetic.

  The eyeliner cosmetic obtained as described above smoothly spreads and spreads when in use, and since it has an excellent drying speed of the decorative film, there is no color transfer, and the decorative film has high flexibility and adhesiveness. No bleeding or partially missing polo drop was suppressed, there was no sense of incongruity in the makeup part, and the gloss of the decorative film was excellent.

Example 9: O / W emulsion type eyeliner cosmetic (component) (%)
(1) Stearic acid 2
(2) Liquid paraffin 2
(3) Glyceryl tri-2-ethylhexanoate 5
(4) Beeswax 1
(5) Purified water Residual amount (6) Polyoxyethylene sorbitan monooleate (20E.O) 1
(7) Triethanolamine 1.8
(8) Composite resin emulsion * 1 60
(9) Alkyl acrylate copolymer emulsion polymer * 8 1
(10) Black iron oxide 3
(11) Black 401 No. 0.5
(12) Polyethylene terephthalate / aluminum / epoxy laminated powder * 15 2
(13) Silicic anhydride * 16 7
(14) Borosilicate (Ca / Al) * 17 1
(15) Tocopherol acetate 0.1
(16) Jojoba oil 0.1
(17) Ethanol 5
(18) Methyl paraoxybenzoate 0.5
* 15: Aluminum flake red 0.15 mm (manufactured by Kakuhachi Fish Foil Co.)
* 16: God ball D11-796C (manufactured by Suzuki Yushi Kogyo Co., Ltd.) (average particle size 3.5 μm, specific surface area 500 m ² / g)
* 17: Microglass Metashine MT1080RR (manufactured by Nippon Sheet Glass Co., Ltd.)

(Production method)
A. Components (1) to (4) are dissolved by heating at 90 ° C.
B. Components (5) to (9) are heated and mixed at 90 ° C.
C. Add B to A and emulsify. Thereafter, components (10) to (18) are added and mixed uniformly.
D. C was filled into a container to obtain an eyeliner cosmetic.

  The eyeliner cosmetic obtained as described above smoothly spreads and spreads when in use, and since it has an excellent drying speed of the decorative film, there is no color transfer, and the decorative film has high flexibility and adhesiveness. No bleeding or partially missing polo drop was suppressed, there was no sense of incongruity in the makeup part, and the gloss of the decorative film was excellent.

Example 10: W / O emulsion type eyeliner cosmetic (component) (%)
(1) Isododecane 40
(2) Candelilla wax 4
(3) Rosin acid pentaerythlit 3
(4) Cetyl 2-ethylhexanoate 5
(5) Trimethylsiloxysilicic acid * 18 10
(6) Decamethylcyclopentasiloxane 10
(7) Sorbitan sesquioleate 2
(8) Purified water remaining amount (9) Composite resin emulsion * 19 1
(10) Alkyl acrylate copolymer emulsion polymer * 8 0.2
(11) Triethanolamine 0.2
(12) Black iron oxide 5
(13) Silicic anhydride * 19 0.3
(14) Talc 2
(15) Natural vitamin E 0.1
(16) Fragrance 0.5
* 18: Silicon KF-7312J (manufactured by Shin-Etsu Chemical Co., Ltd.) 50% decamethylcyclopentasiloxane solution * 19: Composite resin emulsion of Production Example 4 (mass ratio of component (a) to component (b) 60:40, b) Component theory Tg 95 ° C., solid content 40%)
* 20: AEROSIL 380S (manufactured by Nippon Aerosil Co., Ltd.) (average particle size 7 nm, specific surface area 380 m ² / g)

(Production method)
A. Components (1) to (7) are dissolved by heating at 90 ° C.
B. Components (8) to (11) are heated and mixed at 90 ° C.
C. Add B to A and emulsify. Thereafter, components (12) to (16) are added and mixed uniformly.
D. C was filled into a container to obtain an eyeliner cosmetic.

  The eyeliner cosmetic obtained as described above smoothly spreads and spreads when in use, and since it has an excellent drying speed of the decorative film, there is no color transfer, and the decorative film has high flexibility and adhesiveness. No bleeding or partially missing polo drop was suppressed, there was no sense of incongruity in the makeup part, and the gloss of the decorative film was excellent.

  Since the present invention smoothly spreads and has a good feeling of use and has a high drying speed after application, color transfer to portions other than the application site is unlikely to occur, and the formed decorative film has flexibility and adhesion. It is high and has sufficient coating strength, so there is no bleeding or partial missing polo, excellent makeup sustainability, no discomfort in the makeup area, and useful as an eyeliner cosmetic with excellent gloss Is.

Claims (5)

The following components (A) to (D);
(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 (B) alkali thickening emulsion polymer (C) alkali agent (D) anhydrous Eyeliner cosmetic containing silicic acid.   The eyeliner cosmetic according to claim 1, wherein the compounding amount of the component (A) is 1 to 40% by mass in terms of solid content.   The eyeliner cosmetic according to claim 1 or 2, wherein the compounding amount of the component (B) is 0.1 to 4% by mass in terms of solid content.   The eyeliner cosmetic according to any one of claims 1 to 3, wherein the amount of the component (D) is 0.1 to 7% by mass. The average particle diameter of a component (D) is 1-10 micrometers, and a specific surface area is 100-1000 m < ² > / g, Eyeliner cosmetics in any one of Claims 1-4.