Cosmetic composition

Abstract

To provide a cosmetic composition capable of forming a cosmetic coating film having excellent concealing properties and color developing properties even without using an inorganic pigment, a cosmetic method using the cosmetic composition and a cosmetic coating film formed from the cosmetic composition.SOLUTION: There are provided: a cosmetic composition comprising a solvent A, a solvent B, a polymer C and a colorant in which the solvent A is one or more selected from ethanol, n-propanol and isopropanol, the boiling point of the solvent B is 150°C or more, the Hansen solubility parameter distance Ra of the solvent B to water is 40 or more, the solvent B is compatible with the solvent A and the polymer C is soluble in the solvent A and insoluble in the solvent B; a cosmetic method using the cosmetic composition; and a cosmetic coating film formed from the cosmetic composition.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a cosmetic composition, a cosmetic method using the cosmetic composition, and a cosmetic coating film formed from the cosmetic composition.

Background Art

[0002] Conventionally, in makeup cosmetics, in order to cover skin spots, dullness, pores, and improve the brightness of the applied finish, inorganic pigments with high hiding power such as titanium oxide, zinc oxide, and iron oxide have been blended. For example, Patent Document 1 describes a cosmetic containing titanium oxide with an average particle diameter of 0.2 μm or more and resin fine particles with an average particle diameter of 0.01 to 100 μm for the purpose of providing a cosmetic having high whiteness and hiding power. Further, Patent Document 2 describes a cosmetic composition containing a plate-type filler having a predetermined refractive index and particle diameter, a silicone elastomer, and a filler having an oil absorption capacity of 1 ml / g or more in a physiological medium for the purpose of maintaining the hiding effect of skin defects and the like for a long time.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] Here, in base makeup cosmetics such as foundation and concealer mainly for skin tone adjustment, it is required to have high color developability that can cover skin spots, freckles, pores, and color the cosmetic to the original color of the colorant blended in the cosmetic. In addition, for point makeup cosmetics such as eyeshadow, blush, and nail enamel that are applied to facial areas such as the face and nails and are used to apply color partially to emphasize certain points, they are used for the purpose of creating a three-dimensional effect by adding shadows or for the purpose of applying color to emphasize certain parts. Therefore, it is required to have high color-developing properties that can conceal the original color of the skin and nails while coloring to the original color of the colorant contained in the cosmetics. Furthermore, temporary hair dyes such as hair mascara are preferred as they cause less damage to the hair and allow users to easily enjoy hair coloring. In particular, for the purpose of enhancing fashionability, they are used to impart vivid colors to the hair. However, since temporary hair dyes color the hair by forming a colored coating film on the hair, it is required to have high color-developing properties that can conceal the original color of the hair while coloring to the original color of the colorant contained in the temporary hair dye. In the technologies of Patent Documents 1 and 2, hiding power is exhibited by blending inorganic pigments with high refractive indices. However, in recent years, regarding zinc oxide and titanium oxide, the restrictions on their use have been becoming stricter due to various regulations. Therefore, there is a desire to develop a cosmetic composition that can form a cosmetic coating film excellent in hiding properties and color-developing properties without using inorganic pigments. Furthermore, among temporary hair dyes, there are also those used in a form of dyeing the hair in a mesh pattern. Therefore, a simple makeup method that applies color only to some desired hairs is also desired. An object of the present invention is to provide a cosmetic composition that can form a cosmetic coating film excellent in hiding properties and color-developing properties without using inorganic pigments, a cosmetic method using the cosmetic composition, and a cosmetic coating film formed from the cosmetic composition.

Means for Solving the Problems

[0005] The inventor has found that a cosmetic composition containing two types of solvents, a polymer, and a colorant, wherein the first solvent of the two types of solvents is one or more selected from ethanol, n-propanol, and isopropanol, the boiling point of the second solvent and the distance of the Hansen solubility parameter with respect to water are each a specific value or more, and the compatibility of the two types of solvents and the solubility of the polymer in the solvent are each in a specific relationship can solve the above problems. That is, the present invention provides the following [1] to [3]. [1] A cosmetic composition containing solvent A, solvent B, polymer C, and a colorant, wherein the solvent A is one or more selected from ethanol, n-propanol, and isopropanol, the boiling point of the solvent B is 150°C or higher, and the distance Ra of the Hansen solubility parameter of the solvent B represented by the following formula (1) with respect to water is 40 or more, the solvent B is compatible with the solvent A, and the polymer C is soluble in the solvent A and insoluble in the solvent B, a cosmetic composition. Ra = (4 × ΔD 2 + ΔP 2 + ΔH 2 ) 0.5 (1) ΔD: The difference in the dispersion component in the Hansen solubility parameter between the solvent B and water ΔP: The difference in the polar component in the Hansen solubility parameter between the solvent B and water ΔH: The difference in the hydrogen bond component in the Hansen solubility parameter between the solvent B and water [2] A cosmetic method using the cosmetic composition according to [1], Step 1: A step of applying the cosmetic composition to the skin, hair, or nails, and Step 2: A step of applying droplets of a liquid E containing water to the cosmetic composition applied on the skin, hair, or nails, a cosmetic method. [3] A cosmetic coating film formed from the cosmetic composition according to [1].

Advantages of the Invention

[0006] According to the present invention, there can be provided a cosmetic composition capable of forming a cosmetic coating film excellent in hiding power and color developability without using an inorganic pigment, a cosmetic method using the cosmetic composition, and a cosmetic coating film formed from the cosmetic composition.

Mode for Carrying Out the Invention

[0007] [Cosmetic Composition] The cosmetic composition of the present invention is a cosmetic composition containing a solvent A, a solvent B, a polymer C, and a colorant, wherein the solvent A is at least one selected from ethanol, n-propanol, and isopropanol, the boiling point of the solvent B is 150°C or higher, and the distance Ra of the Hansen solubility parameter of the solvent B with respect to water represented by the following formula (1) is 40 or higher, the solvent B is compatible with the solvent A, and the polymer C is soluble in the solvent A and insoluble in the solvent B. Ra=(4×ΔD 2 +ΔP 2 +ΔH 2 ) 0.5 (1) ΔD: Difference in the dispersion component in the Hansen solubility parameter between the solvent B and water ΔP: Difference in the polar component in the Hansen solubility parameter between the solvent B and water ΔH: Difference in the hydrogen bond component in the Hansen solubility parameter between the solvent B and water

[0008] In the present invention, "compatible" means a phenomenon in which the solvent A and the solvent B are mutually dissolved in a mixed system containing the solvent A and the solvent B. When the solvent A and the solvent B are mixed and allowed to stand, if they do not separate into multiple phases, or when they are mixed and stirred, if they do not phase-separate and become turbid, it is determined that the solvent A and the solvent B are in a compatible state. Further, the polymer C is soluble in the solvent A and insoluble in the solvent B, and is dissolved in the cosmetic composition. In the present invention, "Polymer C is soluble in Solvent A" means that when Polymer C dried at 105°C for 2 hours until a constant weight is reached is dissolved in 100 g of Solvent A at 25°C, the amount of dissolution is 5 g or more. From the viewpoint of improving hiding power and color-developing property, the amount of dissolution of Polymer C in Solvent A is preferably 10 g or more. In the present invention, "Polymer C is insoluble in Solvent B" means that when Polymer C dried at 105°C for 2 hours until a constant weight is reached is dissolved in 100 g of Solvent B at 25°C until saturation, the amount of dissolution is less than 5 g. From the viewpoint of improving hiding power and color-developing property, the amount of dissolution of Polymer C in Solvent B is preferably less than 2 g. The determination of whether it is "compatible" or "soluble" as described above is carried out at 25°C.

[0009] In the present invention, the "Hansen solubility parameter" is represented by dividing the solubility parameter (SP value) introduced by Hildebrand into three components (dispersion component D, polar component P, and hydrogen bonding component H). D, P, and H of each solvent are described in detail in "HANSEN SOLBILITY PARAMETERS" A User's Handbook Second Edition. Also, HSP values for many solvents and resins are described in Industrial Solvents Handbook written by Wesley L. Archer, etc. D, P, and H of each solvent can also be obtained using the software HSPiP of Charles Hansen Consulting, Inc. (Horsholm, Denmark, hansen-solubility.com). In the present invention, regarding solvents registered in the database of HSPiP version 4.1.03 (refer to various HSP literatures), their values are used, and regarding solvents not in the database, values estimated by the above HSPiP are used. Also, in the present invention, the unit of the "Hansen solubility parameter" is "(MPa)0.5".

[0010] According to the present invention, a cosmetic coating film excellent in hiding power and color development can be formed without using an inorganic pigment. Although the reason is not clear, it is considered as follows. The cosmetic composition of the present invention contains at least one solvent A selected from ethanol, n-propanol, and isopropanol, a solvent B having a boiling point of 150°C or higher and a Hansen solubility parameter distance Ra with respect to water represented by the formula (1) of 40 or more, a polymer C soluble in the solvent A and insoluble in the solvent B, and a colorant. When such a cosmetic composition is applied to the skin, hair, or nails, the heat of vaporization is taken away by the volatilization of the solvent A in the coating film, and moisture in the atmosphere condenses on the surface of the coating film to form minute water droplets and adhere thereto. In the present invention, since the solvent A is at least one selected from specific alcohols and the distance Ra of the solubility parameter of the solvent B with respect to water is a specific value or more, the solvent B that was compatible with the solvent A is phase-separated due to the adhesion of the minute water droplets to the surface of the coating film. And since the polymer C is insoluble in the solvent B, the phase-separated solvent B is coated with the polymer C, and the coalescence of the solvent B is suppressed, whereby it is considered that primary particles containing a colorant having a core-shell structure with the solvent B as the core and the polymer C as the shell are formed. Further, with the volatilization of the solvent A and the surface alignment of the formed primary particles, a cell-like convection structure regularly partitioned in the coating film, so-called Benard Cells, is generated, and it is considered that a cosmetic coating film containing a colorant in which primary particles are aggregated to form secondary particles is obtained by the Benard convection in each cell. As a result, it is presumed that light is scattered by the particle structure formed in the cosmetic coating film, and high hiding power and color development are exhibited.

[0011] <Solvent A> The cosmetic composition of the present invention contains a solvent A. The solvent A is at least one selected from ethanol, n-propanol, and isopropanol. Further, in the cosmetic composition, the solvent A is compatible with the solvent B and dissolves the polymer C. Thereby, when the cosmetic composition is applied to the skin, hair, or nails, the heat of vaporization is taken away with the volatilization of the solvent A, minute water droplets adhere to the surface of the coating film, and phase separation between the solvent A and the solvent B can be caused. Solvent A may be used alone or in combination of two or more. From the viewpoint of improving the hiding power and color-developing property, Solvent A is preferably at least one selected from ethanol and isopropanol, more preferably ethanol.

[0012] <Solvent B> The cosmetic composition of the present invention contains Solvent B. The boiling point of Solvent B is 150 °C or higher, and the distance Ra of the Hansen solubility parameter of Solvent B with respect to water represented by the formula (1) is 40 or higher. Further, in the cosmetic composition, Solvent B is miscible with Solvent A and does not dissolve Polymer C. Thereby, when minute water droplets adhere to the surface of the coating film due to the volatilization of Solvent A, phase separation of Solvent A and Solvent B occurs, and primary particles in which Solvent B is coated with Polymer C are formed.

[0013] The boiling point of Solvent B is 150 °C or higher from the viewpoint of forming primary particles and improving the hiding power and color-developing property, preferably 155 °C or higher, more preferably 160 °C or higher, still more preferably 165 °C or higher, even more preferably 170 °C or higher, and from the viewpoint of handleability, preferably 300 °C or lower, more preferably 270 °C or lower, still more preferably 250 °C or lower, even more preferably 230 °C or lower, even more preferably 210 °C or lower, even more preferably 180 °C or lower. The distance Ra of the Hansen solubility parameter of Solvent B with respect to water is 40 or higher from the viewpoint of forming primary particles and improving the hiding power and color-developing property, preferably 42 or higher, more preferably 44 or higher, and preferably 60 or lower, more preferably 57 or lower, still more preferably 55 or lower, even more preferably 50 or lower. Solvent B may be used alone or in combination of two or more. When two or more Solvents B are used in combination, the boiling point and the distance Ra of the Hansen solubility parameter with respect to water can be determined as a weighted average value weighted by the content (% by mass) of each solvent.

[0014] Solvent B preferably contains at least one selected from hydrocarbon oils and silicone oils from the viewpoint of improving concealability and color developability. Examples of the hydrocarbon oil include α-olefin oligomers; liquid paraffins; liquid isoparaffins such as isododecane, isohexadecane, and hydrogenated polyisobutene (light liquid isoparaffin, heavy liquid isoparaffin); liquid ozokerite; squalane; pristane; squalene and the like. Among them, the hydrocarbon oil is preferably at least one selected from α-olefin oligomers, liquid paraffins, liquid isoparaffins, liquid ozokerite, squalane, pristane, and squalene, more preferably a liquid isoparaffin, still more preferably at least one selected from isododecane, isohexadecane, and hydrogenated polyisobutene, and even more preferably at least one selected from isododecane and hydrogenated polyisobutene. The weight average molecular weight of the hydrocarbon oil is preferably 150 or more, more preferably 160 or more, and preferably 1,000 or less, more preferably 500 or less, still more preferably 300 or less. The viscosity of the hydrogenated polyisobutene at 20°C is preferably 0.5 mPa·s or more, more preferably 0.7 mPa·s or more, still more preferably 1 mPa·s or more, and preferably 30 mPa·s or less, more preferably 25 mPa·s or less, still more preferably 20 mPa·s or less, even more preferably 15 mPa·s or less, even more preferably 10 mPa·s or less, even more preferably 5 mPa·s or less, even more preferably 3 mPa·s or less, even more preferably 2 mPa·s or less. The viscosity of the hydrogenated polyisobutene at 20°C can be measured by the method described in the examples using an E-type viscometer.

[0015] Examples of silicone oils include linear silicone oils such as trisiloxane; branched silicone oils such as methyltrimethicone; and cyclic silicone oils such as methylcyclopolysiloxane. Among them, the silicone oil is preferably at least one selected from linear silicone oils, branched silicone oils, and cyclic silicone oils, more preferably at least one selected from trisiloxane, methyltrimethicone, and methylcyclopolysiloxane, and still more preferably at least one selected from trisiloxane and methyltrimethicone. The weight average molecular weight of the silicone oil is preferably 150 or more, more preferably 160 or more, and preferably 1,000 or less, more preferably 500 or less, and still more preferably 300 or less. The viscosity of the silicone oil at 25°C is preferably 0.5 mPa·s or more, and preferably 20 mPa·s or less, more preferably 10 mPa·s or less, still more preferably 5 mPa·s or less, even more preferably 3 mPa·s or less, and even more preferably 2 mPa·s or less. The viscosity of the silicone oil at 25°C can be measured by the method described in the examples using an E-type viscometer.

[0016] From the viewpoint of improving the film-forming property of the cosmetic coating film and improving the hiding property and color-developing property, the solvent B preferably has volatility, and more preferably is at least one selected from volatile hydrocarbon oils and volatile silicone oils. In the present invention, "volatility" means that the evaporation amount at 25°C for 6 hours, measured by the following method, is 20% or more. Measurement method: Place a filter paper with a diameter of 90 mm in a glass petri dish with a diameter of 120 mm, place 1 g of the sample on the filter paper, and store it in a room at 65% RH (25°C) for 6 hours. Measure the mass of the sample before and after storage, and calculate the evaporation amount using the following formula. Evaporation amount (%) = [(mass of sample before storage - mass of sample after storage) / mass of sample before storage] × 100

[0017] In the present invention, as described above, primary particles having a core-shell structure with solvent B as the core and polymer C as the shell are formed. Since solvent B is volatile, the solvent B encapsulated in the core part evaporates to form hollow primary particles, thereby improving the hiding power, color-developing property, and film-forming property of the cosmetic coating film. In addition, when forming the hollow primary particles, minute pores (openings) may be formed in the shell part. In this case, for example, in the application of the cosmetic composition of the present invention to the skin, even if the skin grooves and wrinkles are deformed due to changes in facial expressions or the like, the hollow primary particles incorporated into the skin grooves and wrinkles can be reversibly returned to the original state following the volume change of the skin grooves and wrinkles by deforming the particles or extruding air. For this reason, the extrusion of the hollow primary particles onto the skin surface is suppressed, and the state of the cosmetic coating film before deformation of the skin grooves and wrinkles can be maintained well, and it is considered that the cosmetic retention is improved. The hollow primary particles are preferably formed by evaporating the solvent B encapsulated in the core part by adjusting the type of solvent B and the drying conditions of the coating film after application to the skin.

[0018] As the volatile hydrocarbon oil, from the viewpoints of improving the hiding power, color-developing property, and film-forming property of the cosmetic coating film, a saturated or unsaturated hydrocarbon oil having 8 to 16 carbon atoms is preferable. Examples of the volatile hydrocarbon oil include paraffinic hydrocarbon oils such as n-decane, n-undecane, and n-dodecane; isoparaffinic hydrocarbon oils such as isodecane, isododecane, and hydrogenated polyisobutene (light liquid isoparaffin); and cyclic paraffin hydrocarbon oils such as cyclodecane and cyclododecane. Among these, the volatile hydrocarbon oil is preferably liquid isoparaffin, more preferably one or more selected from isodecane, isododecane, and hydrogenated polyisobutene, still more preferably one or more selected from isododecane and hydrogenated polyisobutene, and even more preferably hydrogenated polyisobutene. Examples of commercially available products of the volatile hydrocarbon oil include "Pearl Rim 3" and "Pearl Rim 4" manufactured by NOF Corporation; Marca Sol R manufactured by Maruzen Petrochemical Co., Ltd.

[0019] As the volatile silicone oil, from the viewpoints of hiding power, coloring property, and film-forming property of the cosmetic film, preferably, one or more selected from linear organopolysiloxanes and cyclic organopolysiloxanes are mentioned. Specific examples of the linear organopolysiloxane include octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, 1,1,1,3,5,5,5-heptamethyl-3-[(trimethylsilyl)oxy]-trisiloxane, and the like. Examples of the cyclic organopolysiloxane include 4- to 6-membered cyclic siloxanes having an alkyl group with 1 to 5 carbon atoms as a substituent. Specific examples of the cyclic organopolysiloxane include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like. Commercially available products of the volatile silicone oil include "KF-96A-1cs" (octamethyltrisiloxane), "KF-96L-1.5cs" (decamethyltetrasiloxane), "KF-96L-2cs" (dodecamethylpentasiloxane), "KF-995" (decamethylcyclopentasiloxane), "TMF-1.5" (1,1,1,3,5,5,5-heptamethyl-3-[(trimethylsilyl)oxy]-trisiloxane) manufactured by Shin-Etsu Chemical Co., Ltd.; "SH200C Fluid 1cs" (octamethyltrisiloxane), "SH200C Fluid 1.5cs" (decamethyltetrasiloxane), "SH200C Fluid 2cs" (dodecamethylpentasiloxane), "SH245 Fluid" (decamethylcyclopentasiloxane) manufactured by Toray Dow Corning Co., Ltd.; "TSF405A" (decamethylcyclopentasiloxane) manufactured by Momentive Performance Materials Inc., and the like.

[0020] In addition to the hydrocarbon oil or silicone oil, the solvent B may further contain additives such as a humectant, an ultraviolet absorber, an insect repellent, an anti-wrinkle agent, and a fragrance. When Solvent B contains at least one selected from hydrocarbon oils and silicone oils having a weight average molecular weight of 150 or more and 1,000 or less, the content of at least one selected from hydrocarbon oils and silicone oils having a weight average molecular weight of 150 or more and 1,000 or less in Solvent B is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and preferably 100% by mass or less, still more preferably 100% by mass, from the viewpoint of improving concealability and color developability.

[0021] <Polymer C> In the present invention, Polymer C coats the phase-separated Solvent B and contributes to the formation of primary particles. Polymer C is not particularly limited as long as it is soluble in Solvent A and insoluble in Solvent B. Examples of Polymer C include ionic polymers such as anionic polymers, cationic polymers, and betaine polymers; and nonionic polymers.

[0022] (Anionic polymer) An anionic polymer has an anionic group. Examples of the anionic group include groups that dissociate to release hydrogen ions and exhibit acidity, such as carboxy group (-COOM), sulfonic acid group (-SO 3 M), phosphate group (-OPO 3 M 2 ), or their dissociated ionic forms (-COO - , -SO 3 - , -OPO 3 2- , -OPO 3 - M). In the above chemical formulas, M represents a hydrogen atom, an alkali metal, ammonium, or organic ammonium. The anionic polymer is preferably an anionic polymer CI (hereinafter also referred to as "anionic polymer CI") containing a structural unit derived from a monomer having an acidic group, from the viewpoint of improving concealability and color developability. The monomer having an acidic group is preferably a monomer having a carboxy group from the same viewpoint as described above, more preferably at least one selected from (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, and 2-methacryloyloxymethyl succinic acid, and still more preferably (meth)acrylic acid. Here, “(meth)acrylic acid” means at least one selected from acrylic acid and methacrylic acid.

[0023] From the viewpoint of improving the hiding property and color developing property, the anionic polymer CI is preferably a copolymer further containing a structural unit derived from a monomer other than the monomer having an acidic group. Examples of the other monomer include hydrophobic monomers such as (meth)acrylate having a hydrocarbon group derived from an aliphatic alcohol, and aromatic group-containing monomers; and nonionic monomers. Here, “(meth)acrylate” means one or more selected from acrylate and methacrylate.

[0024] The (meth)acrylate having a hydrocarbon group derived from an aliphatic alcohol preferably has a hydrocarbon group derived from an aliphatic alcohol having 1 to 22 carbon atoms, more preferably 1 to 12 carbon atoms, and still more preferably 1 to 8 carbon atoms. Examples of the (meth)acrylate include (meth)acrylate having a linear alkyl group; (meth)acrylate having a branched alkyl group; and (meth)acrylate having an alicyclic alkyl group.

[0025] The aromatic group-containing monomer is preferably a vinyl monomer having an aromatic group having 6 to 22 carbon atoms, which may have a substituent containing a hetero atom, more preferably at least one selected from styrene-based monomers and aromatic group-containing (meth)acrylates. The molecular weight of the aromatic group-containing monomer is preferably less than 500. Examples of the styrene-based monomer include styrene, α-methylstyrene, 2-methylstyrene, vinyltoluene, and divinylbenzene. Examples of aromatic group-containing (meth)acrylates include phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, etc.

[0026] Examples of nonionic monomers in anionic polymer CI include (meth)acrylamide; N-vinyl-2-pyrrolidone; N-alkyl (meth)acrylamides having a linear, branched or cyclic alkyl group such as N-tert-butylacrylamide, N-tert-octylacrylamide, N-(2-ethylhexyl)acrylamide, N-n-octylacrylamide, N-dodecylacrylamide, N-n-heptylacrylamide, N-hexylacrylamide, N-cyclohexylmethacrylamide, etc.; hydroxyalkyl (meth)acrylate; polyalkylene glycol (meth)acrylate (n = 2 to 30, where n represents the average number of added moles of the oxyalkylene group. The same applies hereinafter); alkoxypolyalkylene glycol (meth)acrylate (n = 1 to 30); phenoxypolyalkylene glycol (meth)acrylate such as phenoxy(ethylene glycol·propylene glycol copolymer) (n = 1 to 30, ethylene glycol in it: n = 1 to 29) (meth)acrylate, etc. Specific examples of commercially available nonionic monomers include NK Ester M-20G, 40G, 90G, 230G, etc. of Shin-Nakamura Chemical Co., Ltd.; Brenmer PE-90, 200, 350, etc., PME-100, 200, 400, etc., PP-500, 800, 1000, etc., AP-150, 400, 550, etc., 50PEP-300, 50POEP-800B, 43PAPE-600B, etc. of NOF Corporation. Each of the aforementioned monomers can be used alone or in combination of two or more.

[0027] The weight-average molecular weight of the anionic polymer CI is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 20,000 or more, and is preferably 1,000,000 or less, more preferably 500,000 or less, still more preferably 200,000 or less. The weight-average molecular weight of the anionic polymer CI is the molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0028] Commercially available anionic polymers CI include acrylic acid / acrylic acid alkyl ester / (N-alkyl)acrylamide copolymers such as Ultrahold 8, Ultrahold Strong, Ultrahold Power manufactured by BASF Japan Ltd., and Unifomer V-42 manufactured by National Starch; carboxyvinyl polymers such as Carbopol series manufactured by Lubrizol Advanced Materials; (meth)acrylic acid / (meth)acrylic acid alkyl ester copolymers such as Diahold manufactured by Mitsubishi Chemical Corporation; ((meth)acrylic acid / diacetoneacrylamide) copolymer AMP, ((meth)acrylic acid / acrylic acid alkyl ester / diacetoneacrylamide) copolymer AMP, ((meth)acrylic acid / (meth)acrylic acid alkyl ester / (N-alkyl)alkylacrylamide) copolymer AMP such as Plasize L series manufactured by Muteki Chemical Industry Co., Ltd.; (meth)acrylic acid / acrylic acid alkyl ester / vinylpyrrolidone copolymers such as Rubiflex VBM35 manufactured by BASF, etc. In addition, as commercially available products of polymers having a structural unit derived from acrylic acid or methacrylic acid as a monomer having an acidic group and used in cosmetic applications, products such as the Aniset series manufactured by Osaka Organic Chemical Industry Co., Ltd. can be used. Here, "(meth)acrylic acid alkyl ester" means one or more selected from acrylic acid alkyl esters and methacrylic acid alkyl esters.

[0029] Anionic polymer CI preferably contains a structural unit derived from a monomer having an acidic group and a structural unit derived from an alkyl (meth)acrylate from the viewpoint of improving concealability and color-developing property. More preferably, it contains a structural unit derived from a monomer having an acidic group, a structural unit derived from an alkyl (meth)acrylate, and a structural unit derived from (N-alkyl)(meth)acrylamide. Even more preferably, it is a (meth)acrylic acid / (meth)acrylic acid alkyl ester / (N-alkyl)(meth)acrylamide copolymer, and even more preferably an acrylic acid / acrylic acid alkyl ester / (N-alkyl)acrylamide copolymer.

[0030] (Cationic polymer) In the present invention, the "cationicity" of the cationic polymer means that when an unneutralized polymer is dispersed or dissolved in pure water, the pH is greater than 7; in the case of a polymer having a quaternary ammonium group or the like, when its counter ion is dispersed or dissolved in pure water as a hydroxide ion, the pH is greater than 7; or when the polymer is insoluble in pure water and the pH cannot be clearly measured, the zeta potential of the dispersion in which the polymer is dispersed in pure water is positive. From the viewpoint of improving concealability and color-developing property, the cationic polymer preferably has a basic group such as a primary to tertiary amino group, a quaternary ammonium group, or a hydrazino group, and more preferably has a quaternary ammonium group. The basic group includes those neutralized with acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, maleic acid, fumaric acid, citric acid, tartaric acid, adipic acid, and lactic acid.

[0031] Examples of the cationic polymer include natural cationic polymers and synthetic cationic polymers. Natural cationic polymers are polymers obtained by operations such as extraction and purification from natural products and those obtained by chemically modifying such polymers, and examples thereof include those having glucose residues in the polymer backbone. Specifically, cationized guar gum; cationized tara gum; cationized locust bean gum; cationized cellulose; cationized hydroxyalkyl cellulose; cationic starch and the like can be mentioned.

[0032] Examples of synthetic cationic polymers include polyethyleneimine, polyallylamine or acid neutralization products thereof, polyglycol-polyamine condensates, cationic polyvinyl alcohol, cationic polyvinylpyrrolidone, cationic silicone polymers, 2-(dimethylamino)ethyl methacrylate polymers or acid neutralization products thereof, poly(trimethyl-2-methacryloyloxyethylammonium chloride), amine / epichlorohydrin copolymers, N,N-dimethylaminoethyl methacrylate diethyl sulfate / vinylpyrrolidone copolymers, N,N-dimethylaminoethyl methacrylate diethyl sulfate / N,N-dimethylacrylamide / dimethacrylic acid polyethylene glycol copolymers, polydiallyldimethylammonium chloride, diallyldimethylammonium chloride / acrylamide copolymers, diallyldimethylammonium chloride / sulfur dioxide copolymers, diallyldimethylammonium chloride / hydroxyethyl cellulose copolymers, 1-allyl-3-methylimidazolium chloride / vinylpyrrolidone copolymers, alkylamino (meth)acrylate / vinylpyrrolidone copolymers, alkylamino (meth)acrylate / vinylpyrrolidone / vinylcaprolactam copolymers, (3-(meth)acrylamidopropyl)trimethylammonium chloride / vinylpyrrolidone copolymers, alkylaminoalkylacrylamide / alkylacrylamide / (meth)acrylate / polyethylene glycol (meth)acrylate copolymers and the like. These cationic polymers can be used alone or in combination of two or more.

[0033] Among these, from the viewpoint of improving concealability and color-developing property, the cationic polymer is preferably a cationic polymer CII-1 (hereinafter also referred to as "cationic polymer CII-1") containing a structural unit derived from a monomer having a basic group, or a cationic silicone polymer (hereinafter also referred to as "cationic silicone polymer CII-2").

[0034] 〔Cationic polymer CII-1〕 The cationic polymer CII-1 contains a structural unit derived from a monomer having a basic group. Examples of the basic group are the same as those described above. Examples of the monomer having a basic group include amino group-containing monomers such as alkylamino (meth)acrylate; N,N-dialkylaminoalkyl (meth)acrylate; N-[3-(dimethylamino)propyl](meth)acrylamide; diallyldialkylammonium, acid neutralization products or quaternized products thereof. These monomers having a basic group can be used alone or in combination of two or more. Examples of the acid for acid neutralization include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, maleic acid, fumaric acid, citric acid, tartaric acid, adipic acid, lactic acid, etc. Examples of the quaternizing agent include alkyl halides such as methyl chloride, ethyl chloride, methyl bromide, methyl iodide; alkylating agents such as dialkyl sulfates such as dimethyl sulfate, diethyl sulfate, di-n-propyl sulfate, etc.

[0035] The cationic polymer CII-1 is preferably a homopolymer of a monomer having a basic group, a copolymer of a monomer having a basic group and another monomer other than the monomer having a basic group, or a polycondensate from the viewpoint of improving the hiding power and color developing property. More preferably, it is a copolymer of a monomer having a basic group and another monomer other than the monomer having a basic group. Still more preferably, it is a copolymer containing a structural unit derived from a monomer having a basic group, a structural unit derived from the hydrophobic monomer exemplified in the above anionic polymer CI, and a structural unit derived from the nonionic monomer exemplified in the above anionic polymer CI. Even more preferably, it is a copolymer containing a structural unit derived from an amino group-containing monomer, a structural unit derived from an alkyl (meth)acrylate, a structural unit derived from N-alkyl (meth)acrylamide, and a structural unit derived from alkoxypolyethylene glycol mono (meth)acrylate. Even more preferably, it is a copolymer containing a structural unit derived from an amino group-containing monomer, a structural unit derived from a hydrocarbon group (meth)acrylate of an aliphatic alcohol having 1 to 22 carbon atoms, a structural unit derived from N-alkyl (meth)acrylamide having a linear, branched or cyclic alkyl group, and a structural unit derived from alkoxypolyethylene glycol mono (meth)acrylate. Even more preferably, it is a copolymer containing a structural unit derived from an amino group-containing monomer, a structural unit derived from a hydrocarbon group (meth)acrylate of an aliphatic alcohol having 1 to 8 carbon atoms, a structural unit derived from N-alkyl (meth)acrylamide having a branched alkyl group having 4 to 8 carbon atoms, and a structural unit derived from methoxypolyethylene glycol mono (meth)acrylate. The cationic polymer CII-1 is produced by copolymerizing raw material monomers containing these monomers by a known polymerization method such as bulk polymerization method, solution polymerization method, suspension polymerization method, emulsion polymerization method, etc. Among these polymerization methods, the solution polymerization method is preferred.

[0036] During the production of the cationic polymer CII-1, the content in the raw material monomers of the monomer having a basic group, the hydrophobic monomer, and the nonionic monomer (content as the unneutralized amount; the same shall apply hereinafter), that is, the content of the structural units derived from each component in the cationic polymer CII-1 is as follows from the viewpoint of improving the concealing property and the coloring property. The content of the monomer having a basic group is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 7% by mass or more, and preferably 35% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, even more preferably 20% by mass or less, and even more preferably 17% by mass or less. The content of the hydrophobic monomer is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 35% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less. The content of the nonionic monomer is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, even more preferably 55% by mass or more, and preferably 85% by mass or less, more preferably 80% by mass or less, still more preferably 75% by mass or less.

[0037] From the viewpoint of improving the concealing property and the coloring property, the weight average molecular weight of the cationic polymer CII-1 is preferably 7,000 or more, more preferably 10,000 or more, still more preferably 50,000 or more, even more preferably 100,000 or more, and preferably 500,000 or less, more preferably 300,000 or less, still more preferably 200,000 or less, even more preferably 150,000 or less. The weight average molecular weight of the cationic polymer CII-1 can be measured by the method described in the examples.

[0038] 〔Cationic silicone polymer CII-2〕 The poly(N-acylalkyleneimine) / organopolysiloxane copolymer containing a cationic silicone polymer CII-2, an organopolysiloxane segment (x) (hereinafter also simply referred to as "segment (x)"), an alkylene group containing a cationic nitrogen atom bonded to at least one of the silicon atoms of the segment (x), and a repeating unit of N-acylalkyleneimine represented by the following general formula (1-1) (hereinafter also simply referred to as "segment (y)") is preferred.

[0039]

Chemical formula

[0040] In the general formula (1-1), as the alkyl group where R 1 is, an alkyl group having 1 or more and 12 or less carbon atoms is preferred, an alkyl group having 1 or more and 3 or less carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group is more preferred, and an ethyl group is even more preferred. Examples of the aryl group where R 1 is include a phenyl group and a naphthyl group. Examples of the arylalkyl group where R 1 is include a phenylalkyl group and a naphthylalkyl group having 1 or more and 20 or less carbon atoms in the alkyl group, and examples of the alkylaryl group include an alkylphenyl group and an alkylnaphthyl group having 1 or more and 20 or less carbon atoms in the alkyl group. In the general formula (1-1), a is preferably 2. The degree of polymerization of the repeating unit represented by the general formula (1-1) in the segment (y) is not particularly limited, but for example, 1 or more and 500 or less is preferred, and 6 or more and 100 or less is more preferred.

[0041] Examples of the organopolysiloxane forming segment (x) include compounds represented by the following general formula (1-2). [Chemical Formula] (In the formula, R 2 represents an alkyl group having 1 to 22 carbon atoms, a phenyl group, or an alkyl group containing a nitrogen atom. A plurality of R 2 may be the same or different, but at least one is an alkyl group containing a cationic nitrogen atom. b is 100 or more and 5,000 or less.)

[0042] In general formula (1-2), among the alkyl groups having 1 to 22 carbon atoms represented by R 2 , an alkyl group having 1 to 12 carbon atoms is preferred, an alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group is even more preferred. Further, examples of the alkyl group containing a nitrogen atom represented by R 2 include alkyl groups having 2 to 20 carbon atoms preferably containing 1 to 3 nitrogen atoms. The alkyl group containing a nitrogen atom may be present in at least one of the silicon atoms at the terminal or side chain of the organopolysiloxane. The number of alkyl groups containing a nitrogen atom in the organopolysiloxane is preferably 1 or more and 300 or less, and more preferably 1 or more and 100 or less.

[0043] In general formula (1-2), b is preferably 100 or more and 2,000 or less, and more preferably 350 or more and 1,500 or less. The weight average molecular weight of the organopolysiloxane forming segment (x) is preferably 1,000 or more, more preferably 10,000 or more, still more preferably 30,000 or more, and preferably 1,000,000 or less, more preferably 500,000 or less, still more preferably 200,000 or less, and even more preferably 150,000 or less.

[0044] In the combination of segment (x) and segment (y), examples of the alkylene group containing an intervening nitrogen atom include alkylene groups having 2 to 20 carbon atoms and preferably containing 1 to 3 nitrogen atoms. Specifically, examples of the nitrogen atom present between carbon-carbon bonds or at the terminal of the alkylene chain include (i) secondary amines or tertiary amines, (ii) ammonium salts in which hydrogen ions are added to secondary amines or tertiary amines, (iii) quaternary ammonium salts, and the like. As the poly(N-acylalkyleneimine) / organopolysiloxane copolymer, those in which segment (y) is bonded to at least one of the silicon atoms at the terminal or side chain of segment (x) via an alkylene group containing a cationic nitrogen atom are preferred. The mass ratio of the content of segment (x) to the total content of segment (x) and segment (y) in the poly(N-acylalkyleneimine) / organopolysiloxane copolymer [content of segment (x) / (total content of segment (x) and segment (y))] is preferably 0.1 or more, more preferably 0.3 or more, still more preferably 0.4 or more, even more preferably 0.5 or more, and preferably 0.99 or less, more preferably 0.95 or less, still more preferably 0.9 or less, from the viewpoint of improving concealment and color development. In this specification, the mass ratio [content of segment (x) / (total content of segment (x) and segment (y))] is the ratio of the mass (Mx) of segment (x) to the total amount of the mass (Mx) of segment (x) and the mass (My) of segment (y) in the poly(N-acylalkyleneimine) / organopolysiloxane copolymer. The mass ratio [content of segment (x) / (total content of segment (x) and segment (y))] can be calculated from the integration ratio of the alkyl group or phenyl group in segment (x) and the methylene group in segment (y) by dissolving the poly(N-acylalkyleneimine) / organopolysiloxane copolymer in deuterated chloroform at 5% by mass and performing nuclear magnetic resonance (1H-NMR) analysis.

[0045] The weight-average molecular weight of the poly(N-acylalkyleneimine) / organopolysiloxane copolymer is preferably 10,000 or more, more preferably 50,000 or more, still more preferably 70,000 or more, and preferably 1,000,000 or less, more preferably 500,000 or less, still more preferably 200,000 or less, from the viewpoint of improving hiding power and color-developing property. The weight-average molecular weight of the poly(N-acylalkyleneimine) / organopolysiloxane copolymer can be calculated from the weight-average molecular weight of the organopolysiloxane forming segment (x) and the aforementioned mass ratio [content of segment (x) / [total content of segment (x) and segment (y)]].

[0046] Preferable examples of the poly(N-acylalkyleneimine) / organopolysiloxane copolymer include poly(N-formylethyleneimine) / organopolysiloxane copolymer, poly(N-acetylethyleneimine) / organopolysiloxane copolymer, poly(N-propionylethyleneimine) / organopolysiloxane copolymer, and the like.

[0047] The poly(N-acylalkyleneimine) / organopolysiloxane copolymer can be obtained, for example, by reacting poly(N-acylalkyleneimine), which is a ring-opening polymer of a cyclic imino ether, with an organopolysiloxane forming segment (x). More specifically, it can be obtained, for example, by the method described in JP-A-2011-126978. The poly(N-acylalkyleneimine) / organosiloxane copolymer used as the cationic silicone polymer CII-2 can be used alone or in combination of two or more.

[0048] (Betaine polymer) In the present invention, the betaine polymer includes a copolymer of a monomer having an anionic group and a monomer having a cationic group, a polymer or copolymer of a betaine monomer, a product obtained by introducing an anionic group into a cationic polymer, a product obtained by introducing the aforementioned basic group into an anionic polymer, and the like. Among them, from the viewpoint of improving the concealing property and the coloring property, the betaine polymer is preferably a polymer containing a betaine structure in the side chain, and more preferably a betaine polymer containing a structural unit derived from a betaine monomer (hereinafter, also referred to as "betaine polymer CIII"). From the viewpoint of improving the concealing property and the coloring property, the betaine monomer is preferably a monomer containing a betaine structure and a (meth)acrylamide structure, more preferably at least one selected from carboxybetaine monomers, sulfobetaine monomers, and phosphobetaine monomers, and still more preferably a carboxybetaine monomer.

[0049] Examples of the betaine polymer include polymethacryloylethyldimethylbetaine (homopolymer of N-methacryloyloxyethyl-N,N-dimethylammonium-α-N-methylcarboxybetaine), N-methacryloyloxyethyl-N,N-dimethylammonium-α-N-methylcarboxybetaine / alkyl methacrylate copolymer, methacryloylethyldimethylbetaine / methacryloylethyltrimethylammonium chloride / 2-hydroxyethyl methacrylate copolymer, methacryloylethyldimethylbetaine / methacryloylethyltrimethylammonium chloride / methoxypolyethylene glycol methacrylate copolymer, octylacrylamide / (meth)acrylic acid or (meth)acrylic acid alkyl ester / butylaminoethyl methacrylate copolymer, and the like. Among them, as the betaine polymer CIII, from the viewpoint of improving the concealing property and color-developing property, a copolymer containing a structural unit derived from a betaine monomer and a hydrocarbon group derived from an aliphatic alcohol having 1 to 22 carbon atoms and a structural unit derived from an alkyl (meth)acrylate is preferable, a copolymer containing a structural unit derived from a carboxybetaine monomer and a hydrocarbon group derived from an aliphatic alcohol having 1 to 22 carbon atoms and a structural unit derived from an alkyl (meth)acrylate is more preferable, and an N-methacryloyloxyethyl-N,N-dimethylammonium-α-N-methylcarboxybetaine / alkyl methacrylate copolymer is even more preferable.

[0050] From the viewpoint of improving the concealing property and color-developing property, the weight average molecular weight of the betaine polymer is preferably 5,000 or more, more preferably 10,000 or more, and preferably 1,000,000 or less, more preferably 500,000 or less, and even more preferably 300,000 or less. The weight average molecular weight of the betaine polymer is the molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0051] Examples of commercially available betaine polymers include, for example, Plus Size L-410W, L-402W, L-440, L-440W, K-450, L-450W (above, manufactured by Gohsei Chemical Industry Co., Ltd., trade names); Yukafoamer SM, 301 (above, manufactured by Mitsubishi Chemical Corporation, trade names); RAM Resin-1000, -2000, -3000, -4000 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd., trade names); Mercote Plus 3330 (manufactured by Nippon Lubrizol Corporation, trade name), Amphoamer 28-4910, LV-71 (above, manufactured by AkzoNobel, trade names), etc.

[0052] (Nonionic polymer) Examples of nonionic polymers include polymers having structural units derived from nonionic monomers, water-soluble polysaccharides (cellulose-based, gum-based, starch-based, etc.) and their derivatives, etc. Examples of nonionic monomers in nonionic polymers include (meth)acrylates having a hydrocarbon group derived from an aliphatic alcohol having 1 to 22 carbon atoms; N-vinyl-2-pyrrolidone; vinyl alcohol; polyalkylene glycol (meth)acrylate (n = 1 to 30); alkoxypolyalkylene glycol mono(meth)acrylate (n = 1 to 30); (meth)acrylamide and its derivatives, etc. Furthermore, the nonionic polymer may further contain structural units derived from other monomers other than nonionic monomers. Examples of other monomers include the aforementioned styrene-based monomers; the aforementioned aromatic group-containing (meth)acrylates; vinyl acetate, etc.

[0053] Nonionic polymers specifically include vinyl pyrrolidone copolymers with other nonionic monomers such as polyvinyl alcohol, polyvinyl acetal, polyurethane polyurea, polyvinyl pyrrolidone, vinyl pyrrolidone / vinyl acetate copolymer, cellulose polymers such as hydroxyalkyl cellulose, polyethylene glycol, polypropylene glycol, polyglycerin, polyvinyl alcohol, pullulan, guar gum, poly N,N-dimethylacrylamide, poly N-vinyl acetamide, poly N-vinyl formamide, poly(2-alkyl-2-oxazoline), etc. Among them, from the perspective of improving concealment and color development properties, polyvinyl acetal and polyurethane polyurea are preferred nonionic polymers. When using polyvinyl butyral as the polyvinyl acetal, from the perspective of improving concealment and color development properties, the degree of acetalization of polyvinyl butyral is preferably 50 mol% or more, more preferably 55 mol% or more, still more preferably 60 mol% or more, and preferably 80 mol% or less, more preferably 75 mol% or less, still more preferably 70 mol% or less.

[0054] Commercially available nonionic polymers include polyvinyl butyral such as Esrec B series (trade name, manufactured by Sekisui Chemical Co., Ltd.); polyurethane polyurea such as BAYCUSAN series (trade name, manufactured by Covestro Japan Co., Ltd.); hydroxyethyl cellulose such as HEC Daicel SE900, SE850, SE600, SE550, SE400 (above, trade name, manufactured by Daicel Finechem Co., Ltd.); high molecular weight polyethylene glycol such as Polyox WSR N-12K, WSR N-60K, WSR-301 (above, trade name, manufactured by The Dow Chemical Company); polyethylene oxide such as PEO-27, PEO-18, PEO-15, PEO-8 (above, trade name, manufactured by Sumitomo Seika Chemicals Co., Ltd.); polyvinyl pyrrolidone such as Luviskol K90, K80, K30 (above, trade name, manufactured by BASF SE); polyvinyl alcohol such as Gohsenol series (above, trade name, manufactured by Mitsubishi Chemical Corporation), etc.

[0055] In the present invention, the amount of Polymer C dissolved in water is preferably less than 5 g, as the amount of Polymer C dissolved in 100 g of water at 25°C when Polymer C dried at 105°C for 2 hours until a constant weight is reached is considered from the viewpoint of improving hiding power and color development. When Polymer C is an anionic polymer, the dissolution amount is the amount of dissolution when the anionic groups of Polymer C are 100% neutralized with sodium hydroxide. When Polymer C is a cationic polymer, the dissolution amount is the amount of dissolution when the cationic groups of Polymer C are 100% neutralized with hydrochloric acid.

[0056] From the viewpoint of improving hiding power and color development, Polymer C is preferably an amphiphilic polymer that is insoluble in Solvent B but has an affinity for Solvent B and also has an affinity for water. More preferably, it is one or more selected from ionic polymers and nonionic polymers. Even more preferably, it contains a polymer containing at least one selected from monomers having an acidic group, monomers having a basic group, and betaine monomers as monomer structural units. Even more preferably, it contains a polymer containing at least one selected from monomers having an acidic group and betaine monomers as monomer structural units. Even more preferably, it contains one or more selected from anionic polymer CI and betaine polymer CIII. Even more preferably, it contains betaine polymer CIII. Also, from the viewpoint of improving the water resistance of the cosmetic coating film while improving hiding power and color development, Polymer C preferably contains a polymer having a cationic group. As the polymer having a cationic group, from the same viewpoint as above, more preferably, it is one or more selected from cationic polymers and betaine polymers. Even more preferably, it is a cationic polymer. Even more preferably, it is one or more selected from cationic polymer CII-1 and cationic silicone polymer CII-2. Even more preferably, it is cationic polymer CII-1.

[0057] Furthermore, from the viewpoint of improving the water resistance of the cosmetic coating film while improving hiding power and color development, two or more kinds of Polymer C may be used in combination. When two or more kinds of Polymer C are used in combination, from the same viewpoint as above, preferably, it contains at least two kinds selected from anionic polymer CI, cationic polymer CII-1, cationic silicone polymer CII-2, and betaine polymer CIII. More preferably, it is a combination of anionic polymer CI and cationic polymer CII-1, a combination of anionic polymer CI and cationic silicone polymer CII-2, a combination of cationic polymer CII-1 and cationic silicone polymer CII-2, a combination of anionic polymer CI and betaine polymer CIII, a combination of cationic polymer CII-1 and betaine polymer CIII, a combination of cationic silicone polymer CII-2 and betaine polymer CIII, or a combination of anionic polymer CI, cationic silicone polymer CII-2, and betaine polymer CIII. Even more preferably, it is a combination of anionic polymer CI, cationic silicone polymer CII-2, and betaine polymer CIII.

[0058] <Colorant> The colorant used in the present invention is not particularly limited as long as it is used in ordinary cosmetics, and examples include organic pigments, hydrophobic dyes (oil-soluble dyes, disperse dyes), water-soluble dyes (acid dyes, reactive dyes, direct dyes, etc.). Note that the hydrophobic dye refers to a dye having a solubility in 100 g of water (20 °C) of preferably less than 6% by mass. Specific examples of the colorant include organic pigments such as Red No. 201, Red No. 202, Yellow No. 401, and Blue No. 404; lake pigments such as Red No. 104, Red No. 230, Yellow No. 4, Yellow No. 5, and Blue No. 1; dyes such as Red No. 226, Acid Yellow 1, Acid Orange 7, Food Blue 2, and Acid Red 52; and those obtained by coating these pigments and dyes with a resin such as polymethacrylic acid ester. In the present invention, as long as the effects of the present invention can be obtained, the use of inorganic pigments is not hindered. Examples of such inorganic pigments include white inorganic pigments such as titanium oxide and zinc oxide; non-white inorganic pigments such as yellow iron oxide, red iron oxide, black iron oxide, carbon black, ultramarine, cobalt blue, cobalt blue titanium oxide, black titanium oxide, chromium oxide, chromium hydroxide, and titanium / titanium oxide sintered products; extender pigments such as calcium carbonate, silica, and talc. When the colorant contains an inorganic pigment, from the viewpoints of hiding power and color development, at least one selected from non-white inorganic pigments and extender pigments is preferable. The colorant can be used alone or in combination of two or more. From the viewpoint of improving color development, colored hues such as yellow, magenta, cyan, blue, red, orange, and green are preferable as the hue of the colorant.

[0059] From the viewpoints of improving the dispersibility in the cosmetic composition and the water resistance of the cosmetic coating film, the surface of the colorant may be hydrophobically treated. From the same viewpoints as above, when the colorant contains an inorganic pigment, the inorganic pigment preferably has a hydrophobically treated surface. As the hydrophobization treatment, the hydrophobization treatment usually applied to powders for cosmetics using various hydrophobizing agents is preferable. Examples of the hydrophobization treatment include silicone treatment, fatty acid treatment, lauroyl lysine treatment, surfactant treatment, metal soap treatment, fluorine compound treatment, lecithin treatment, nylon treatment, and polymer treatment.

[0060] Examples of the form of the colorant in the cosmetic composition of the present invention include a form dispersed in the cosmetic composition and a form dissolved in the cosmetic composition. Among them, from the viewpoints of improving hiding power and color development and improving the dispersibility in the cosmetic composition, the form of the colorant is preferably a form dispersed in the cosmetic composition, more preferably a form dispersed using a dispersant or a self-dispersing type form without using a dispersant, and still more preferably a form dispersed using a dispersant. As the self-dispersing type form, a self-dispersing type pigment is preferable. A self-dispersible pigment means a pigment that can be incorporated into a cosmetic composition without using a surfactant or a dispersant by bonding a functional group that imparts dispersibility directly to the surface of the pigment or via another atomic group. Examples of the functional group that imparts dispersibility include anionic functional groups such as a carboxy group and a sulfonic acid group, or a polyethylene oxide group and a polypropylene oxide group. Specifically, commercially available self-dispersible pigments include the CAB-O-JET200 series, the 300 series, and the 400 series of Cabot Corporation.

[0061] From the viewpoints of the homogeneity of coloring and the improvement of hiding power and color development, the colorant is preferably dispersed with a dispersible polymer D as a dispersant. In this specification, the "dispersible polymer" means a polymer capable of dispersing a colorant in the medium of a cosmetic composition. The dispersible polymer D is preferably soluble in either one of the solvent A and the solvent B and insoluble in the other from the viewpoints of improving hiding power and color development. When the dispersible polymer D is soluble in the solvent A and insoluble in the solvent B, in the process of phase separation of the solvent A and the solvent B when forming a cosmetic coating film, the colorant in the system coexists with the dispersing polymer D and hardly exists in the solvent B due to the solubility of the dispersible polymer D in the solvent B. Therefore, in the cosmetic coating film, it is mainly included as a constituent of the shell of the primary particles together with the polymer C. On the other hand, when the dispersible polymer D is insoluble in the solvent A and soluble in the solvent B, in the process of phase separation of the solvent A and the solvent B when forming a cosmetic coating film, the colorant is distributed in the droplets of the phase-separated solvent B. Therefore, particularly when the solvent B has volatility, the colorant exists in the cavity of the hollow primary particles in the cosmetic coating film.

[0062] From the perspective of improving concealment and color development properties, the dispersible polymer D is preferably soluble in solvent A and insoluble in solvent B. Examples of the dispersible polymer D include ionic polymers such as anionic polymers, cationic polymers, and betaine polymers exemplified by the aforementioned polymer C; nonionic polymers, etc. Among them, the dispersible polymer D is more preferably at least one selected from ionic polymers and nonionic polymers, and even more preferably at least one selected from the aforementioned anionic polymer CI, cationic polymer CII-1, cationic silicone polymer CII-2, betaine polymer CIII, and nonionic polymer, and still more preferably at least one selected from anionic polymer CI and nonionic polymer.

[0063] The anionic polymer CI used as the dispersible polymer D preferably contains a structural unit derived from a monomer having an acidic group and a structural unit derived from an alkyl (meth)acrylate, more preferably contains a structural unit derived from a monomer having an acidic group, a structural unit derived from an alkyl (meth)acrylate, and a structural unit derived from (N-alkyl)(meth)acrylamide, still more preferably is a (meth)acrylic acid / (meth)acrylic acid alkyl ester / (N-alkyl)(meth)acrylamide copolymer, and even more preferably is an acrylic acid / acrylic acid alkyl ester / (N-alkyl)acrylamide copolymer. The nonionic polymer used as the dispersible polymer D is preferably at least one selected from polyvinyl acetal and polyurethane polyurea, more preferably polyvinyl acetal, and still more preferably polyvinyl butyral. From the perspective of improving concealment and color development properties, the degree of acetalization of polyvinyl butyral is preferably 50 mol% or more, more preferably 55 mol% or more, still more preferably 60 mol% or more, and preferably 80 mol% or less, more preferably 75 mol% or less, still more preferably 70 mol% or less.

[0064] When the colorant is dispersed by the dispersing polymer D, it is preferable that both the polymer C and the dispersing polymer D are each preferably at least one selected from ionic polymers and nonionic polymers. Examples of the combination of the polymer C and the dispersing polymer D include a combination in which the polymer C is an ionic polymer and the dispersing polymer D is an ionic polymer, a combination in which the polymer C is an ionic polymer and the dispersing polymer D is a nonionic polymer, and a combination in which the polymer C is a nonionic polymer and the dispersing polymer D is an ionic polymer. The combination of the polymer C and the dispersing polymer D is preferably such that the polymer C is at least one selected from anionic polymer CI, cationic polymer CII-1, cationic silicone polymer CII-2, betaine polymer CIII, and nonionic polymers, and the polymer D is at least one selected from anionic polymer CI and nonionic polymers. More preferably, the polymer C is at least one selected from anionic polymer CI, cationic polymer CII-1, cationic silicone polymer CII-2, and betaine polymer CIII, and the polymer D is at least one selected from anionic polymer CI and nonionic polymers. Among them, from the viewpoint of improving hiding power and color development property, the combination of the polymer C and the dispersing polymer D is more preferably such that the polymer C is an anionic polymer or a betaine polymer and the polymer D is an anionic polymer. From the viewpoint of improving the water resistance of the cosmetic coating film, the combination of the polymer C and the dispersing polymer D is more preferably such that the polymer C is a cationic polymer or a betaine polymer and the polymer D is an anionic polymer. From the viewpoints of improving hiding power and color development property and the water resistance of the cosmetic coating film, the combination of the polymer C and the dispersing polymer D is even more preferably such that the polymer C is a betaine polymer and the polymer D is an anionic polymer.

[0065] When the colorant is dispersed by the dispersible polymer D, the volume-average particle diameter of the colorant particles dispersed by the polymer D is preferably 10 nm or more, more preferably 50 nm or more, still more preferably 100 nm or more, and preferably 1,000 nm or less, more preferably 900 nm or less, still more preferably 500 nm or less, even more preferably 300 nm or less, even more preferably 200 nm or less. The volume-average particle diameter of the colorant particles is measured by the method described in the examples.

[0066] In the cosmetic composition of the present invention, within a range not inhibiting the effects of the present invention, as optional components, components used in cosmetic compositions such as ultraviolet scattering agents, ultraviolet absorbers, fragrances, beauty components, medicinal components, pH adjusters, moisturizing agents, antioxidants, bactericides, preservatives, etc. may be contained. These can be used alone or in combination of two or more.

[0067] The viscosity of the cosmetic composition of the present invention at 20°C is preferably 1 mPa·s or more, more preferably 2 mPa·s or more, still more preferably 3 mPa·s or more, and preferably 1,000 mPa·s or less, more preferably 700 mPa·s or less, still more preferably 300 mPa·s or less, even more preferably 100 mPa·s or less, even more preferably 50 mPa·s or less, even more preferably 30 mPa·s or less, even more preferably 20 mPa·s or less, even more preferably 10 mPa·s or less, even more preferably 7 mPa·s or less. The viscosity of the cosmetic composition at 20°C is measured by the method described in the examples.

[0068] (Manufacture of Cosmetic Composition) The cosmetic composition can be obtained by mixing the solvent A, solvent B, polymer C, colorant, and, if necessary, the above-mentioned optional components and stirring them. When the colorant is dispersed by the dispersible polymer D, it is preferable to mix the colorant as a colorant dispersion containing colorant particles dispersed by the dispersible polymer D. There are no particular restrictions on the order of mixing Solvent A, Solvent B, Polymer C, the colorant dispersion, and the optional components. However, preferably, first Solvent A and Polymer C are mixed to dissolve Polymer C in Solvent A to obtain a solution of Polymer C, and then Solvent B and the colorant dispersion are added to and mixed with the solution. If necessary, the optional components may be further added and mixed.

[0069] The colorant dispersion can be obtained by subjecting a colorant, a dispersible polymer D, etc. to a dispersion treatment by a known method. Specifically, it is preferably obtained by a production method including a step of subjecting a colorant mixture containing a colorant, a dispersible polymer D, and an organic solvent to a dispersion treatment to obtain a colorant dispersion, but is not necessarily limited to this method. The organic solvent used in the production of the colorant dispersion preferably has a high affinity with the dispersible polymer D and good wettability to the colorant. From the viewpoints of improving the wettability to the colorant and the adsorbability of the dispersible polymer to the colorant, and the safety from the organic solvent remaining after the application of the cosmetic composition, ethanol and isopropanol are preferable. In the dispersion treatment for the production of the colorant dispersion, as means for applying a shear stress, for example, a kneader such as a roll mill, a kneader, an extruder, a high-pressure homogenizer such as a Microfluidizer (manufactured by Microfluidics, trade name), a paint shaker, a media type disperser such as a bead mill can be used. Among these, from the viewpoint of reducing the particle size of the colorant, it is preferable to use a high-pressure homogenizer. When performing the dispersion treatment using a high-pressure homogenizer, the colorant particles can be controlled to have a desired particle size by controlling the treatment pressure and the number of passes of the dispersion treatment.

[0070] The content of each component in the cosmetic composition of the present invention is as follows from the viewpoints of improving concealing power and color development. The content of solvent A in the cosmetic composition of the present invention is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 55% by mass or less. The content of solvent B in the cosmetic composition of the present invention is preferably 5% by mass or more, more preferably 7% by mass or more, still more preferably 10% by mass or more, and even more preferably 13% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, even more preferably 20% by mass or less, and even more preferably 17% by mass or less. The content of polymer C in the cosmetic composition of the present invention is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 1.3% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, even more preferably 3% by mass or less, and even more preferably 2% by mass or less.

[0071] The total content of solvent A and solvent B in the cosmetic composition of the present invention is preferably 50% by mass or more, more preferably 55% by mass or more, still more preferably 60% by mass or more, even more preferably 63% by mass or more, even more preferably 65% by mass or more, and even more preferably 67% by mass or more, from the viewpoint of improving concealment and color development, and preferably 85% by mass or less, more preferably 80% by mass or less, still more preferably 75% by mass or less, and even more preferably 70% by mass or less. The mass ratio [solvent A / solvent B] of the content of solvent A to the content of solvent B in the cosmetic composition of the present invention is preferably 0.5 or more, more preferably 1 or more, still more preferably 1.5 or more, and even more preferably 2 or more, from the viewpoints of improving concealment and color development and promoting the development rate of color development, and preferably 15 or less, more preferably 13 or less, still more preferably 11 or less, even more preferably 8 or less, even more preferably 6 or less, even more preferably 4 or less, and even more preferably 3 or less.

[0072] When the polymer C contains, as a constituent unit, at least one selected from a monomer having an acidic group, a monomer having a basic group, and a betaine monomer, the content of the polymer containing, as a constituent unit, at least one selected from a monomer having an acidic group, a monomer having a basic group, and a betaine monomer in the polymer C is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, even more preferably 90% by mass or more, and preferably 100% by mass or less, and even more preferably 100% by mass, from the viewpoints of improving concealing property and color-developing property. When the polymer C contains one or more selected from a cationic polymer and a betaine polymer as the polymer having a cationic group, from the viewpoint of improving the water resistance of the cosmetic coating film while improving the concealing property and color-developing property, the content of the polymer having a cationic group in the polymer C is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, even more preferably 60% by mass or more, and preferably 100% by mass or less, more preferably 90% by mass or less, still more preferably 80% by mass or less. When two or more kinds of the polymer C are used in combination, it is preferable to adjust so that the contents of the respective polymers C in the cosmetic composition become the same amount.

[0073] The content of the colorant in the cosmetic composition of the present invention is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, even more preferably 4% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 7% by mass or less, from the viewpoints of improving concealing property and color-developing property. When the colorant is dispersed by the dispersing polymer D, the content of the dispersing polymer D in the cosmetic composition of the present invention is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 1.3% by mass or more, and preferably 7% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, even more preferably 2% by mass or less. When the colorant is dispersed with the dispersible polymer D, the mass ratio [colorant / dispersible polymer D] of the content of the colorant in the cosmetic composition of the present invention to the content of the dispersible polymer D is preferably 0.5 or more, more preferably 1 or more, still more preferably 2 or more, and preferably 5 or less, more preferably 4 or less, still more preferably 3 or less. When the colorant is dispersed with the dispersible polymer D, the mass ratio [polymer C / dispersible polymer D] of the content of polymer C and the content of the dispersible polymer D in the cosmetic composition of the present invention is preferably 0.3 or more, more preferably 0.5 or more, still more preferably 0.7 or more, and preferably 3 or less, more preferably 2 or less, still more preferably 1.5 or less, even more preferably 1.3 or less.

[0074] The cosmetic composition of the present invention may contain water as long as the effects of the present invention are not inhibited. The water content in the cosmetic composition of the present invention is preferably 5% by mass or less, more preferably less than 5% by mass, still more preferably 4% by mass or less, even more preferably 3% by mass or less, even more preferably 2% by mass or less, even more preferably 1% by mass or less, even more preferably substantially 0% by mass, and even more preferably 0% by mass, from the viewpoint of suppressing the phase separation of the solvent B in the cosmetic composition and improving the hiding power and color development. In addition, the water content in the cosmetic composition of the present invention means the total amount of water contained in the cosmetic composition including the amount brought in from the raw materials of each component such as the solvent A such as ethanol and the amount mixed in due to dew condensation during the manufacturing process of the cosmetic composition, in addition to the intentionally blended amount.

[0075] The cosmetic composition of the present invention does not prevent the use of inorganic pigments as long as the effects of the present invention can be obtained as described above. However, the content of the inorganic pigment in the cosmetic composition is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 2% by mass or less, even more preferably 1% by mass or less, and even more preferably 0% by mass.

[0076] The cosmetic composition of the present invention can be applied to the skin (including the lips), hair, or nails, and is preferably used by application. Thereby, concealability and coloring properties can be imparted. That is, the cosmetic composition of the present invention is preferably used as a skin cosmetic composition, a hair cosmetic composition, or a nail cosmetic composition, and is preferably used as a hair cosmetic composition. Examples of skin cosmetic compositions include base makeup cosmetics such as makeup bases, foundations, and concealers; point makeup cosmetics such as blush, eyeshadow, mascara, eyeliner, eyebrows, overcoat agents, and lipsticks; sunscreen cosmetics such as sunscreen lotions and sunblock creams; skin cleansing cosmetics such as facial cleansers and cleansing cosmetics; and basic cosmetics such as beauty essences, packs, and massage cosmetics. Among them, from the viewpoints of concealability and coloring properties, it is preferably applied to base makeup cosmetics such as makeup bases and foundations, and point makeup cosmetics. Examples of hair cosmetic compositions preferably include hair dyes such as hair mascara and hair color; styling agents such as hair wax, hair spray, hair mousse, and hair foam; and hair growth agents. Examples of nail cosmetic compositions preferably include nail cosmetics such as nail enamels and nail glosses. The dosage form of the cosmetic composition of the present invention can be adapted to solutions, emulsions, creams, gels, pastes, solids, multilayers, etc., and can also be applied as sprays, sheets, and mousses.

[0077] [Cosmetic method] The cosmetic method of the present invention can be applied by a coating method commonly used when applying to the skin, hair, or nails under the temperature and humidity conditions of daily life, and coating the cosmetic composition on the skin, hair, or nails.

[0078] The coating amount of the cosmetic composition is preferably 1 mg / cm 2 or more, more preferably 2 mg / cm 2 or more, and even more preferably 3 mg / cm 2or less, preferably 10 mg / cm 2 or less, more preferably 7 mg / cm 2 or less, still more preferably 5 mg / cm 2 or less. The thickness of the coating film before drying is preferably 10 μm or more, more preferably 20 μm or more, still more preferably 30 μm or more, and preferably 300 μm or less, more preferably 200 μm or less, still more preferably 150 μm or less.

[0079] In the makeup method of the present invention, from the viewpoint of improving concealment and color development, it is preferable to use patterning printing used in a printing system as the coating method of the makeup composition. By using the patterning printing, the coating amount, coating area, etc. of the makeup composition can be controlled. Further, by designing the printing pattern to be used, the makeup image to be applied can be designed in advance. Furthermore, by using the patterning printing, the reproducibility of a makeup coating film having a complicated makeup image can also be enhanced. Examples of the patterning printing include on-demand printing such as an inkjet method and a dispenser method; and analog printing such as screen printing, flexographic printing, gravure printing, and offset printing, and it can be selected and used according to the viscosity of the makeup composition and the like. On-demand printing is a plate-less method that does not require a printing plate and is a method of printing in a non-contact state on an object to be printed such as skin, hair, or nails. Analog printing is a plate-making method that requires a printing plate and is a method of printing in a contact state on an object to be printed such as skin, hair, or nails. Among these, on-demand printing can eject droplets of the cosmetic composition to apply a desired amount of droplets to a desired area of the skin, hair, or nails, and can control the amount applied per unit area of the droplets, the application area, etc., facilitating fine control of the cosmetic image. From this perspective, the method for applying the cosmetic composition is more preferably a method of ejecting the cosmetic composition by one or more selected from the inkjet method and the dispenser method to apply droplets of the cosmetic composition to the skin, hair, or nails, and even more preferably a method of ejecting the cosmetic composition by the inkjet method to apply droplets of the cosmetic composition to the skin, hair, or nails.

[0080] From the perspective of improving concealment and color development properties, the applied voltage of the inkjet head is preferably 5 V or more, more preferably 10 V or more, still more preferably 15 V or more, and preferably 50 V or less, more preferably 45 V or less, still more preferably 40 V or less. From the perspective of improving concealment and color development properties, the driving frequency of the inkjet head is preferably 1 kHz or more, more preferably 3 kHz or more, and preferably 300 kHz or less, more preferably 150 kHz or less, still more preferably 90 kHz or less, even more preferably 50 kHz or less. From the perspective of improving concealment and color development properties, the ejected droplet volume of the cosmetic composition is preferably 0.01 pL or more, more preferably 0.1 pL or more, still more preferably 1 pL or more, even more preferably 4 pL or more per droplet, and preferably 50 pL or less, more preferably 40 pL or less, still more preferably 35 pL or less.

[0081] The driving density p of the droplets of the cosmetic composition, expressed as the number of dots per square inch, is preferably 10,000 or more, more preferably 30,000 or more, still more preferably 50,000 or more, even more preferably 100,000 or more, and preferably 3,000,000 or less, more preferably 1,000,000 or less, still more preferably 500,000 or less. The driving density p of the droplets is calculated from the product of the dot density (dpi) in the direction perpendicular to the printing direction and the dot density (dpi) in the printing direction.

[0082] In the present invention, after applying the cosmetic composition to the skin, hair or nails to form a coating film, it is preferable to dry the coating film under atmospheric pressure conditions. Thereby, a cosmetic coating film excellent in concealability and color developability can be formed. In the present invention, the drying of the coating film can be sufficiently performed by natural drying under the temperature and humidity conditions of daily life. However, from the viewpoint of accelerating the drying, blowing drying, warm air drying, etc. may be performed. Further, when the cosmetic composition is applied to the skin, it may be performed by natural drying at the temperature of the skin. When performing warm air drying, the temperature during drying of the coating film is not particularly limited, but is preferably 40°C or higher, more preferably 50°C or higher, still more preferably 55°C or higher, and preferably 80°C or lower, more preferably 70°C or lower, still more preferably 65°C or lower. The drying time of the coating film is preferably 5 minutes or more, more preferably 7 minutes or more, still more preferably 10 minutes or more, and preferably 30 minutes or less, more preferably 20 minutes or less.

[0083] From the viewpoint of further improving the concealability and color developability, the cosmetic method of the present invention includes, after the step of applying the cosmetic composition to the skin, hair, or nails (hereinafter, also referred to as "step 1"), before drying the coating film composed of the cosmetic composition, a step of applying droplets of liquid E containing water to the cosmetic composition applied on the skin, hair, or nails (hereinafter, also referred to as "step 2"). Thereby, the phase separation of solvent A and solvent B proceeds rapidly, the formation of primary particles in which solvent B is coated with polymer C is promoted, and the concealability and color developability can be improved.

[0084] <Liquid E> The liquid E according to the present invention contains water, but may contain other liquids in addition to water. As other liquids, monohydric alcohols having 1 to 4 carbon atoms are preferred, and examples thereof include ethanol, n-propanol, isopropanol, tert-butyl alcohol, and the like. Among them, from the viewpoint of improving concealability and color development, other liquids are preferably at least one selected from ethanol, n-propanol, isopropanol, and tert-butyl alcohol, and more preferably ethanol. The water content in liquid E is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 97% by mass or more, even more preferably 99% by mass or more, and is preferably 100% by mass or less, and even more preferably 100% by mass. The ethanol content as other liquids in liquid E is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, even more preferably 20% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, even more preferably 3% by mass or less, even more preferably 1% by mass or less.

[0085] The method for applying droplets of liquid E in step 2 is not particularly limited as long as it can apply minute droplets to the surface of the cosmetic composition on the skin, hair, or nails. However, from the viewpoint of improving concealability and color development, it is preferable to use a device that generates minute droplets of liquid E containing water. The device for generating minute droplets is not particularly limited, and examples thereof include devices using a piezo type, thermal type, pressurized type, rotary type, steam type, ultrasonic type, electrostatic type, and the like. Among these, a method of spraying droplets using an atomizing device (spray) or the like or a method of applying droplets by pattern printing used in a printing system is preferable, and a method of spraying droplets using an atomizing device or a method of discharging droplets by an inkjet method is more preferable. From the viewpoint of improving concealability and color development, the application amount of droplets of liquid E is preferably 0.01 mg / cm 2More preferably, it is 0.05 mg / cm or more 2 More preferably still, it is 0.1 mg / cm or more 2 or more, and preferably 10 mg / cm or less 2 More preferably, it is 7 mg / cm or less 2 More preferably still, it is 5 mg / cm or less 2 or less. From the viewpoint of improving concealment and color development properties, the average diameter of the droplets of Liquid E is preferably 0.01 μm or more, more preferably 0.1 μm or more, and even more preferably 1 μm or more, and preferably 50 μm or less, more preferably 30 μm or less, and even more preferably 10 μm or less.

[0086] Examples of the atomizing device include a jet atomizing device, an ultrasonic atomizing device, a mesh atomizing device, and the like. The spraying ability of the atomizing device is preferably 0.01 mL / min or more, more preferably 0.1 mL / min or more, and even more preferably 0.3 mL / min or more, and preferably 10 mL / min or less, more preferably 7 mL / min or less, and even more preferably 5 mL / min or less. The spraying time of the atomizing device is preferably 1 second or more, more preferably 3 seconds or more, and preferably 30 seconds or less, more preferably 20 seconds or less, and even more preferably 10 seconds or less. As a method of discharging droplets by an inkjet method, the same method as the above-described method of applying the cosmetic composition can be used.

[0087] The application of the droplets of Liquid E in Step 2 may be applied to the entire area where the cosmetic composition was applied in Step 1, or may be applied to a part of the area. The time interval between Step 1 and Step 2 is not particularly limited as long as Step 2 is performed before the cosmetic composition on the skin, hair, or nails dries, but is preferably 0.01 seconds or more, more preferably 0.1 seconds or more, and from the viewpoint of improving concealment and color development properties, is preferably 10 seconds or less, more preferably 5 seconds or less.

[0088] [Cosmetic coating film] The average particle size of the primary particles contained in the cosmetic coating film formed according to the present invention is preferably 0.1 μm or more, more preferably 0.2 μm or more, from the viewpoint of improving the strength and color development property of the cosmetic coating film, and is preferably 5 μm or less, more preferably 3 μm or less, from the viewpoint of improving the hiding property. The average particle size of the primary particles contained in the cosmetic coating film can be measured by observing the formed cosmetic coating film using a scanning electron microscope and performing image processing on the obtained scanning electron micrograph using image analysis software "ImageJ" (manufactured by the National Institutes of Health, USA). Specifically, using an optical microscope (manufactured by Hylocks Corporation, product name: RH-2000), an observation image of the polymer coating film surface is taken at a magnification of 2,500 times, and image processing is performed using image analysis software (manufactured by the National Institutes of Health, USA, ImageJ) to measure the average particle size of the primary particles contained in the coating film. When taking a photograph with an optical microscope, adjust the brightness and contrast so that the ratio of pixels reaching the maximum brightness value is 1% or less and the average value of the brightness values falls within the range of 40% to 60% of the maximum brightness value, and save the observation image. Convert the observation image into an 8-bit grayscale image using the image conversion function of ImageJ. Next, perform scale setting according to the magnification of the optical microscope. With this scale setting, the particle size data calculated in subsequent calculations is converted into the actual size. For example, when the magnification is 2,500 times, convert so that a length of 1 mm becomes 15,840 pixels. Next, perform Subtract Background processing. At this time, set the Rolling Ball Radius to approximately the same size as the observed primary particle size. Specifically, when the majority of the primary particles have a diameter of about 3 μm and 1 mm has 15,840 pixels, the Rolling Ball Radius is set to 50 pixels. Thereby, it is possible to cut out the noise components in the photographing that are smaller than the primary particle size. Next, perform binarization processing on the region of the primary particles using the Threshold function, which is an image adjustment function of ImageJ. In this specification, "binarization processing" refers to a process in which, when the luminance value of an image is equal to or greater than a specified value (threshold value), it is set to white, and when it is less than the specified value, it is set to black. In the image obtained by observation, the shell of the primary particle is represented by high luminance because the polymer density is high, and the core part is represented by low luminance. As a result, it becomes possible to obtain an image with clear shadows sufficient to measure the average particle diameter of the primary particles. For the obtained binary image, "Analyze Particles" of ImageJ is executed. In addition, particles that are cut off at the image edge, particles with a major axis that is one-tenth of the generally observed primary particle diameter (particles less than 5 pixels in the above settings), and particles with a circularity of less than 0.5 are excluded from the measurement targets, and the average value of the major axes of at least 300 or more particles is taken as the average particle diameter of the primary particles.

[0089] Moreover, the cosmetic coating film formed by the present invention preferably contains secondary particles in which primary particles are aggregated. In the present invention, with the volatilization of solvent A and the surface alignment of the formed primary particles, a cell-like convection structure regularly partitioned in the coating film, so-called Benard Cells, is generated, and it is considered that the primary particles can be aggregated by the Benard convection in each cell to form secondary particles. Such a cosmetic coating film containing secondary particles has a structure close to the actual surface relief structure of the skin, especially when applied to the skin, and thus can form a cosmetic coating film that gives a natural impression.

Examples

[0090] In the following synthesis examples, production examples, examples and comparative examples, "parts" and "%" are "parts by mass" and "% by mass" unless otherwise specified. The physical properties of polymers and the like were measured by the following methods.

[0091] (1) Measurement of the weight average molecular weight of cationic polymer CII-1 Using a solution prepared by dissolving phosphoric acid and lithium bromide in N,N-dimethylformamide at concentrations of 60 mmol / L and 50 mmol / L, respectively, as the eluent, gel permeation chromatography [GPC apparatus (HLC-8320GPC) manufactured by Tosoh Corporation, columns (TSKgel SuperAWM-H, TSKgel SuperAW3000, TSKgel guardcolum Super AW-H) manufactured by Tosoh Corporation, flow rate: 1 mL / min] was used to measure with a monodisperse polystyrene kit of known molecular weight [PStQuick B (F-550, F-80, F-10, F-1, A-1000), PStQuick C (F-288, F-40, F-4, A-5000, A-500), manufactured by Tosoh Corporation] as the standard substance. The measurement sample used was prepared by mixing 0.1 g of cationic polymer CII-1 with 10 mL of the above eluent in a glass vial, stirring with a magnetic stirrer at 25°C for 10 hours, and filtering through a syringe filter (DISMIC-13HP PTFE 0.2 μm, manufactured by Advantec Co., Ltd.).

[0092] (2) Number average molecular weight of poly(N-propionylethyleneimine) Using 1 mmol / L Farmine DM20 (trade name, manufactured by Kao Corporation) / chloroform as the eluent, gel permeation chromatography [measurement columns: two columns (K-804L) manufactured by Showa Denko KK connected in series, flow rate: 1 mL / min, column temperature: 40°C, detector: differential refractometer] was used to measure with polystyrene of known molecular weight as the standard substance. The measurement sample used was 100 μL at a concentration of 5 mg / mL.

[0093] (3) Measurement of viscosity Using an E-type viscometer RE80 manufactured by Toki Sangyo Co., Ltd., the viscosity was measured with a measurement time of 1 minute, a rotation speed of 100 rpm, and a standard rotor (1°34'×R24). Note that the viscosity was measured at 20°C for hydrogenated polyisobutene, 25°C for silicone oil, and 20°C for the cosmetic composition.

[0094] (4) Measurement of volume average particle diameter of colorant particles The volume-average particle diameter of the colorant particles in the colorant dispersion was measured using a zeta potential and particle size measurement system "ELS-8000" (manufactured by Otsuka Electronics Co., Ltd.). A dispersion diluted with water so that the concentration of the particles to be measured was about 5×10-3 mass% was placed in a measurement cell, the temperature was 25°C, the number of integration times was 100, the refractive index of water (1.333) was input as the refractive index of the dispersion solvent, and the measurement was performed by the cumulant analysis method.

[0095] Details of each component are as follows. (Anionic polymer CI) Ultrahold 8: A copolymer of acrylic acid / acrylic acid alkyl ester / (N-alkyl)acrylamide (manufactured by BASF Japan Ltd., trade name: Ultrahold 8), 100% solid powder Ultrahold Strong: A copolymer of acrylic acid / acrylic acid alkyl ester / (N-alkyl)acrylamide (manufactured by BASF Japan Ltd., trade name: Ultrahold Strong), 100% solid powder Ultrahold Power-dry: A powder obtained by drying a solution (solid content 32%) of a copolymer of acrylic acid / acrylic acid alkyl ester / (N-alkyl)acrylamide (manufactured by BASF Japan Ltd., trade name: Ultrahold Power)

[0096] (Cationic polymer CII-1) Cationic polymer 1: The copolymer obtained in Synthesis Example 1 below Cationic polymer 2: The copolymer obtained in Synthesis Example 2 below (Cationic silicone polymer CII-2) Cationic silicone polymer 1: The poly(N-propionylethyleneimine) / dimethylpolysiloxane copolymer obtained in Synthesis Example 3 below Cationic silicone polymer 2: The poly(N-propionylethyleneimine) / dimethylpolysiloxane copolymer obtained in Synthesis Example 4 below Cationic silicone polymer 3: The poly(N-propionylethyleneimine) / dimethylpolysiloxane copolymer obtained in Synthesis Example 5 below

[0097] (Betaine Polymer CIII) Powder obtained by drying an ethanol solution (solid content: 30%) of Yukafoamer SM-dry: N-methacryloyloxyethyl-N,N-dimethylammonium-α-N-methylcarboxybetaine / alkyl methacrylate copolymer (manufactured by Mitsubishi Chemical Corporation, trade name: Yukafoamer SM)

[0098] (Nonionic Polymer) Polyvinyl butyral: Esrec BM-1 (manufactured by Sekisui Chemical Co., Ltd., trade name, degree of acetalization: about 65 mol% (catalog value)), powder with 100% solid content Polyurethane-polyurea: Powder obtained by drying BAYCUSAN C2000 (manufactured by Covestro Japan Co., Ltd., trade name, ethanol solution with 40% solid content of polyurethane-64)

[0099] (Solvent B) [Hydrocarbon oil] Pearl Lime 3: Hydrogenated polyisobutene (manufactured by NOF Corporation, trade name: Pearl Lime 3, boiling point: 179°C, Ra45, viscosity: 1.4 mPa·s) Pearl Lime 4: Hydrogenated polyisobutene (manufactured by NOF Corporation, trade name: Pearl Lime 4, boiling point: 262°C, Ra45, viscosity: 3.7 mPa·s) [Silicone oil] KF-96A-1cs: Trisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-96A-1cs, boiling point: 153°C, Ra45, viscosity: 0.9 mPa·s) TMF-1.5: Methyltrimethicone (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: TMF-1.5, boiling point: 191°C, Ra45, viscosity: 1.4 mPa·s)

[0100] Synthesis Example 1 (Synthesis of Cationic Polymer 1) Into a reaction vessel equipped with two dropping funnels 1 and 2, the monomers and organic solvents having the compositions shown in the "Initial Charge Monomer Solution" column of Table 1 were placed, and nitrogen gas substitution was performed. On one hand, the monomer and organic solvent with the composition shown in the "Dropwise Monomer Solution" column of Table 1 were mixed to prepare a dropwise monomer solution. Separately, the polymerization initiator (2,2'-azobis(2,4-dimethylvaleronitrile): manufactured by Fujifilm Wako Pure Chemical Corporation, trade name: V-65) and organic solvent shown in the "Polymerization Initiator Solution" column of Table 1 were mixed to prepare a polymerization initiator solution, which were respectively placed into dropping funnels 1 and 2, and nitrogen gas substitution was carried out. Under a nitrogen atmosphere, while stirring the initial charged monomer solution in the reaction vessel, it was maintained at 62 °C, and the dropwise monomer solution and the polymerization initiator solution were gradually dropped into the reaction vessel over 2 hours so that the ratio of the dropped polymerization initiator to the dropped monomer was constant. After the dropping was completed, while maintaining at 62 °C, it was stirred for 1 hour, and then 47 parts of acetone was added. While further stirring, it was maintained at 62 °C and subjected to heat aging for 4 hours. Next, an ultrafiltration membrane (manufactured by Nippon Gaishi Co., Ltd., ceramic ultrafiltration membrane, trade name: Sepfiltr, pore size 10 nm) was used to remove unreacted monomers and polymerization initiator residues from the reaction product, and it was dried to obtain a cationic amphiphilic polymer (hereinafter, also referred to as "cationic polymer 1"). The weight average molecular weight of the obtained cationic polymer 1 was 130,000.

[0101] Synthesis Example 2 (Synthesis of cationic polymer 2) Into a reaction vessel equipped with two dropping funnels 1 and 2, the monomer and organic solvent with the composition shown in the "Initial Charged Monomer Solution" column of Table 1 were put in, and nitrogen gas substitution was carried out. On one hand, the monomer and organic solvent with the composition shown in the "Dropwise Monomer Solution" column of Table 1 were mixed to prepare a dropwise monomer solution. Separately, the polymerization initiator (V-65) and organic solvent shown in the "Polymerization Initiator Solution" column of Table 1 were mixed to prepare a polymerization initiator solution, which were respectively placed into dropping funnels 1 and 2, and nitrogen gas substitution was carried out. Under a nitrogen atmosphere, while stirring the initial charged monomer solution in the reaction vessel, it was maintained at 55 °C, and the dropwise monomer solution and the polymerization initiator solution were gradually dropped into the reaction vessel over 2 hours so that the ratio of the dropped polymerization initiator to the dropped monomer was constant. After the dropping was completed, the mixture was maintained at 55°C with stirring and heated and aged for 5 hours. Subsequently, an ultrafiltration membrane (manufactured by Nippon Gaishi Co., Ltd., ceramic ultrafiltration membrane, trade name: Cefilt, pore size 10 nm) was used to remove unreacted monomers and polymerization initiator residues from the reaction product, followed by drying to obtain a cationic amphiphilic polymer (hereinafter also referred to as "cationic polymer 2"). The weight-average molecular weight of the obtained cationic polymer 2 was 120,000.

[0102]

Table 1

[0103] Synthesis Example 3 (Synthesis of Cationic Silicone Polymer 1) 12.9 g (0.13 mol) of 2-ethyl-2-oxazoline and 27.7 g of ethyl acetate were mixed, and the mixture was dehydrated at 28°C for 15 hours using 2.0 g of molecular sieve (Zeolam A-4, manufactured by Tosoh Corporation). 0.77 g (0.005 mol) of diethyl sulfate was added to the obtained ethyl acetate solution of dehydrated 2-ethyl-2-oxazoline, and the mixture was heated to reflux at 80°C for 8 hours under a nitrogen atmosphere to obtain a solution of terminal-reactive poly(N-propionylethyleneimine) (number-average molecular weight 2,700). Separately, 100.0 g of side-chain primary aminopropyl-modified polydimethylsiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-8015, weight-average molecular weight 100,000 (catalog value), amine equivalent 20,000) and 203.0 g of ethyl acetate were mixed, and the mixture was dehydrated at 28°C for 15 hours using 15.2 g of molecular sieve. Next, the terminal-reactive poly(N-propionylethyleneimine) solution obtained above was added all at once to the dehydrated side-chain primary aminopropyl-modified polydimethylsiloxane solution, and the mixture was heated under reflux at 80 °C for 10 hours. The resulting reaction mixture was concentrated under reduced pressure to obtain a poly(N-propionylethyleneimine) / dimethylpolysiloxane copolymer (hereinafter also referred to as "cationic silicone polymer 1") as a white rubbery solid (108 g). The weight-average molecular weight of cationic silicone polymer 1 was 115,000 (calculated value), and the mass ratio [content of organopolysiloxane segment (x) / [total content of organopolysiloxane segment (x) and poly(N-acylalkyleneimine) segment (y)]] was 0.87.

[0104] Synthesis Example 4 (Synthesis of cationic silicone polymer 2) 53.3 g (0.54 mol) of 2-ethyl-2-oxazoline and 127.5 g of ethyl acetate were mixed, and the mixture was dehydrated with 9.0 g of molecular sieve (Zeolam A-4, manufactured by Tosoh Corporation) for 15 hours. 9.48 g (0.061 mol) of diethyl sulfate was added to the resulting ethyl acetate solution of dehydrated 2-ethyl-2-oxazoline, and the mixture was heated under reflux at 80 °C for 8 hours in a nitrogen atmosphere to obtain a terminal-reactive poly(N-propionylethyleneimine) (number-average molecular weight 1,300) solution. Separately, 153.7 g of side-chain primary aminopropyl-modified polydimethylsiloxane (trade name: KF-8003, manufactured by Shin-Etsu Chemical Co., Ltd., weight-average molecular weight 40,000 (catalog value), amine equivalent 2,000) and 312.1 g of ethyl acetate were mixed, and the mixture was dehydrated with 23.3 g of molecular sieve at 28 °C for 15 hours. Next, the terminal-reactive poly(N-propionylethyleneimine) solution obtained above was added all at once to a dehydrated side-chain primary aminopropyl-modified polydimethylsiloxane solution, and the mixture was heated under reflux at 80 °C for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain a poly(N-propionylethyleneimine) / dimethylpolysiloxane copolymer (hereinafter also referred to as "cationic silicone polymer 2") as a pale yellow rubbery solid (200 g). The weight-average molecular weight of the cationic silicone polymer 2 was 56,000 (calculated value), and the mass ratio [content of organopolysiloxane segment (x) / [total content of organopolysiloxane segment (x) and poly(N-acylalkyleneimine) segment (y)]] was 0.71.

[0105] Synthesis Example 5 (Synthesis of cationic silicone polymer 3) 73.7 g (0.74 mol) of 2-ethyl-2-oxazoline and 156.0 g of ethyl acetate were mixed, and the resulting mixture was dehydrated with 12.0 g of molecular sieve (Zeolam A-4, manufactured by Tosoh Corporation) at 28 °C for 15 hours. 2.16 g (0.014 mol) of diethyl sulfate was added to the obtained dehydrated 2-ethyl-2-oxazoline ethyl acetate solution, and the mixture was heated under reflux at 80 °C for 8 hours in a nitrogen atmosphere to obtain a terminal-reactive poly(N-propionylethyleneimine) (number-average molecular weight: 6,000) solution. Separately, 70.0 g of side-chain primary aminopropyl-modified polydimethylsiloxane (KF-864, manufactured by Shin-Etsu Silicone Co., Ltd., weight-average molecular weight 50,000 (catalog value), amine equivalent 3,800) and 140.0 g of ethyl acetate were mixed, and the mixture was dehydrated with 15.0 g of molecular sieve at 28 °C for 15 hours. Next, the terminal-reactive poly(N-propionylethyleneimine) solution obtained above was added all at once to the dehydrated side-chain primary aminopropyl-modified polydimethylsiloxane solution described above, and the mixture was heated under reflux at 80°C for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain a poly(N-propionylethyleneimine) / dimethylpolysiloxane copolymer (hereinafter also referred to as "cationic silicone polymer 3") as a white rubbery solid (135 g). The weight-average molecular weight of the cationic silicone polymer 3 was 100,000 (calculated value), and the mass ratio [content of organopolysiloxane segment (x) / (total content of organopolysiloxane segment (x) and poly(N-acylalkyleneimine) segment (y))] was 0.50.

[0106] Production Example 1-1 (Production of Colorant Dispersion 1) Into a glass jacket that can be sealed and temperature-controlled, 250 g of an ethanol solution of an anionic acrylic polymer "Plussize L-9909U" (manufactured by Gohsei Chemical Industry Co., Ltd., acid value: 50 mgKOH / g, 100% neutralized, neutralizing agent: 2-amino-2-methyl-1-propanol, ethanol solution with a solid content concentration of 40% by mass) as a dispersible polymer D (anionic polymer CI) was charged. While stirring at 1,400 rpm under the condition of a jacket temperature of 15°C using a high-speed disperser "T.K. Robomix" (manufactured by Primix Corporation) (agitation part: Homodisper 2.5 type (blade diameter 40 mm)), 300 g of Red No. 226 K (manufactured by Kisuika Kasei Co., Ltd., red dye (C.I. Vat Red 1)) as a colorant was added, and further stirred at 2,000 rpm for 1 hour under the condition of a jacket temperature of 15°C to make the colorant conform to the solution of the anionic acrylic polymer. Next, while maintaining the jacket temperature at 15°C, the rotation speed was changed to 8,000 rpm, and 1450 g of primary ethanol was added and stirred for 3 hours to obtain a colorant mixture 1 (solid content concentration: 20% by mass). The obtained colorant mixture 1 was subjected to a 10-pass dispersion treatment at a pressure of 150 MPa using a microfluidizer (manufactured by Microfluidics, model: M-140K) to obtain a colorant dispersion 1 with a solid content concentration of 20% by mass. In addition, the amount of the anionic acrylic polymer used as the dispersible polymer D (anionic polymer CI) dissolved in each 100 g of the solvent B used in the following Examples and Comparative Examples was less than 5 g, and the amount dissolved in each 100 g of the solvent A was 5 g or more.

[0107] Production Example 1-2 (Production of Colorant Dispersion 2) In a glass jacket capable of being sealed and temperature-controlled, 100 g of nonionic polyvinyl butyral “Esrec BM-1” (powder with 100% active ingredient, manufactured by Sekisui Chemical Co., Ltd.) as the dispersible polymer D (nonionic polymer) was dissolved in 900 g of primary ethanol to obtain an ethanol solution of nonionic polyvinyl butyral with a solid content concentration of 10% by mass. Next, in Production Example 1-1, a solution of nonionic polyvinyl butyral was used instead of the ethanol solution of the anionic acrylic polymer, and Colorant Dispersion 2 was obtained in the same manner except that the blending composition of the colorant mixture described in Table 2 was changed. In addition, the amount of the nonionic polyvinyl butyral used as the dispersible polymer D (nonionic polymer) dissolved in each 100 g of the solvent B used in the following Examples and Comparative Examples was less than 5 g, and the amount dissolved in each 100 g of the solvent A was 5 g or more.

[0108]

Table 2

[0109] Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-7 (Production of Cosmetic Composition) 1.5 parts of Yukafoamer SM-dry as the polymer C (betaine polymer CIII) was dissolved in 58.5 parts of the solvent A shown in Table 3. After confirming that it was transparent and there were no floating substances and precipitates, 10 parts of the solvent B shown in Table 3 was added, then 30 parts of Colorant Dispersion 1 was added, and the mixture was stirred and homogenized. The obtained mixed solution was filtered to obtain Cosmetic Compositions X-1 to X-5 and XC-1 to XC-7, respectively. The viscosities of the obtained cosmetic compositions at 20°C are shown in Table 3. The membrane filter used for filtering the above-mentioned mixed solution was a cellulose acetate syringe filter with a pore size of 1.20 μm (manufactured by Sartorius) for the production of cosmetic compositions X-1 to X-5 and XC-1 to XC-2, XC-7 from the perspective of the solvent resistance of the filter itself, and a hydrophilic PTFE syringe filter with a pore size of 0.45 μm (manufactured by Advantec) for the production of cosmetic compositions XC-3 to XC-6. The amount of Polymer C (Yukafoamer SM-dry) dissolved in 100 g of Solvent A (absolute ethanol) used in Example 1-1 was 50 g, and the amount dissolved in 100 g of Solvent B (Pearl Ream 3) was 0.3 g. Also, the amount of Polymer C (Yukafoamer SM-dry) dissolved in 100 g of each Solvent B used in Examples 1-2 to 1-5 was less than 5 g, and the amount dissolved in 100 g of each Solvent A was 5 g or more.

[0110] (Cosmetic method (manufacture of cosmetic coating film)) After washing the inside of the ink cartridge "TK403 Black-CS Cartridge" (manufactured by Kishu Giken Kogyo Co., Ltd.) with ion-exchanged water and ethanol, each cosmetic composition obtained in the examples and comparative examples was filled, and it was mounted on a handy inkjet printer (manufactured by Kishu Giken Kogyo Co., Ltd., trade name: KGKJET HQ1000H) modified so that printing could be performed at a printing condition of 600 dpi. Next, in an environmental chamber where the temperature and humidity were controlled at 25°C and 50% humidity, a black PET film "Lumirror S10" (manufactured by Toray Industries, Inc.) was fixed as an evaluation substrate on a horizontal table, and using the handy inkjet printer, the cosmetic composition was printed solidly on the evaluation substrate from the vertical upper surface direction. The printing was performed using a solid image (printing density p: 360,000 (dots per square inch)) with a resolution of 600 dpi vertically and 600 dpi horizontally, and a size of 12.7 mm in length and 50.8 mm in width. Immediately after printing, ultrasonic nebulizer "COMFORT OASIS" (manufactured by Shin-Ei Kogyo Co., Ltd., model: KU-200, average droplet diameter: 1 - 5 μm) was used to spray fine droplets of ion-exchanged water as liquid E onto the surface of the coating film, imitating chasing the inkjet head of a handy inkjet printer. The power of the ultrasonic nebulizer was turned off 1 second after the completion of the solid image printing to stop the droplet spraying. Subsequently, it was left in an environmental chamber with controlled temperature and humidity of 25 °C and 50% humidity for 30 minutes to obtain printed materials on which cosmetic coating films 1-1 to 1-5 and 1-C1 to 1-C7 formed from each cosmetic composition were formed.

[0111] (Evaluation of hiding power and color development) Using the printed materials obtained in the examples and comparative examples, the magenta image density (hereinafter also referred to as "magenta density") and the black image density (hereinafter also referred to as "black density") were measured under the following measuring devices and measuring conditions. The results are shown in Table 3. Measuring device: Spectrophotometer / densitometer "SpectroEye" (manufactured by X-Rite Inc.) Measuring conditions: Light source D65, observation field of view 2°, density standard DIN, white base "Abs", built-in filter "No" When the black PET film used as the evaluation substrate was measured, the measured values of both the black density and the magenta density were 1.90. For the evaluation of hiding power and color development, from the perspective of color vividness, it is desirable that the black density is low and the magenta density is high. If the hiding power of the cosmetic coating film is insufficient, the black density will increase, making it difficult for the magenta color development to appear. From this perspective, the density difference between the magenta density and the black density (magenta density - black density) is preferably 0.8 or more, more preferably 0.9 or more, and still more preferably 1.0 or more. In addition, in the examples and comparative examples, a black PET film was used for the evaluation of hiding power and color development as a substitute for skin, hair, and nails. It was confirmed that the effects can be evaluated on the same scale even when applied to skin, hair, and nails.

[0112]

Table 3

[0113] From Table 3, it can be seen that in Examples 1-1 to 1-5, the black density is low, the hiding power is excellent, the magenta density is high, and the density difference between the magenta density and the black density is 0.8 or more, so it is excellent in color development. On the other hand, in Comparative Examples 1-1 to 1-7, the black density is high, the hiding power is poor, and the density difference between the magenta density and the black density is small, so it can be seen that the color development is poor.

[0114] Examples 2-1 to 2-30 (Manufacture of Cosmetic Composition) Polymer C (anionic polymer CI, cationic polymer CII-1, cationic silicone polymer CII-2, betaine polymer CIII, or nonionic polymer) shown in Tables 4 and 5 was dissolved in absolute ethanol (boiling point 78 °C, Ra24) as solvent A, and after confirming that it was transparent and had no floating matter and precipitate, Pearl Ream 3 (boiling point 179 °C, Ra45) was added as solvent B, then a colorant dispersion was added, stirred to homogenize, and the resulting mixture was filtered using a cellulose acetate syringe filter with a pore size of 1.20 μm (manufactured by Sartorius) to obtain cosmetic compositions Y-1 to Y-30. The dissolution amount of Polymer C used in Examples 2-1 to 2-30 in 100 g of solvent B (Pearl Ream 3) was less than 5 g, and the dissolution amount in 100 g of solvent A (absolute ethanol) was 5 g or more.

[0115] (Cosmetic Method (Manufacture of Cosmetic Coating Film) and Evaluation of Hiding Power and Color Development) After obtaining a printed matter having cosmetic coating films 2-1 to 2-30 by the same method as in Example 1-1, the image density was measured and the hiding power and color development were evaluated. The results are shown in Tables 4 and 5.

[0116] (Evaluation of Water Resistance) The obtained printed matter was placed on a horizontal surface, 0.1 g of ion-exchanged water was dropped onto the decorative coating film with a dropper, and it was left for 1 minute in an environmental chamber where the temperature and humidity were controlled at 25°C and 50% humidity. Next, the surface state of the decorative coating film was observed while rubbing 5 times with a cotton swab with a diameter of 5 mm moistened with ion-exchanged water at the location where the ion-exchanged water was dropped. After that, it was dried with a warm air dryer until the water droplets at the dropped location dried and became invisible. Then, the surface state of the decorative coating film after rubbing was further observed, and evaluation was performed according to the following 5-level evaluation criteria. The results are shown in Tables 4 and 5. 〔Evaluation Criteria〕 5: During rubbing in a state wet with water, there is no change in the surface state of the decorative coating film, and there is no color fading. 4: During rubbing in a state wet with water, there is a slight color change in the decorative coating film, but after drying, it returns to the original surface state and there is no color fading, and there is no practical problem. 3: During rubbing in a state wet with water, there is a slight color change and streaking in the decorative coating film, but after drying, it returns to the original surface state and there is no color fading, and there is no practical problem. 2: During rubbing in a state wet with water, obvious color fading is seen in the decorative coating film, and color fading is clearly recognized even after drying. 1: During rubbing in a state wet with water, the decorative coating film is torn, and even after drying, it is very different from the original surface state.

[0117]

Table 4

[0118]

Table 5

[0119] From Tables 4 and 5, it can be seen that Examples 2-1 to 2-30 have a low black density, excellent hiding properties, a high magenta density, and a density difference between the magenta density and the black density of 0.8 or more, so they have excellent color development and also excellent water resistance. In addition, in Examples 2-1 to 2-6, 2-12 to 2-13, 2-17, and 2-29 to 2-30, an anionic polymer was used as the dispersing polymer D for the colorant, and any one of an anionic polymer CI, a cationic polymer CII, a betaine polymer CIII, and a nonionic polymer was used alone as the polymer C. From these results, Example 2-1 using the betaine polymer CIII showed the lowest black density, and then Examples 2-2 to 2-4 using the anionic polymer CI showed relatively low black densities. It can be seen that these examples are more excellent in hiding power and color development. Also, it can be seen that Examples 2-5 to 2-6 using the cationic polymer CII-1 are more excellent in water resistance. Further, from Tables 4 and 5, in Examples 2-7 to 2-11, 2-14 to 2-16, and 2-18 to 2-27, when an anionic polymer or a nonionic polymer was used as the dispersing polymer D for the colorant and two types were used in combination as the polymer C, Examples 2-7 to 2-9 using a combination of the anionic polymer CI and the betaine polymer CIII showed the lowest black density, and then Examples 2-10 to 2-11 using a combination of the cationic polymer CII-1 and the betaine polymer CIII showed relatively low black densities. It can be seen that these examples are more excellent in hiding power and color development. It can be seen that Examples 2-14 to 2-16 and 2-18 to 2-22 using a combination of the anionic polymer CI and the cationic polymer CII-1 or the cationic silicone polymer CII-2 are more excellent in water resistance. Furthermore, from Table 5, Example 2-28 used a combination of three types, namely, the anionic polymer CI, the cationic silicone polymer CII-2, and the betaine polymer CIII, as the polymer C. It can be seen that it shows a relatively low black density, is excellent in hiding power and color development, and is excellent in water resistance.

[0120] Examples 3-1 to 3-11 (Manufacture of Cosmetic Composition) Using the compositions shown in Table 6, as polymer C (betaine polymer CIII and cationic silicone polymer CII-2), Yukafoamer SM-dry or Yukafoamer SM-dry and cationic silicone polymer 3 were dissolved in absolute ethanol or isopropyl alcohol as solvent A. After confirming that the solution was transparent and free of suspended matter and precipitate, each solvent B and water shown in Table 6 were added, stirred for homogenization, and filtered using a cellulose acetate syringe filter with a pore size of 0.20 μm (manufactured by Advantec) to obtain cosmetic compositions Z-1 to Z-11. In Examples 3-8 to 3-9, the dissolution amount of the polymer C (Yukafoamer SM-dry and cationic silicone polymer 3) used in each 100 g of solvent B shown in Table 6 was less than 5 g, and the dissolution amount in 100 g of solvent A (absolute ethanol) was 5 g or more.

[0121] (Cosmetic method (manufacture of cosmetic coating film) and evaluation of hiding power and color development) After obtaining printed matter having cosmetic coating films 3-1 to 3-11 by the same method as in Example 1-1, the image density was measured and the hiding power and color development were evaluated. The results are shown in Table 6. In the evaluation of hiding power and color development, after stopping the spraying of minute droplets of ion-exchanged water, the magenta density was measured every 5 minutes, the time required for the value of the magenta density to become stable was measured, and the color development rate was evaluated. When measuring the magenta density, when the difference from the magenta density measured 5 minutes before became 0.1 or less, it was considered that the magenta density was stable, the time was recorded, and the magenta density at that time was evaluated. The results are shown in Table 6. The shorter the time until the value of the magenta density becomes stable, the more preferable it is. If it is within 30 minutes, there is no practical problem as the color development rate.

[0122]

Table 6

[0123] From Table 6, in Examples 3-1 to 3-11, since the time for color development is within 30 minutes, the black density is low, the concealing property is excellent, the magenta density is high, and the density difference between the magenta density and the black density is 0.8 or more, it can be seen that the color development property is excellent.

Industrial Applicability

[0124] The cosmetic composition of the present invention can obtain a good cosmetic coating film that is excellent in concealing property and color development property and can be applied to the skin, hair, or nails without using an inorganic pigment.

Claims

1. A cosmetic composition comprising a solvent A, a solvent B, a polymer C, and a colorant, The solvent A is at least one selected from ethanol, n-propanol, and isopropanol; The boiling point of the solvent B is 150° C. or higher, and the distance Ra of the Hansen solubility parameter of the solvent B in water represented by the following formula (1) is 40 or higher, the solvent B is compatible with the solvent A, and the polymer C is soluble in the solvent A but insoluble in the solvent B; The content of solvent A in the cosmetic composition is 30% by mass or more and 90% by mass or less, A cosmetic composition, wherein the content of solvent B in the cosmetic composition is 15% by mass or more and 25% by mass or less. Ra=(4×ΔD ２ +ΔP ２ +ΔH ２ ) ０．５ (1) ΔD: Difference in dispersion components in Hansen solubility parameters between solvent B and water ΔP: Difference in polar components in Hansen solubility parameters between solvent B and water ΔH: Difference in hydrogen bond components in the Hansen solubility parameters between solvent B and water

2. The cosmetic composition according to claim 1 , wherein the content of solvent A in the cosmetic composition is 40% by mass or more and 80% by mass or less.

3. The cosmetic composition according to claim 1 or 2, wherein the colorant is dispersed in a dispersing polymer D.

4. 4. The cosmetic composition according to claim 3, wherein the dispersible polymer D is soluble in solvent A and insoluble in solvent B.

5. The cosmetic composition according to any one of claims 1 to 4, wherein polymer C contains a polymer containing at least one monomer selected from the group consisting of a monomer having an acidic group, a monomer having a basic group, and a betaine monomer as a structural unit.

6. The cosmetic composition according to any one of claims 1 to 5, wherein solvent B is at least one selected from the group consisting of volatile hydrocarbon oils and volatile silicone oils.

7. The cosmetic composition according to any one of claims 1 to 6, wherein the water content is 5% by mass or less.

8. The cosmetic composition according to any one of claims 1 to 7, wherein the content of polymer C is 0.5% by mass or more and 15% by mass or less.

9. The cosmetic composition according to any one of claims 1 to 8, wherein the content of the colorant is from 1% by mass to 15% by mass.

10. The cosmetic composition according to any one of claims 1 to 9, which is a cosmetic composition for hair.

11. A cosmetic coating film formed from the cosmetic composition according to any one of claims 1 to 10.

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