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 method of applying cosmetic products using the cosmetic composition, and a cosmetic coating film formed from the cosmetic composition. [Background technology]

[0002] Traditionally, makeup cosmetics have incorporated highly opaque inorganic pigments such as titanium dioxide, zinc oxide, and iron oxide to cover blemishes, dullness, and pores on the skin, and to improve the brightness of the applied finish. For example, Patent Document 1 describes a cosmetic composition containing titanium dioxide with an average particle size of 0.2 μm or more and resin fine particles with an average particle size of 0.01 to 100 μm, with the aim of providing a cosmetic composition that provides high whiteness and opacity. Furthermore, Patent Document 2 describes a cosmetic composition that, for the purpose of providing long-lasting concealment of skin imperfections, contains a plate-type filler having a predetermined refractive index and particle size, a silicone elastomer, and a filler having an oil absorption capacity of 1 ml / g or more in a physiological medium. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2016-121137 [Patent Document 2] Special Publication No. 2015-520120 [Overview of the project] [Problems that the invention aims to solve]

[0004] In this context, base makeup cosmetics such as foundations and concealers, which are primarily intended for adjusting skin tone, are required to have high color development properties that can conceal blemishes, birthmarks, and pores, and color the skin with the original color of the colorants contained in the cosmetics. Furthermore, point makeup cosmetics such as eyeshadow, blush, and nail polish, which are applied to parts of the face or nails to add color and accentuate specific areas, are used to create shadows and add dimension, or to add color and accentuate specific areas. Therefore, they are required to have high color development that can conceal the natural color of the skin or nails while simultaneously coloring them with the original color of the colorants contained in the cosmetics. Furthermore, temporary hair dyes such as hair mascaras are popular because they cause less damage to the hair and allow people to easily enjoy hair coloring. They are especially used to enhance fashionability by adding vibrant colors to the hair. However, since temporary hair dyes color the hair by forming a colored film on the hair surface, they are required to have high color development that can conceal the hair's natural color while simultaneously coloring it with the original color of the colorants contained in the temporary hair dye. The technologies described in Patent Documents 1 and 2 achieve opacity by incorporating inorganic pigments with high refractive indices. However, in recent years, the use of zinc oxide and titanium dioxide has been increasingly restricted due to various legal regulations. Therefore, there is a need for the development of cosmetic compositions that can form cosmetic coatings with excellent opacity and color development without using inorganic pigments. Furthermore, since some temporary hair dyes are used to color hair in a mesh-like pattern, there is a desire for a simpler cosmetic method that allows for coloring only specific sections of hair. The present invention aims to provide a cosmetic composition that can form a cosmetic coating film with excellent opacity and color development 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 problem]

[0005] The inventor has found that a cosmetic composition containing two types of solvents, a polymer, and a colorant, where the first solvent among 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 in specific relationships, 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, where 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].

Effects 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 development 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 [[ID=--]] ΔH: Difference in the hydrogen bond component in the Hansen solubility parameter between the solvent B and water

[0008] In the present invention, "compatible" refers to 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, and do not separate into multiple phases, or when they are mixed and stirred, and no phase separation occurs and no cloudiness is generated, 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, which has been dried at 105°C for 2 hours to reach a constant weight, is dissolved in 100g of solvent A at 25°C, the amount dissolved is 5g or more. From the viewpoint of improving opacity and color development, the amount of polymer C dissolved in solvent A is preferably 10g or more. In the present invention, "polymer C is insoluble in solvent B" means that when polymer C is dried at 105°C for 2 hours to reach a constant weight and then dissolved in 100g of solvent B at 25°C until saturated, the amount of polymer C that dissolves is less than 5g. From the viewpoint of improving opacity and color development, the amount of polymer C that dissolves in solvent B is preferably less than 2g. The determination of whether something is "miscible" or "soluble" as described above should be made at 25°C.

[0009] In this invention, the "Hansen solubility parameter" is expressed by dividing the solubility parameter (SP value) introduced by Hildebrand into three components (dispersion component D, polar component P, and hydrogen bonding component H). The D, P, and H values ​​for each solvent are described in detail in "HANSEN SOLBILITY PARAMETERS" A User's Handbook Second Edition. In addition, HSP values ​​for many solvents and resins are also described in books such as the Industrial Solvents Handbook by Wesley L. Archer. The D, P, and H values ​​for each solvent can also be determined using the HSPiP software from Charles Hansen Consulting, Inc. (Horsholm, Denmark, hansen-solubility.com). In this invention, for solvents registered in the HSPiP version 4.1.03 database (see various HSP literature), the values ​​are used, and for solvents not in the database, the values ​​estimated by HSPiP are used. Furthermore, in this invention, the unit of the "Hansen solubility parameter" is "(MPa)0.5".

[0010] According to the present invention, a cosmetic coating film with excellent opacity and color development can be formed without using inorganic pigments. The reason for this is not entirely clear, but it is thought to be as follows. The cosmetic composition of the present invention contains one or more solvents A selected from ethanol, n-propanol, and isopropanol; solvent B having a boiling point of 150°C or higher and a Hansen solubility parameter distance Ra with respect to water represented by formula (1) of 40 or higher; polymer C soluble in solvent A and insoluble in solvent B; and a coloring agent. When such a cosmetic composition is applied to the skin, hair, or nails, the volatilization of solvent A within the coating film removes heat of vaporization, causing moisture in the atmosphere to condense on the surface of the coating film and adhere as tiny water droplets. In this invention, solvent A is one or more alcohols selected from specific alcohols, and the distance Ra of the solubility parameter of solvent B in water is above a specific value. Therefore, due to the adhesion of these tiny water droplets to the surface of the coating film, solvent B, which was miscible with solvent A, undergoes phase separation. Since polymer C is insoluble in solvent B, polymer C coats the phase-separated solvent B, suppressing the coalescence of solvent B. This is thought to form primary particles containing a colorant having a core-shell structure with solvent B as the core and polymer C as the shell. Furthermore, with the volatilization of solvent A and the surface alignment of the formed primary particles, regularly separated cellular convection structures, so-called Benard cells, are generated within the coating film. Benard convection within each cell causes the primary particles to accumulate, forming secondary particles. As a result, it is presumed that light is scattered by the particle structure formed within the cosmetic coating, resulting in high opacity and color development.

[0011] <Solvent A> The cosmetic composition of the present invention contains solvent A. Solvent A is one or more selected from ethanol, n-propanol, and isopropanol. Furthermore, in the cosmetic composition, solvent A is miscible with solvent B and dissolves polymer C. As a result, when the cosmetic composition is applied to the skin, hair, or nails, the evaporation of solvent A removes heat of vaporization, causing tiny water droplets to adhere to the surface of the applied film and inducing phase separation between solvent A and solvent B. Solvent A may be used alone or in combination of two or more types. From the viewpoint of improving opacity and color development, solvent A is preferably at least one selected from ethanol and isopropanol, and 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 in water, represented by formula (1), is 40 or higher. Furthermore, in the cosmetic composition, solvent B is miscible with solvent A but does not dissolve polymer C. As a result, when tiny water droplets adhere to the surface of the coating film due to the volatilization of solvent A, phase separation occurs between solvent A and solvent B, forming primary particles in which solvent B is coated with polymer C.

[0013] The boiling point of solvent B is 150°C or higher, preferably 155°C or higher, more preferably 160°C or higher, even more preferably 165°C or higher, and even more preferably 170°C or higher, and from the viewpoint of ease of handling, preferably 300°C or lower, more preferably 270°C or lower, even more preferably 250°C or lower, even more preferably 230°C or lower, even more preferably 210°C or lower, and even more preferably 180°C or lower. The distance Ra of the Hansen solubility parameter for solvent B in water is 40 or greater, preferably 42 or greater, more preferably 44 or greater, and preferably 60 or less, more preferably 57 or less, even more preferably 55 or less, and even more preferably 50 or less, from the viewpoint of forming primary particles and improving opacity and color development. Solvent B may be used alone or in combination of two or more types. When two or more solvents are used in combination as solvent B, the boiling point and the distance Ra of the Hansen solubility parameter in water can be determined as a weighted average value weighted by the content (mass%) of each solvent.

[0014] From the viewpoint of improving opacity and color development, solvent B preferably contains at least one selected from hydrocarbon oils and silicone oils. Examples of hydrocarbon oils include α-olefin oligomers; liquid paraffins; liquid isoparaffins such as isododecane, isohexadecane, and hydrogenated polyisobutene (light liquid isoparaffins, heavy liquid isoparaffins); liquid ozokerite; squalane; pristane; and squalene. In particular, the hydrocarbon oil is preferably one or more selected from α-olefin oligomers, liquid paraffins, liquid isoparaffins, liquid ozokerite, squalane, pristane, and squalene, more preferably liquid isoparaffins, even more preferably one or more selected from isododecane, isohexadecane, and hydrogenated polyisobutene, and even more preferably one or more 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, and even more preferably 300 or less. The viscosity of hydrogenated polyisobutene at 20°C is preferably 0.5 mPa·s or more, more preferably 0.7 mPa·s or more, even more preferably 1 mPa·s or more, and preferably 30 mPa·s or less, more preferably 25 mPa·s or less, even 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, and even more preferably 2 mPa·s or less. The viscosity of hydrogenated polyisobutene at 20°C can be measured using an E-type viscometer by the method described in the examples.

[0015] Examples of silicone oils include linear silicone oils such as trisiloxane; branched silicone oils such as methyl trimethicone; and cyclic silicone oils such as methyl cyclopolysiloxane. In particular, one or more silicone oils selected from linear silicone oils, branched silicone oils, and cyclic silicone oils are preferred, one or more selected from trisiloxane, methyl trimethicone, and methyl cyclopolysiloxane are more preferred, and one or more selected from trisiloxane and methyl trimethicone are even more preferred. 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 even more preferably 300 or less. The viscosity of the silicone oil at 25°C is preferably 0.5 mPa·s or more, preferably 20 mPa·s or less, more preferably 10 mPa·s or less, even 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 using an E-type viscometer by the method described in the examples.

[0016] Solvent B is preferably volatile, and more preferably one or more selected from volatile hydrocarbon oils and volatile silicone oils, from the viewpoint of improving the film-forming properties of the cosmetic coating film and improving its opacity and color development. In this invention, "volatility" means that the amount of evaporation measured at 25°C for 6 hours is 20% or more, as measured by the following method. Measurement method: Place a 90mm diameter filter paper in a 120mm diameter glass petri dish, place 1g of sample on the filter paper, and store in a 65% RH room (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 rate (%) = [(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. However, because solvent B is volatile, the solvent B contained within the core evaporates, forming hollow primary particles, which improves opacity, color development, and film formation of cosmetic coatings. Furthermore, when forming hollow primary particles, minute pores (openings) may be formed in the shell portion. In this case, for example, when applying the cosmetic composition of the present invention to the skin, even if the skin furrows and wrinkles are deformed due to changes in facial expression, the hollow primary particles incorporated into the skin furrows and wrinkles can reversibly return to their original state by deforming or pushing out air, following the volume change of the skin furrows and wrinkles. Therefore, the extrusion of hollow primary particles onto the skin surface is suppressed, and the state of the cosmetic coating film before deformation of the skin furrows and wrinkles can be well maintained, which is thought to improve the retention of the cosmetic. The hollow primary particles are preferably formed by adjusting the type of solvent B and the drying conditions of the coating film after application to the skin, and by evaporating the solvent B contained in the core portion.

[0018] As for volatile hydrocarbon oils, saturated or unsaturated hydrocarbon oils with 8 to 16 carbon atoms are preferred from the viewpoint of improving opacity, color development, and film formation of cosmetic coatings. Examples of volatile hydrocarbon oils 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 paraffinic 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, even more preferably one or more selected from isododecane and hydrogenated polyisobutene, and even more preferably hydrogenated polyisobutene. Examples of commercially available volatile hydrocarbon oils include "Pearlream 3" and "Pearlream 4" manufactured by NOF Corporation, and Marcazole R manufactured by Maruzen Petrochemical Co., Ltd.

[0019] As for volatile silicone oils, from the viewpoint of improving opacity, color development, and film formation of cosmetic coatings, preferably one or more selected from linear organopolysiloxanes and cyclic organopolysiloxanes are used. Specific examples of linear organopolysiloxanes include octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and 1,1,1,3,5,5,5-heptamethyl-3-[(trimethylsilyl)oxy]-trisiloxane. Examples of cyclic organopolysiloxanes include cyclic siloxanes with 4 to 6 membered rings having an alkyl group with 1 to 5 carbon atoms as a substituent. Specific examples of cyclic organopolysiloxanes include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. Commercially available volatile silicone oils include "KF-96A-1cs" (octamethyltrisiloxane), "KF-96L-1.5cs" (decamethyltetrasiloxane), "KF-96L-2cs" (dodecamethylpentasiloxane), "KF-995" (decamethylcyclopentasiloxane), and "TMF-1.5" (1,1,1,3,5,5,5-heptamethyl-3-[(trimethylsilyl)oxy]-trisiloxane) from Shin-Etsu Chemical Co., Ltd.; and "SH200C Fluid 1cs" (octamethyltrisiloxane), "SH200C Fluid 1.5cs" (decamethyltetrasiloxane), "SH200C Fluid 2cs" (dodecamethylpentasiloxane), and "SH245" from Toray Dow Corning Co., Ltd. Examples include "Fluid" (decamethylcyclopentasiloxane) and "TSF405A" (decamethylcyclopentasiloxane) manufactured by Momentive Performance Materials.

[0020] Solvent B may also contain additives such as humectants, UV absorbers, insect repellents, wrinkle inhibitors, and fragrances, in addition to hydrocarbon oil or silicone oil. 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 viewpoints of improving concealability and color development.

[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; nonionic polymers, and the like.

[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 (-SO3M), and phosphate group (-OPO3M2), or their dissociated ionic forms (-COO - , -SO3 - , -OPO3 2- , -OPO3 - M), and the like. In the above chemical formulas, M represents a hydrogen atom, an alkali metal, ammonium, or an organic ammonium. From the viewpoints of improving concealability and color development, 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 same viewpoint as described above, the monomer having an acidic group is preferably a monomer having a carboxyl group, more preferably at least one selected from (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, and 2-methacryloyloxymethylsuccinate, and even 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 opacity and color development, the anionic polymer CI is preferably a copolymer that further contains constituent units derived from monomers other than monomers having acidic groups. Examples of other monomers include hydrophobic monomers such as (meth)acrylates having hydrocarbon groups derived from aliphatic alcohols and aromatic group-containing monomers; and nonionic monomers. Here, "(meth)acrylate" means one or more selected from acrylates and methacrylates.

[0024] (Meth)acrylates having hydrocarbon groups derived from aliphatic alcohols are preferably those having hydrocarbon groups derived from aliphatic alcohols with 1 to 22 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 8 carbon atoms. Examples of such (meth)acrylates include (meth)acrylates having linear alkyl groups; (meth)acrylates having branched alkyl groups; and (meth)acrylates having alicyclic alkyl groups.

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

[0026] Nonionic monomers in anionic polymers CI include (meth)acrylamide; N-vinyl-2-pyrrolidone; N-alkyl(meth)acrylamides having linear, branched, or cyclic alkyl groups such as N-tert-butylacrylamide, N-tert-octylacrylamide, N-(2-ethylhexyl)acrylamide, Nn-octylacrylamide, N-dodecylacrylamide, Nn-heptylacrylamide, N-hexylacrylamide, and N-cyclohexylmethacrylamide; Examples include droxyalkyl (meth)acrylates; polyalkylene glycol (meth)acrylates (n=2-30, where n represents the average number of moles added of the oxyalkylene group; the same applies hereafter); alkoxy polyalkylene glycol (meth)acrylates (n=1-30); phenoxy(ethylene glycol-propylene glycol copolymer) (n=1-30, where ethylene glycol: n=1-29) (meth)acrylates, and other phenoxy polyalkylene glycol (meth)acrylates. Specific examples of commercially available nonionic monomers include NK ester M-20G, 40G, 90G, and 230G from Shin Nakamura Chemical Industry Co., Ltd.; and Bremmer PE-90, 200, and 350 from NOF Corporation, PME-100, 200, and 400 from NOF Corporation, PP-500, 800, and 1000 from NOF Corporation, AP-150, 400, and 550 from NOF Corporation, 50PEP-300, 50POEP-800B, and 43PAPE-600B. Each of the aforementioned monomers can be used individually 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, even more preferably 20,000 or more, and preferably 1,000,000 or less, more preferably 500,000 or less, and even more preferably 200,000 or less. The weight-average molecular weight of the anionic polymer CI is the molecular weight on a polystyrene basis measured by gel permeation chromatography (GPC).

[0028] Examples of commercially available anionic polymers (CIs) include acrylic acid / alkyl acrylate / (N-alkyl)acrylamide copolymers such as Ultrahold 8, Ultrahold Strong, and Ultrahold Power from BASF Japan Ltd., and Unformer V-42 from National Starch Corporation; carboxyvinyl polymers such as the Carbopol series from Lubrizol Advanced Materials; (meth)acrylic acid / (meth)acrylate / alkyl acrylate copolymers such as Diahold from Mitsubishi Chemical Corporation; ((meth)acrylic acid / diacetone acrylamide) copolymer AMP, ((meth)acrylic acid / alkyl acrylate / diacetone acrylamide) copolymer AMP, and ((meth)acrylic acid / (meth)acrylate / alkyl acrylate / (N-alkyl)alkylacrylamide) copolymer AMP from Go-O Chemical Industry Co., Ltd., such as the Plussize L series; and (meth)acrylic acid / alkyl acrylate / vinylpyrrolidone copolymers such as Rubiflex VBM35 from BASF. In addition, commercially available polymers containing acrylic acid or methacrylic acid-derived monomers with acidic groups, used in cosmetic applications, include the Aniset series manufactured by Osaka Organic Chemical Industry Co., Ltd. Here, "(meth)acrylate alkyl ester" means one or more selected from alkyl acrylates and alkyl methacrylates.

[0029] The anionic polymer CI preferably contains constituent units derived from monomers having acidic groups and constituent units derived from alkyl (meth)acrylates, from the viewpoint of improving opacity and color development, more preferably contains constituent units derived from monomers having acidic groups, constituent units derived from alkyl (meth)acrylates, and constituent units derived from (N-alkyl)(meth)acrylamide, even more preferably is a (meth)acrylic acid / alkyl (meth)acrylate / (N-alkyl)(meth)acrylamide copolymer, and even more preferably is an acrylic acid / alkyl acrylate / (N-alkyl)acrylamide copolymer.

[0030] (cationic polymer) In the present invention, "cationic" in cationic polymers means that when an unneutralized polymer is dispersed or dissolved in pure water, the pH is greater than 7; in the case of polymers having quaternary ammonium groups, etc., when their counterions are dispersed or dissolved in pure water as hydroxide ions, the pH is greater than 7; or, if the polymer is insoluble in pure water and the pH cannot be clearly measured, the zeta potential of the dispersion of the polymer in pure water is positive. From the viewpoint of improving opacity and color development, the cationic polymer preferably has basic groups such as primary to tertiary amino groups, quaternary ammonium groups, and hydrazino groups, and more preferably has quaternary ammonium groups. The basic group includes those neutralized by 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 cationic polymers include natural cationic polymers and synthetic cationic polymers. Natural cationic polymers include polymers obtained by extraction, purification, and other operations from natural products, as well as chemically modified polymers, which have glucose residues in their polymer backbone. Specifically, these include cationized guar gum, cationized tara gum, cationized locust bean gum, cationized cellulose, cationized hydroxyalkyl cellulose, and cationic starch.

[0032] Examples of synthetic cationic polymers include polyethyleneimine, polyallylamine or their acid neutralized products, polyglycol-polyamine condensates, cationic polyvinyl alcohol, cationic polyvinylpyrrolidone, cationic silicone polymers, 2-(dimethylamino)ethyl methacrylate polymers or their acid neutralized products, 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 / polyethylene glycol dimethacrylate copolymers, polydiallyldimethylammonium chloride, Examples include diallyldimethylammonium chloride / acrylamide copolymer, diallyldimethylammonium chloride / sulfur dioxide copolymer, diallyldimethylammonium chloride / hydroxyethylcellulose copolymer, 1-allyl-3-methylimidazolium chloride / vinylpyrrolidone copolymer, alkylamino(meth)acrylate / vinylpyrrolidone copolymer, alkylamino(meth)acrylate / vinylpyrrolidone / vinylcaprolactam copolymer, (3-(meth)acrylamidopropyl)trimethylammonium chloride / vinylpyrrolidone copolymer, and alkylaminoalkylacrylamide / alkylacrylamide / (meth)acrylate / polyethylene glycol (meth)acrylate copolymer. These cationic polymers can be used individually or in combination of two or more.

[0033] Among these, cationic polymers are preferably cationic polymer CII-1 (hereinafter also referred to as "cationic polymer CII-1") and cationic silicone polymer (hereinafter also referred to as "cationic silicone polymer CII-2") which contain constituent units derived from monomers having basic groups, from the viewpoint of improving opacity and color development.

[0034] [Cationic polymer CII-1] The cationic polymer CII-1 contains constituent units derived from monomers having basic groups. Examples of such basic groups include those described above. Examples of monomers having basic groups include alkylamino(meth)acrylates; N,N-dialkylaminoalkyl(meth)acrylates; N-[3-(dimethylamino)propyl](meth)acrylamide; amino group-containing monomers such as diallyldialkylammonium, their acid neutralized products, or quaternized products. These monomers having basic groups can be used individually or in combination of two or more. Acids used for acid neutralization include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, maleic acid, fumaric acid, citric acid, tartaric acid, adipic acid, and lactic acid. Quaternizing agents include alkyl halides such as methyl chloride, ethyl chloride, methyl bromide, and methyl iodide; and alkylating agents such as dialkyl sulfates such as dimethyl sulfate, diethyl sulfate, and di-n-propyl sulfate.

[0035] 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 condensed polymer, more preferably a copolymer of a monomer having a basic group and another monomer other than the monomer having a basic group, even more preferably a copolymer containing a structural unit derived from a monomer having a basic group, a structural unit derived from a hydrophobic monomer as listed in the aforementioned anionic polymer CI, and a structural unit derived from a nonionic monomer as listed in the aforementioned anionic polymer CI, and even more preferably a copolymer containing a structural unit derived from an amino group-containing monomer, a structural unit derived from an alkyl (meth)acrylate ester, a structural unit derived from an N-alkyl (meth)acrylamide, and an alkoxy polyethylene glycol mono(meth)acrylate ester. A copolymer comprising a constituent unit derived from acrylate, more preferably a constituent unit derived from an amino group-containing monomer, a constituent unit derived from an alkyl (meth)acrylate hydrocarbon group of an aliphatic alcohol having 1 to 22 carbon atoms, a constituent unit derived from an N-alkyl (meth)acrylamide having a linear, branched, or cyclic alkyl group, and a constituent unit derived from alkoxy polyethylene glycol mono(meth)acrylate, more preferably a copolymer comprising a constituent unit derived from an amino group-containing monomer, a constituent unit derived from an alkyl (meth)acrylate hydrocarbon group of an aliphatic alcohol having 1 to 8 carbon atoms, a constituent unit derived from an N-alkyl (meth)acrylamide having a branched alkyl group of 4 to 8 carbon atoms, and a constituent unit derived from methoxy polyethylene glycol mono(meth)acrylate. Cationic polymer CII-1 is produced by copolymerizing raw material monomers containing these monomers using known polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Among these polymerization methods, solution polymerization is preferred.

[0036] In the production of the cationic polymer CII-1, the content of monomers having basic groups, hydrophobic monomers, and nonionic monomers in the raw material monomers (content as unneutralized amounts; the same applies hereinafter), that is, the content of constituent units derived from each component in the cationic polymer CII-1, is as follows, from the viewpoint of improving opacity and color development. The content of monomers having basic groups is preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 7% by mass or more, and preferably 35% by mass or less, more preferably 30% by mass or less, even 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 hydrophobic monomer content is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and preferably 35% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less. The nonionic monomer content is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, and even more preferably 55% by mass or more, and preferably 85% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less.

[0037] The weight-average molecular weight of the cationic polymer CII-1 is preferably 7,000 or more, more preferably 10,000 or more, even more preferably 50,000 or more, and even more preferably 100,000 or more, and preferably 500,000 or less, more preferably 300,000 or less, even more preferably 200,000 or less, and even more preferably 150,000 or less, from the viewpoint of improving opacity and color development. 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 cationic silicone polymer CII-2 is preferably a poly(N-acylalkyleneimine) / organopolysiloxane copolymer comprising an organopolysiloxane segment (x) (hereinafter also simply referred to as "segment (x)") and a poly(N-acylalkyleneimine) segment (y) (hereinafter also simply referred to as "segment (y)") consisting of an alkylene group containing a cationic nitrogen atom bonded to at least one silicon atom of segment (x) and a repeating unit of an N-acylalkyleneimine represented by the following general formula (1-1).

[0039] [ka] (In the formula, R 1 (where a represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an aryl group having 6 to 22 carbon atoms, or an arylalkyl group or alkylaryl group having 7 to 22 carbon atoms, and a is 2 or 3.)

[0040] In general formula (1-1), R 1 The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and even more preferably an ethyl group. R 1 Examples of aryl groups include phenyl groups and naphthyl groups. R 1 Examples of arylalkyl groups include phenylalkyl groups and naphthylalkyl groups, which have 1 to 20 carbon atoms in the alkyl group, while examples of alkylaryl groups include alkylphenyl groups and alkylnaphthyl groups, which have 1 to 20 carbon atoms in the alkyl group. In general formula (1-1), a is preferably 2. There are no particular restrictions on the degree of polymerization of the repeating unit represented by general formula (1-1) in segment (y), but for example, it is preferably between 1 and 500, and more preferably between 6 and 100.

[0041] Examples of organopolysiloxanes that form segment (x) include compounds represented by the following general formula (1-2). [ka] (In the formula, R 2 R represents an alkyl group having 1 to 22 carbon atoms, a phenyl group, or an alkyl group containing a nitrogen atom, and multiple R 2 The elements may be the same or different, but at least one of them is an alkyl group containing a cationic nitrogen atom. b is between 100 and 5,000.

[0042] In general formula (1-2), R 2 Among the alkyl groups having 1 to 22 carbon atoms as shown, alkyl groups having 1 to 12 carbon atoms are preferred, alkyl groups having 1 to 3 carbon atoms are more preferred, and methyl groups are even more preferred. Also, R 2 Examples of alkyl groups containing nitrogen atoms, as shown, include alkyl groups having 2 to 20 carbon atoms and preferably containing 1 to 3 nitrogen atoms. The alkyl group containing nitrogen atoms may be at least one silicon atom at the terminal or side chain of the organopolysiloxane, and the number of alkyl groups containing nitrogen atoms in the organopolysiloxane is preferably 1 to 300, and more preferably 1 to 100.

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

[0044] In the bond between segment (x) and segment (y), an alkylene group containing intervening nitrogen atoms is an alkylene group having 2 to 20 carbon atoms and preferably containing 1 to 3 nitrogen atoms. Specifically, examples of nitrogen atoms present between carbon atoms or at the ends of an alkylene chain include (i) secondary or tertiary amines, (ii) ammonium salts obtained by adding hydrogen ions to secondary or tertiary amines, and (iii) quaternary ammonium salts. As a poly(N-acylalkyleneimine) / organopolysiloxane copolymer, it is preferable that segment (y) is bonded to at least one silicon atom at the terminal or side chain of segment (x) via an alkylene group containing a cationic nitrogen atom. 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 higher, more preferably 0.3 or higher, even more preferably 0.4 or higher, even more preferably 0.5 or higher, and preferably 0.99 or lower, more preferably 0.95 or lower, and even more preferably 0.9 or lower. In this specification, the mass ratio [content of segment (x) / [total content of segment (x) and segment (y)]] is the ratio of the mass of segment (x) (Mx) to the total amount of the mass of segment (x) (Mx) and the mass of segment (y) (My) 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 by dissolving a poly(N-acylalkyleneimine) / organopolysiloxane copolymer at a mass of 5% in deuterated chloroform and performing nuclear magnetic resonance (1H-NMR) analysis, using the integral ratio of alkyl or phenyl groups in segment (x) to methylene groups in segment (y).

[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, even more preferably 70,000 or more, and preferably 1,000,000 or less, more preferably 500,000 or less, and even more preferably 200,000 or less, from the viewpoint of improving opacity and color development. 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] Preferred examples of poly(N-acylalkyleneimine) / organopolysiloxane copolymers include poly(N-formylethyleneimine) / organopolysiloxane copolymer, poly(N-acetylethyleneimine) / organopolysiloxane copolymer, and poly(N-propionylethyleneimine) / organopolysiloxane copolymer.

[0047] Poly(N-acylalkyleneimine) / organopolysiloxane copolymers can be obtained, for example, by reacting poly(N-acylalkyleneimine), which is a ring-opening polymer of a cyclic imino ether, with an organopolysiloxane that forms a segment (x). More specifically, they can be obtained by the method described in Japanese Patent Application Publication No. 2011-126978. Poly(N-acylalkyleneimine) / organosiloxane copolymers used as cationic silicone polymer CII-2 can be used individually or in combination of two or more.

[0048] (Betaine polymer) In the present invention, betaine polymers include copolymers of monomers having anionic groups and monomers having cationic groups, polymers or copolymers of betaine monomers, polymers in which anionic groups are introduced into cationic polymers, and polymers in which the aforementioned basic groups are introduced into anionic polymers. Among these, from the viewpoint of improving opacity and color development, the betaine polymer is preferably a polymer containing a betaine structure in its side chains, and more preferably a betaine polymer containing constituent units derived from betaine monomers (hereinafter also referred to as "betaine polymer CIII"). The betaine monomer is preferably a monomer containing a betaine structure and a (meth)acrylamide structure, from the viewpoint of improving opacity and color development, more preferably at least one selected from carboxybetaine monomer, sulfobetaine monomer, and phosphobetaine monomer, and even more preferably carboxybetaine monomer.

[0049] Examples of betaine polymers include polymethacryloylethyldimethylbetaine (a 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, and octylacrylamide / (meth)acrylic acid or (meth)acrylic acid alkyl ester / butylaminoethyl methacrylate copolymer. In particular, as the betaine polymer CIII, a copolymer containing a structural unit derived from a betaine monomer and a structural unit derived from an alkyl methacrylate (hydrocarbon group) derived from an aliphatic alcohol having 1 to 22 carbon atoms is preferred from the viewpoint of improving opacity and color development, a copolymer containing a structural unit derived from a carboxybetaine monomer and a structural unit derived from an alkyl methacrylate (hydrocarbon group) derived from an aliphatic alcohol having 1 to 22 carbon atoms is more preferred, and an N-methacryloyloxyethyl-N,N-dimethylammonium-α-N-methylcarboxybetaine / alkyl methacrylate copolymer is even more preferred.

[0050] 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, from the viewpoint of improving opacity and color development. The weight-average molecular weight of the betaine polymer is the molecular weight in polystyrene terms, measured by gel permeation chromatography (GPC).

[0051] Examples of commercially available betaine polymers include Plussize L-410W, L-402W, L-440, L-440W, K-450, and L-450W (all manufactured by Go-O Chemical Industry Co., Ltd., trade names); Yukaformer SM and 301 (both manufactured by Mitsubishi Chemical Corporation, trade names); RAM Resin-1000, -2000, -3000, and -4000 (all manufactured by Osaka Organic Chemical Industry Co., Ltd., trade names); Marcoat Plus 3330 (manufactured by Nippon Lubrizol Co., Ltd., trade name), Unformer 28-4910, and LV-71 (both manufactured by AkzoNobel K.K., trade names).

[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. Examples of nonionic monomers in nonionic polymers include (meth)acrylates having hydrocarbon groups derived from aliphatic alcohols with 1 to 22 carbon atoms; N-vinyl-2-pyrrolidone; vinyl alcohol; polyalkylene glycol (meth)acrylate (n=1 to 30); alkoxy polyalkylene glycol mono(meth)acrylate (n=1 to 30); (meth)acrylamide and its derivatives. Furthermore, nonionic polymers may also contain constituent units derived from monomers other than nonionic monomers. Examples of other monomers include the aforementioned styrene monomers; the aforementioned aromatic group-containing (meth)acrylates; and vinyl acetate.

[0053] Nonionic polymers specifically include polyvinyl alcohol, polyvinyl acetal, polyurethane polyurea, polyvinylpyrrolidone, copolymers of vinylpyrrolidone and other nonionic monomers such as vinylpyrrolidone / vinyl acetate copolymer, cellulosic polymers such as hydroxyalkylcellulose, polyethylene glycol, polypropylene glycol, polyglycerin, polyvinyl alcohol, pullulan, guar gum, poly-N,N-dimethylacrylamide, poly-N-vinylacetamide, poly-N-vinylformamide, and poly(2-alkyl-2-oxazoline). Among these, polyvinyl acetal and polyurethane polyurea are preferred nonionic polymers from the viewpoint of improving opacity and color development. When polyvinyl butyral is used as the polyvinyl acetal, the degree of acetalization of polyvinyl butyral is preferably 50 mol% or more, more preferably 55 mol% or more, even more preferably 60 mol% or more, and preferably 80 mol% or less, more preferably 75 mol% or less, and even more preferably 70 mol% or less, from the viewpoint of improving opacity and color development.

[0054] Commercially available nonionic polymers include polyvinyl butyral such as the Esrec B series (manufactured by Sekisui Chemical Co., Ltd., trade name); polyurethane polyurea such as the BAYCUSAN series (manufactured by Covestro Japan, trade name); hydroxyethylcellulose such as HEC Daicel SE900, SE850, SE600, SE550, and SE400 (all manufactured by Daicel Finechem Co., Ltd., trade name); highly polymerized polyethylene glycol such as Polyox WSRN-12K, WSRN-60K, and WSR-301 (all manufactured by Dow Chemical Co., Ltd., trade name); polyethylene oxide such as PEO-27, PEO-18, PEO-15, and PEO-8 (all manufactured by Sumitomo Seika Co., Ltd., trade name); polyvinylpyrrolidone such as Rubiscol K90, K80, and K30 (all manufactured by BASF, trade name); and polyvinyl alcohol such as the Gosenol series (all manufactured by Mitsubishi Chemical Corporation, trade name).

[0055] In the present invention, the amount of polymer C that dissolves in water is preferably less than 5 g, as determined by dissolving polymer C, which has been dried at 105°C for 2 hours and reached a constant weight, in 100 g of water at 25°C, from the viewpoint of improving opacity and color development. Furthermore, if polymer C is an anionic polymer, the amount of solubility is the amount that dissolves when the anionic groups of polymer C are 100% neutralized with sodium hydroxide. If polymer C is a cationic polymer, the amount of solubility is the amount that dissolves when the cationic groups of polymer C are 100% neutralized with hydrochloric acid.

[0056] From the viewpoint of improving opacity and color development, polymer C is preferably an amphiphilic polymer that is insoluble in solvent B but has affinity for solvent B and also has affinity for water, more preferably one or more selected from ionic polymers and nonionic polymers, even more preferably a polymer containing at least one selected from an acidic group monomer, a basic group monomer, and a betaine monomer as a monomer constituent unit, even more preferably a polymer containing at least one selected from an acidic group monomer and a betaine monomer as a monomer constituent unit, even more preferably a polymer containing one or more selected from anionic polymer CI and betaine polymer CIII, and even more preferably a polymer containing betaine polymer CIII. Furthermore, from the viewpoint of improving the opacity and color development while also improving the water resistance of the cosmetic coating film, polymer C preferably contains a polymer having cationic groups. From the same viewpoint as above, the polymer having cationic groups is more preferably one or more selected from cationic polymers and betaine polymers, even more preferably a cationic polymer, even more preferably one or more selected from cationic polymer CII-1 and cationic silicone polymer CII-2, and even more preferably cationic polymer CII-1.

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

[0058] <Coloring agent> The colorants used in the present invention are not particularly limited as long as they are commonly used in cosmetics, and include organic pigments, hydrophobic dyes (oil-soluble dyes, disperse dyes), water-soluble dyes (acid dyes, reactive dyes, direct dyes, etc.). A hydrophobic dye is a dye whose solubility in 100g of water (at 20°C) is preferably less than 6% by mass. Specific examples of colorants 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 pigments and dyes coated with resins such as polymethacrylate esters. Furthermore, in the present invention, the use of inorganic pigments is not prohibited as long as the effects of the present invention are obtained. Examples of such inorganic pigments include white inorganic pigments such as titanium dioxide and zinc oxide; non-white inorganic pigments such as yellow iron oxide, red iron oxide, black iron oxide, carbon black, ultramarine, Prussian blue, Prussian blue titanium dioxide, black titanium dioxide, chromium oxide, chromium hydroxide, and titanium / titanium oxide sintered products; and extender pigments such as calcium carbonate, silica, and talc. When the coloring agent contains an inorganic pigment, at least one of the non-white inorganic pigments and extender pigments is preferred from the viewpoint of opacity and color development. The aforementioned colorants can be used individually or in combination of two or more. As for the hue of the coloring agent, from the viewpoint of improving color development, chromatic colors such as yellow, magenta, cyan, blue, red, orange, and green are preferred.

[0059] The colorant may have its surface hydrophobic treated, from the viewpoint of improving its dispersibility in the cosmetic composition and the water resistance of the cosmetic coating film. From the same viewpoint, if the colorant contains an inorganic pigment, it is preferable that the inorganic pigment has its surface hydrophobic treated. As for the hydrophobic treatment, a hydrophobic treatment applied to ordinary cosmetic powders using various hydrophobic treatment agents is preferred. Examples of such hydrophobic treatments 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] The colorant in the cosmetic composition of the present invention can take the form of being dispersed in the cosmetic composition or dissolved in the cosmetic composition. Among these, the form of the colorant is preferably dispersed in the cosmetic composition, from the viewpoint of improving opacity and color development and improving dispersibility in the cosmetic composition, more preferably dispersed using a dispersant or self-dispersing without a dispersant, and even more preferably dispersed using a dispersant. As a self-dispersing form, self-dispersing pigments are preferred. Self-dispersing pigments are pigments that can be incorporated into cosmetic compositions without the use of surfactants or dispersants by attaching functional groups that impart dispersibility to the pigment surface directly or via other atomic groups. Examples of functional groups that impart dispersibility include anionic functional groups such as carboxyl groups and sulfonic acid groups, or polyethylene oxide groups and polypropylene oxide groups. Commercially available self-dispersing pigments include Cabot's CAB-O-JET 200 series, 300 series, and 400 series.

[0061] From the viewpoint of homogeneity of coloring, as well as improving opacity and color development, the aforementioned coloring agent is preferably dispersed in a dispersible polymer D as a dispersant. In this specification, "dispersible polymer" means a polymer that can disperse a colorant in a medium of a cosmetic composition. From the viewpoint of improving opacity and color development, the dispersible polymer D is preferably soluble in either solvent A or solvent B, and insoluble in the other. If the dispersible polymer D is soluble in solvent A but insoluble in solvent B, then during the phase separation process between solvent A and solvent B when forming the cosmetic coating film, the colorant in the system will be present together with the dispersible polymer D. Due to the solubility of the dispersible polymer D in solvent B, it will be present in almost no place in solvent B, and therefore in the cosmetic coating film, it will mainly be included together with polymer C as a component of the primary particle shell. On the other hand, if the dispersible polymer D is insoluble in solvent A but soluble in solvent B, then during the phase separation process between solvent A and solvent B when forming the cosmetic coating film, the colorant is distributed into droplets of the separated solvent B. Therefore, especially if solvent B is volatile, the colorant will be present in the cavities of the hollow primary particles within the cosmetic coating film.

[0062] From the viewpoint of improving opacity and color development, the dispersible polymer D is preferably soluble in solvent A and insoluble in solvent B. Examples of dispersible polymer D include ionic polymers such as anionic polymers, cationic polymers, and betaine polymers, as exemplified by polymer C above; and nonionic polymers. Among these, at least one selected from ionic polymers and nonionic polymers is more preferable for dispersible polymer D, 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 is even more preferable, and at least one selected from anionic polymer CI and nonionic polymer is even more preferable.

[0063] The anionic polymer CI used as the dispersible polymer D preferably comprises constituent units derived from monomers having acidic groups and constituent units derived from alkyl (meth)acrylates, more preferably comprising constituent units derived from monomers having acidic groups, constituent units derived from alkyl (meth)acrylates, and constituent units derived from (N-alkyl)(meth)acrylamide, even more preferably being a (meth)acrylic acid / alkyl (meth)acrylate / (N-alkyl)(meth)acrylamide copolymer, and even more preferably being an acrylic acid / alkyl acrylate / (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 even more preferably polyvinyl butyral. From the viewpoint of improving opacity and color development, the degree of acetalization of polyvinyl butyral is preferably 50 mol% or more, more preferably 55 mol% or more, even more preferably 60 mol% or more, and preferably 80 mol% or less, more preferably 75 mol% or less, and even more preferably 70 mol% or less.

[0064] When the coloring agent is dispersed in a dispersible polymer D, it is preferable that both polymer C and dispersible polymer D are one or more selected from ionic polymers and nonionic polymers. Combinations of polymer C and dispersing polymer D include a combination in which polymer C is an ionic polymer and dispersing polymer D is an ionic polymer, a combination in which polymer C is an ionic polymer and dispersing polymer D is a nonionic polymer, and a combination in which polymer C is a nonionic polymer and dispersing polymer D is an ionic polymer. The combination of polymer C and dispersible polymer D is preferably such that polymer C is one or more selected from anionic polymer CI, cationic polymer CII-1, cationic silicone polymer CII-2, betaine polymer CIII, and nonionic polymer, and polymer D is one or more selected from anionic polymer CI and nonionic polymer. More preferably, polymer C is one or more selected from anionic polymer CI, cationic polymer CII-1, cationic silicone polymer CII-2, and betaine polymer CIII, and polymer D is one or more selected from anionic polymer CI and nonionic polymer. In particular, from the viewpoint of improving opacity and color development, the combination of polymer C and dispersible polymer D is even more preferably such that polymer C is an anionic polymer or betaine polymer and polymer D is an anionic polymer. From the viewpoint of improving the water resistance of the cosmetic coating film, the combination of polymer C and dispersible polymer D is more preferably such that polymer C is a cationic polymer or a betaine polymer and polymer D is an anionic polymer. From the viewpoint of improving opacity and color development, and from the viewpoint of the water resistance of the cosmetic coating film, the combination of polymer C and dispersible polymer D is more preferably such that polymer C is a betaine polymer and polymer D is an anionic polymer.

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

[0066] The cosmetic composition of the present invention may contain, as an optional component, any component used in cosmetic compositions, such as ultraviolet scattering agents, ultraviolet absorbing agents, fragrances, beauty ingredients, medicinal ingredients, pH adjusters, moisturizers, antioxidants, bactericidal agents, and preservatives, provided that it does not impair the effects of the present invention. Each of these can be used individually 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, even more preferably 3 mPa·s or more, and preferably 1,000 mPa·s or less, more preferably 700 mPa·s or less, even 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, and 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] (Manufacturing of cosmetic compositions) The cosmetic composition can be obtained by mixing and stirring solvent A, solvent B, polymer C, a colorant, and optionally the aforementioned optional components. If the colorant is dispersed in a dispersible polymer D, it is preferable to mix the colorant as a colorant dispersion containing colorant particles dispersed in the dispersible polymer D. There are no particular restrictions on the mixing order of solvent A, solvent B, polymer C, colorant dispersion, and the optional components, but it is preferable to first mix solvent A and polymer C to dissolve polymer C in solvent A to obtain a solution of polymer C, and then add and mix solvent B and colorant dispersion to the solution. The optional components may be further added and mixed as needed.

[0069] A colorant dispersion can be obtained by dispersing a colorant, a dispersible polymer D, etc., by a known method. Specifically, it is preferable to obtain it by a manufacturing method that includes a step of dispersing a colorant mixture containing a colorant, a dispersible polymer D, and an organic solvent to obtain a colorant dispersion, but the method is not necessarily limited to this method. The organic solvent used in the production of the colorant dispersion preferably has high affinity for the dispersible polymer D and good wettability to the colorant. From the viewpoint of improving wettability to the colorant and the adsorption of the dispersible polymer to the colorant, as well as from the viewpoint of safety due to residual organic solvents after application of the cosmetic composition, ethanol and isopropanol are preferred. In the dispersion process for manufacturing colorant dispersions, means of applying shear stress can be, for example, kneaders such as roll mills, kneaders, and extruders; high-pressure homogenizers such as Microfluidics (product name); and media-type dispersers such as paint shakers and bead mills. Among these, a high-pressure homogenizer is preferred from the viewpoint of reducing the particle size of the colorant. When performing dispersion processing using a high-pressure homogenizer, the size of the colorant particles can be controlled to a desired size by controlling the processing pressure and the number of passes in the dispersion process.

[0070] The content of each component in the cosmetic composition of the present invention is as follows, from the viewpoint of improving opacity 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, even more preferably 50% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, even 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, even 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, even 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, even more preferably 1.3% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, even 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, even more preferably 60% by mass or more, even more preferably 63% by mass or more, even more preferably 65% ​​by mass or more, even more preferably 67% by mass or more, and preferably 85% by mass or less, more preferably 80% by mass or less, even more preferably 75% by mass or less, and even more preferably 70% by mass or less. The mass ratio of the content of solvent A to the content of solvent B in the cosmetic composition of the present invention [solvent A / solvent B] is preferably 0.5 or more, more preferably 1 or more, even more preferably 1.5 or more, even more preferably 2 or more, and preferably 15 or less, more preferably 13 or less, even 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 polymer C contains a polymer that comprises at least one selected from an acidic monomer, a basic monomer, and a betaine monomer as a constituent unit, the content of the polymer comprising at least one selected from an acidic monomer, a basic monomer, and a betaine monomer as a constituent unit in polymer C is preferably 60% by mass or more, more preferably 70% by mass or more, even 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 viewpoint of improving opacity and color development. When polymer C contains one or more polymers selected from cationic polymers and betaine polymers as polymers having cationic groups, from the viewpoint of improving the water resistance of the cosmetic coating film while improving opacity and color development, the content of polymers having cationic groups in polymer C is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, and even more preferably 60% by mass or more, and preferably 100% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less. When using two or more types of polymer C in combination, it is preferable to adjust the amount of each polymer C in the cosmetic composition to be equal.

[0073] The content of the coloring agent in the cosmetic composition of the present invention is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, and even more preferably 4% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 7% by mass or less, from the viewpoint of improving opacity and color development. When the coloring agent is dispersed in a dispersible polymer D, the content of the dispersible 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, even more preferably 1.3% by mass or more, and preferably 7% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, and even more preferably 2% by mass or less. When the colorant is dispersed in a dispersible polymer D, the mass ratio [colorant / dispersible polymer D] of the colorant content 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, even more preferably 2 or more, and preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less. When the colorant is dispersed in a dispersible polymer D, the mass ratio [polymer C / dispersible polymer D] of the content of polymer C to the content of dispersible polymer D in the cosmetic composition of the present invention is preferably 0.3 or more, more preferably 0.5 or more, even more preferably 0.7 or more, and preferably 3 or less, more preferably 2 or less, even more preferably 1.5 or less, and even more preferably 1.3 or less.

[0074] The cosmetic composition of the present invention may contain water to the extent that it does not impair the effects of the present invention. 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, even 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 solvent B in the cosmetic composition and improving opacity and color development. In this invention, the water content in the cosmetic composition refers to the total amount of water contained in the cosmetic composition, including the amount intentionally added, the amount of each component such as solvent A (ethanol, etc.) brought in from the raw materials, and the amount mixed in due to condensation during the manufacturing process of the cosmetic composition.

[0075] As long as the effects of the present invention are obtained as described above, the cosmetic composition of the present invention does not prevent the use of inorganic pigments, however, the content of inorganic pigments in the cosmetic composition is preferably 5% by mass or less, more preferably 3% by mass or less, even 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. This provides concealing and color-developing properties. In other words, the cosmetic composition of the present invention is preferably used as a cosmetic composition for skin, a cosmetic composition for hair, or a cosmetic composition for nails, and is preferably used as a cosmetic composition for hair. Examples of skin cosmetic compositions include base makeup cosmetics such as makeup bases, foundations, and concealers; point makeup cosmetics such as blushes, eyeshadows, mascaras, eyeliners, eyebrow products, overcoats, and lipsticks; UV protection cosmetics such as sunscreen lotions and sunscreen creams; skin cleansing cosmetics such as facial cleansers and makeup removers; and basic cosmetics such as serums, masks, and massage cosmetics. In particular, from the viewpoint of concealing properties and color development, it is preferable to apply it to base makeup cosmetics such as makeup bases and foundations, and point makeup cosmetics. The hair cosmetic composition is preferably used for hair dyes such as hair mascara and hair color; styling products such as hair wax, hair spray, hair mousse, and hair foam; and hair growth products. As a cosmetic composition for nails, it is preferable to apply it to cosmetic products for beautifying nails, such as nail enamel and nail gloss. The cosmetic composition of the present invention can be applied in various forms, including solution, emulsion, cream, gel, paste, solid, and multilayer forms, and can also be used as a spray, sheet, or mousse.

[0077] [Makeup Method] The present invention allows for the application of the cosmetic composition to the skin, hair, or nails using a method of application commonly used when applying to the skin, hair, or nails under the temperature and humidity conditions of daily life.

[0078] The amount of the cosmetic composition to be applied is preferably 1 mg / cm². 2 More preferably 2 mg / cm³ 2 More preferably 3 mg / cm³ 2The above is true, and preferably 10 mg / cm³ 2 More preferably, 7 mg / cm³ 2 More preferably 5 mg / cm³ 2 The following applies: The thickness of the coating film before drying is preferably 10 μm or more, more preferably 20 μm or more, even more preferably 30 μm or more, and preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 150 μm or less.

[0079] In the cosmetic method of the present invention, the method for applying the cosmetic composition preferably uses patterning printing, which is used in printing systems, from the viewpoint of improving opacity and color development. By using such patterning printing, the amount of cosmetic composition applied, the application area, etc., can be controlled. Furthermore, by designing the printing pattern to be used, the cosmetic image to be applied can be designed in advance. Moreover, by using such patterning printing, the reproducibility of cosmetic coatings with complex cosmetic images can also be improved. The aforementioned patterning printing methods include on-demand printing such as inkjet and dispenser methods; and analog printing such as screen printing, flexographic printing, gravure printing, and offset printing, which can be selected and used depending on the viscosity of the cosmetic composition. On-demand printing is a plateless printing method that does not require printing plates and prints on the surface, such as skin, hair, or nails, without contact. Analog printing is a plate-based method that requires printing plates and involves printing while the plate is in contact with the printing surface, such as skin, hair, or nails. Among these methods, on-demand printing can dispense droplets of a cosmetic composition and apply a desired amount of droplets to a desired area of ​​the skin, hair, or nails. It can also control the amount applied per unit area of ​​droplets, the application area, etc., making it easy to finely control the cosmetic image. From this viewpoint, the method of applying the cosmetic composition is more preferably one in which the cosmetic composition is dispensed by one or more methods selected from an inkjet method and a dispenser method to apply droplets of the cosmetic composition to the skin, hair, or nails, and even more preferably one in which the cosmetic composition is dispensed by an inkjet method to apply droplets of the cosmetic composition to the skin, hair, or nails.

[0080] From the viewpoint of improving opacity and color development, the applied voltage to the inkjet head is preferably 5V or higher, more preferably 10V or higher, even more preferably 15V or higher, and preferably 50V or lower, more preferably 45V or lower, and even more preferably 40V or lower. The drive frequency of the inkjet head is preferably 1 kHz or higher, more preferably 3 kHz or higher, and more preferably 300 kHz or lower, more preferably 150 kHz or lower, even more preferably 90 kHz or lower, and even more preferably 50 kHz or lower, from the viewpoint of improving opacity and color development. From the viewpoint of improving opacity and color development, the amount of liquid dispensed from the cosmetic composition is preferably 0.01 pL or more, more preferably 0.1 pL or more, even more preferably 1 pL or more, and even more preferably 4 pL or more per drop, and preferably 50 pL or less, more preferably 40 pL or less, and even more preferably 35 pL or less.

[0081] The droplet density p of the cosmetic composition is preferably 10,000 or more, more preferably 30,000 or more, even more preferably 50,000 or more, and even more preferably 100,000 or more, as dots per square inch, and preferably 3,000,000 or less, more preferably 1,000,000 or less, and even more preferably 500,000 or less. The droplet density p 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, it is preferable to apply the cosmetic composition to the skin, hair, or nails to form a coating film, and then dry the coating film under atmospheric pressure. This makes it possible to form a cosmetic coating film with excellent opacity and color development. In the present invention, the coating film can be sufficiently dried by natural drying under everyday temperature and humidity conditions, but from the viewpoint of accelerating drying, air drying, hot air drying, etc. may be performed. Furthermore, when the cosmetic composition is applied to the skin, it may be dried by natural drying at skin temperature. When hot air drying is performed, there are no particular restrictions on the temperature at which the coating film dries, but it is preferably 40°C or higher, more preferably 50°C or higher, even more preferably 55°C or higher, and preferably 80°C or lower, more preferably 70°C or lower, and even more preferably 65°C or lower. The drying time of the coated film is preferably 5 minutes or more, more preferably 7 minutes or more, even 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 opacity and color development, the present invention preferably includes a step of applying the cosmetic composition to the skin, hair, or nails (hereinafter also referred to as "step 1"), and then, before the coating film made of the cosmetic composition dries, a step of further applying droplets of liquid E containing water to the cosmetic composition applied to the skin, hair, or nails (hereinafter also referred to as "step 2"). This allows for rapid phase separation of solvent A and solvent B, promotes the formation of primary particles in which solvent B is coated with polymer C, and improves opacity and color development.

[0084] <Liquid E> Liquid E according to the present invention contains water, but may also contain other liquids besides water. Other liquids that are suitable include monohydric alcohols with 1 to 4 carbon atoms, such as ethanol, n-propanol, isopropanol, and tert-butyl alcohol. In particular, from the viewpoint of improving opacity and color development, the other liquid is 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, even 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 preferably 100% by mass or less, and even more preferably 100% by mass. The content of ethanol as another liquid in liquid E is preferably 50% by mass or less, more preferably 40% by mass or less, even 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, and 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 opacity and color development, it is preferable to use a device that generates minute droplets of liquid E containing water. The device that generates minute droplets is not particularly limited and examples include devices using piezoelectric, thermal, pressurized, rotary, steam, ultrasonic, and electrostatic methods. Among these methods, a method of spraying droplets using an atomizing device (spray) or a method of applying droplets by patterning printing used in a printing system is preferred, and a method of spraying droplets using an atomizing device or a method of ejecting droplets by an inkjet method is more preferred. From the viewpoint of improving opacity and color development, the amount of liquid E droplets applied is preferably 0.01 mg / cm². 2More preferably 0.05 mg / cm³ 2 More preferably 0.1 mg / cm³ 2 The above is true, and preferably 10 mg / cm³ 2 More preferably, 7 mg / cm³ 2 More preferably 5 mg / cm³ 2 The following applies: From the viewpoint of improving opacity and color development, the average diameter of the droplets of liquid E is preferably 0.01 μm or more, more preferably 0.1 μm or more, 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 atomizing devices include jet atomizers, ultrasonic atomizers, and mesh atomizers. The atomizing capacity of the atomizer is preferably 0.01 mL / min or more, more preferably 0.1 mL / min or more, 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 for ejecting liquid droplets using an inkjet method, the same method as the application method for the cosmetic composition described above can be used.

[0087] The application of droplets of liquid E in step 2 may be applied to the entire area to which the cosmetic composition was applied in step 1, or to only a part of that 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 opacity and color development, is preferably 10 seconds or less, more preferably 5 seconds or less.

[0088] [Decorative coating] The average particle size of the primary particles contained in the cosmetic coating film formed by the present invention is preferably 0.1 μm or more, more preferably 0.2 μm or more, from the viewpoint of improving the strength of the cosmetic coating film and improving color development, and preferably 5 μm or less, more preferably 3 μm or less, from the viewpoint of improving opacity. The average particle size of primary particles contained in a cosmetic coating can be measured by observing the formed cosmetic coating using a scanning electron microscope and processing the resulting scanning electron microscope image using the image analysis software "ImageJ" (manufactured by the National Institutes of Health, USA). Specifically, an optical microscope (manufactured by Hirox Co., Ltd., product name: RH-2000) is used to capture observation images of the polymer coating surface at a magnification of 2,500x. These images are then processed using image analysis software (manufactured by the National Institutes of Health, USA, ImageJ) to measure the average particle size of primary particles contained in the coating. When taking images with an optical microscope, the brightness and contrast are adjusted so that the percentage of pixels reaching the maximum brightness value is 1% or less, and the average brightness value falls within the range of 40% to 60% of the maximum brightness value. The observed image is then saved. This observed image is then converted to an 8-bit grayscale image using the image conversion function of ImageJ. Next, the scale is set to match the magnification of the optical microscope. This scale setting converts the particle size data calculated in subsequent calculations to actual sizes. For example, at a magnification of 2,500x, the conversion is such that a length of 1 mm corresponds to 15,840 pixels. Next, subtract background processing is performed. In this process, the Rolling Ball Radius is set to approximately the same size as the observed primary particle diameter. Specifically, if the majority of primary particles are about 3 μm in diameter and the length of 1 mm is 15,840 pixels, the Rolling Ball Radius should be set to 50 pixels. This allows for the removal of imaging noise components smaller than the primary particle diameter. Next, the Threshold function, an image adjustment feature of ImageJ, is used to perform a binarization process on the region of the primary particles. In this specification, "binarization" refers to the process of treating an image as white if its brightness value is above a specified value (threshold), and as black if it is below the specified value. In the image obtained through observation, the shell of the primary particle is represented as high brightness due to the high density of polymer, while the core is represented as low brightness. This makes it possible to obtain an image with clear shading sufficient to measure the average particle size of the primary particle. The obtained binary image is then subjected to "Analyze Particles" in ImageJ. Furthermore, particles cut off at the edges of the image, particles with a major axis that is roughly one-tenth the 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, and the average of the major axes of at least 300 particles is taken as the average particle size of the primary particles.

[0089] Furthermore, it is preferable that the cosmetic coating film formed by the present invention contains secondary particles formed by the accumulation of primary particles. In the present invention, it is believed that as solvent A volatilizes and the surface of the formed primary particles aligns, regularly partitioned cellular convection structures, so-called Benard cells, are generated within the coating film, and that primary particles can accumulate and form secondary particles through Benard convection within each cell. A cosmetic coating film containing such secondary particles has a structure that is close to the surface relief structure of actual skin, especially when applied to the skin, and can therefore form a cosmetic coating film that gives a natural impression. [Examples]

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

[0091] (1) Measurement of the weight-average molecular weight of cationic polymer CII-1 The molecules were measured using gel permeation chromatography (using a Tosoh Corporation GPC instrument (HLC-8320GPC), Tosoh Corporation columns (TSKgel SuperAWM-H, TSKgel SuperAW3000, TSKgel guardcolum Super AW-H), flow rate: 1 mL / min) with known molecular weight monodisperse polystyrene kits (PStQuick B (F-550, F-80, F-10, F-1, A-1000), PStQuick C (F-288, F-40, F-4, A-5000, A-500), Tosoh Corporation)) as standard substances. The sample used for measurement was prepared by mixing 0.1 g of cationic polymer CII-1 with 10 mL of the 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 Advantech Co., Ltd.).

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

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

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

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

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

[0097] (Betaine polymer CIII) Yukaformer SM-dry: A powder obtained by drying an ethanol solution (30% solids content) of N-methacryloyloxyethyl-N,N-dimethylammonium-α-N-methylcarboxybetaine / alkyl methacrylate copolymer (manufactured by Mitsubishi Chemical Corporation, product name: Yukaformer SM).

[0098] (Nonionic polymer) Polyvinyl butyral: Esrec BM-1 (Sekisui Chemical Co., Ltd., product name, acetalization degree approximately 65 mol% (catalog value)), 100% solids powder Polyurethane polyurea: Dried powder of BAYCUSAN C2000 (Covestro Japan Co., Ltd., product name, a 40% solids ethanol solution of polyurethane-64)

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

[0100] Synthesis Example 1 (Synthesis of Cationic Polymer 1) In a reaction vessel equipped with two dropping funnels 1 and 2, monomers and organic solvents with the composition shown in the "Initial Monomer Solution" column of Table 1 were placed, and the vessel was purged with nitrogen gas. On the other hand, a dropper monomer solution was prepared by mixing monomers and organic solvents with the compositions shown in the "Dropper Monomer Solution" column of Table 1. Separately, a polymerization initiator solution was prepared by mixing a polymerization initiator (2,2'-azobis(2,4-dimethylvaleronitrile): manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name: V-65) and organic solvent shown in the "Polymer Initiator Solution" column of Table 1. These solutions were then placed in dropper funnels 1 and 2, respectively, and subjected to nitrogen gas purging. Under a nitrogen atmosphere, the initial monomer solution in the reaction vessel was maintained at 62°C while being stirred. The dropwise monomer solution and polymerization initiator solution were gradually added to the reaction vessel over 2 hours, ensuring that the ratio of polymerization initiator added to monomer remained constant. After the dropwise addition was complete, the mixture was stirred for 1 hour while maintaining a temperature of 62°C, and then 47 parts of acetone were added. The mixture was then heated and aged for 4 hours while continuing to stir at a temperature of 62°C. Next, an ultrafiltration membrane (a ceramic ultrafiltration membrane manufactured by NGK Insulators, Ltd., trade name: Sefilt, pore size 10 nm) was used to remove unreacted monomers and polymerization initiator residues from the reactants, and the mixture 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) In a reaction vessel equipped with two dropping funnels 1 and 2, monomers and organic solvents with the composition shown in the "Initial Monomer Solution" column of Table 1 were placed, and the vessel was purged with nitrogen gas. On the other hand, a dropper monomer solution was prepared by mixing the monomer and organic solvent with the composition shown in the "Dropper Monomer Solution" column of Table 1. Separately, a polymerization initiator solution was prepared by mixing the polymerization initiator (V-65) and organic solvent shown in the "Polymerization Initiator Solution" column of Table 1. These solutions were then placed in dropper funnels 1 and 2, respectively, and subjected to nitrogen gas purging. Under a nitrogen atmosphere, the initial monomer solution in the reaction vessel was maintained at 55°C while being stirred. The dropwise monomer solution and polymerization initiator solution were gradually added to the reaction vessel over 2 hours, ensuring that the ratio of polymerization initiator added to monomer remained constant. After the dripping was complete, the mixture was heated and aged for 5 hours while being stirred at a constant temperature of 55°C. Next, an ultrafiltration membrane (a ceramic ultrafiltration membrane manufactured by NGK Insulators, Ltd., trade name: Sefilt, pore size 10 nm) was used to remove unreacted monomers and polymerization initiator residues from the reactants, and the mixture was dried 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 with 2.0 g of molecular sieve (Zeolam A-4, manufactured by Tosoh Corporation) at 28°C for 15 hours. 0.77 g (0.005 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 under a nitrogen atmosphere for 8 hours to obtain a solution of terminally 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., product 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 with 15.2 g of molecular sieve at 28°C for 15 hours. Next, the terminally reactive poly(N-propionylethyleneimine) solution obtained above was added in one go 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 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 for 15 hours using 9.0 g of molecular sieves (Zeolam A-4, manufactured by Tosoh Corporation). To the resulting ethyl acetate solution of dehydrated 2-ethyl-2-oxazoline, 9.48 g (0.061 mol) of diethyl sulfate was added, and the mixture was heated under reflux at 80°C under a nitrogen atmosphere for 8 hours to obtain a solution of terminally reactive poly(N-propionylethyleneimine) (number average molecular weight 1,300). Separately, 153.7 g of side-chain primary aminopropyl-modified polydimethylsiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KF-8003, 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 terminally reactive poly(N-propionylethyleneimine) solution obtained above was added in one go to the dehydrated side-chain primary aminopropyl-modified polydimethylsiloxane solution and heated under reflux at 80°C for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain 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 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 in 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 resulting ethyl acetate solution of dehydrated 2-ethyl-2-oxazoline, and the mixture was heated under reflux at 80°C under a nitrogen atmosphere for 8 hours to obtain a terminally reactive poly(N-propionylethyleneimine) solution (number average molecular weight: 6,000). 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 terminally reactive poly(N-propionylethyleneimine) solution obtained above was added in one go to the dehydrated side-chain primary aminopropyl-modified polydimethylsiloxane solution and heated under reflux at 80°C for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain 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 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] Manufacturing Example 1-1 (Manufacturing of Colorant Dispersion 1) 250g of "Plus Size L-9909U" (manufactured by Go-O Chemical Industry Co., Ltd., acid value: 50mgKOH / g, 100% neutralized, neutralizing agent: 2-amino-2-methyl-1-propanol, ethanol solution with solid content concentration of 40% by mass), an ethanol solution of an anionic acrylic polymer, was added as dispersible polymer D (anionic polymer CI) to a sealed and temperature-controllable glass jacket. 300g of Red No. 226 K (manufactured by Kiseki Chemical Co., Ltd., red dye (CIVat Red 1)) was added as a coloring agent while stirring at 1,400 rpm at a jacket temperature of 15°C using a high-speed disperser "TK Robomix" (manufactured by Primix Co., Ltd.) (stirring section: Homodisper 2.5 type (blade diameter 40mm)). The mixture was then stirred at 1,400 rpm at a jacket temperature of 15°C for 1 hour to allow the coloring agent to blend with the anionic acrylic polymer solution. Next, while maintaining the jacket temperature at 15°C, the rotation speed was changed to 8,000 rpm, 1,450 g of primary ethanol was added, and the mixture was stirred for 3 hours to obtain 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 (Microfluidics, model: M-140K) to obtain a colorant dispersion 1 with a solid content of 20% by mass. Furthermore, the amount of the anionic acrylic polymer used as the dispersible polymer D (anionic polymer CI) that could be dissolved in 100g of each solvent B used in the examples and comparative examples described later was less than 5g, while the amount that could be dissolved in 100g of each solvent A was 5g or more.

[0107] Manufacturing Example 1-2 (Manufacturing of Colorant Dispersion 2) In a sealed and temperature-controllable glass jacket, 100 g of nonionic polyvinyl butyral "Eslec BM-1" (manufactured by Sekisui Chemical Co., Ltd., 100% active ingredient powder) was dissolved in 900 g of primary ethanol as dispersible polymer D (nonionic polymer) to obtain an ethanol solution of nonionic polyvinyl butyral with a solid content concentration of 10% by mass. Next, in the same manner as in Production Example 1-1, a solution of nonionic polyvinyl butyral was used instead of an ethanol solution of anionic acrylic polymer, and the composition of the colorant mixture was changed to that shown in Table 2 to obtain colorant dispersion 2. Furthermore, the amount of nonionic polyvinyl butyral used as dispersible polymer D (nonionic polymer) that could be dissolved in 100g of each solvent B used in the examples and comparative examples described later was less than 5g, while the amount that could be dissolved in 100g of each solvent A was 5g or more.

[0108] [Table 2]

[0109] Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-7 (Manufacturing of cosmetic compositions) 1.5 parts of Yukaformer SM-dry, used as polymer C (betaine polymer CIII), were dissolved in 58.5 parts of solvent A shown in Table 3. After confirming that the solution was clear and free of suspended and precipitated particles, 10 parts of solvent B shown in Table 3 were added, followed by 30 parts of colorant dispersion 1. The mixture was stirred to homogenize it, and the resulting mixture was filtered to obtain cosmetic compositions X-1 to X-5 and XC-1 to XC-7, respectively. The viscosity of each obtained cosmetic composition at 20°C is shown in Table 3. Furthermore, regarding the membrane filters used for filtering the above-mentioned mixtures, from the viewpoint of the solvent resistance of the filter itself, a 1.20 μm pore size cellulose acetate syringe filter (manufactured by Sartorius) was used in the production of cosmetic compositions X-1 to X-5 and XC-1 to XC-2, XC-7, while a 0.45 μm pore size hydrophilic PTFE syringe filter (manufactured by Advantec) was used in the production of cosmetic compositions XC-3 to XC-6. In Example 1-1, the amount of polymer C (Yukaformer SM-dry) that could be dissolved in 100g of solvent A (anhydrous ethanol) was 50g, and the amount that could be dissolved in 100g of solvent B (Pearlream 3) was 0.3g. In Examples 1-2 to 1-5, the amount of polymer C (Yukaformer SM-dry) that could be dissolved in 100g of each solvent B was less than 5g, and the amount that could be dissolved in 100g of each solvent A was 5g or more.

[0110] (Cosmetic method (manufacturing of cosmetic coating film)) The inside of the ink cartridge "TK403 Black-CS Cartridge" (manufactured by Kishu Giken Kogyo Co., Ltd.) was cleaned with deionized water and ethanol, and then filled with the respective cosmetic compositions obtained in the examples and comparative examples. These cartridges were then installed in a modified handheld inkjet printer (manufactured by Kishu Giken Kogyo Co., Ltd., product name: KGKJET HQ1000H) that was configured to print at a printing speed of 600 dpi. Next, in an environment controlled to a temperature of 25°C and humidity of 50%, a black PET film "Lumirror S10" (manufactured by Toray Industries, Inc.) was fixed on a horizontal table as an evaluation substrate, and the cosmetic composition was solid-printed onto the evaluation substrate from a vertical top direction using the aforementioned handheld inkjet printer. The printing was performed using a solid image measuring 12.7 mm in height and 50.8 mm in width, with a resolution of 600 dpi vertically and 600 dpi horizontally (dot density p: 360,000 (dots / square inch)). Immediately after printing, a COMFORT OASIS ultrasonic nebulizer (manufactured by Shin-ei Kogyo Co., Ltd., model: KU-200, average droplet diameter: 1-5 μm) was used to spray tiny droplets of deionized water as liquid E onto the surface of the coated film, following the inkjet head of the handheld inkjet printer. One second after the completion of printing the solid image, the power to the ultrasonic nebulizer was turned off to stop the spraying of droplets. Next, the printed materials were left for 30 minutes in an environment controlled to a temperature of 25°C and a humidity of 50%, to obtain printed materials on which cosmetic coatings 1-1 to 1-5 and 1-C1 to 1-C7 formed from each cosmetic composition were created.

[0111] (Evaluation of opacity 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 using the following measuring device and measurement conditions. The results are shown in Table 3. Measurement device: Spectrophotometer / densitometer "SpectroEye" (manufactured by X-Rite Corporation) Measurement conditions: Light source D65, observation field 2 degrees, density reference DIN, white base "Abs", built-in filter "No". When the black PET film used as the evaluation substrate was measured, the measured values ​​for both black and magenta density were 1.90. In evaluating opacity and color development, it is desirable to have a low black density and a high magenta density from the viewpoint of color vividness. If the opacity of the decorative coating is insufficient, the black density will be high, and the magenta color will not develop well. From this viewpoint, the density difference between magenta density and black density (magenta density - black density) is preferably 0.8 or higher, more preferably 0.9 or higher, and even more preferably 1.0 or higher. In the examples and comparative examples, black PET film was used as a substitute for skin, hair, and nails to evaluate opacity and color development. However, it was confirmed that the same scale can be used to evaluate the effects when applied to skin, hair, and nails.

[0112] [Table 3]

[0113] Table 3 shows that Examples 1-1 to 1-5 have low black density and excellent opacity, high magenta density, and a density difference of 0.8 or more between magenta and black density, indicating excellent color reproduction. On the other hand, Comparative Examples 1-1 to 1-7 have high black density, poor opacity, and a small density difference between magenta and black, indicating poor color development.

[0114] Examples 2-1 to 2-30 (Manufacturing of cosmetic compositions) 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 anhydrous ethanol (boiling point 78°C, Ra24) as solvent A. After confirming that the mixture was clear and free of suspended solids and precipitates, Pearlream 3 (boiling point 179°C, Ra45) was added as solvent B, followed by the addition of a colorant dispersion. The mixture was stirred to homogenize it, 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. In Examples 2-1 to 2-30, the amount of polymer C that could be dissolved in 100g of solvent B (Pearlream 3) was less than 5g, while the amount that could be dissolved in 100g of solvent A (anhydrous ethanol) was 5g or more.

[0115] (Method of applying cosmetics (manufacturing of cosmetic coatings) and evaluation of opacity and color development) Printed materials having decorative coatings 2-1 to 2-30 were obtained using the same method as in Example 1-1. After obtaining these materials, the image density was measured and the opacity and color development were evaluated. The results are shown in Tables 4 and 5.

[0116] (Evaluation of water resistance) The obtained printed material was placed on a horizontal surface, and 0.1 g of deionized water was dropped onto the decorative coating using a dropper. The material was then left for 1 minute in an environment controlled to 25°C and 50% humidity. Next, the surface condition of the decorative coating was observed while rubbing the area where the deionized water was dropped five times with a 5 mm diameter cotton swab moistened with deionized water. The area was then dried with a hot air dryer until the water droplets were completely dry and no longer visible. The surface condition of the decorative coating was then observed again and evaluated using the following five-level evaluation criteria. The results are shown in Tables 4 and 5. [Evaluation Criteria] 5: There was no change in the surface condition of the cosmetic coating during rubbing while wet, and no color fading occurred. 4. While rubbing the coating film when wet, a slight color change may be observed. However, after drying, the surface returns to its original state with no color fading, and there are no practical problems. 3. While rubbing the coating film while wet may cause slight color changes and wrinkles, it returns to its original surface condition after drying, with no color fading, and poses no practical problems. 2: Obvious color fading was observed in the cosmetic coating during rubbing while wet, and the color fading was clearly noticeable even after drying. 1: The cosmetic coating may tear during rubbing while wet, and even after drying, the surface may differ significantly from its original state.

[0117] [Table 4]

[0118] [Table 5]

[0119] Tables 4 and 5 show that Examples 2-1 to 2-30 have low black density and excellent opacity, high magenta density, and a density difference of 0.8 or more between magenta and black density, indicating excellent color development and also excellent water resistance. Furthermore, in Examples 2-1 to 2-6, 2-12 to 2-13, 2-17, 2-29 to 2-30, an anionic polymer was used as the dispersible polymer D of the colorant, and one of the following polymers C was used alone: ​​anionic polymer CI, cationic polymer CII, betaine polymer CIII, and nonionic polymer. From these results, it can be seen that Example 2-1, which used betaine polymer CIII, showed the lowest black concentration, followed by Examples 2-2 to 2-4, which used anionic polymer CI, showing relatively low black concentrations, indicating that these examples have superior opacity and color development. In addition, it can be seen that Examples 2-5 to 2-6, which used cationic polymer CII-1, have superior water resistance. Furthermore, from Tables 4 and 5, it can be seen that when an anionic polymer or a nonionic polymer is used as the dispersible polymer D of the colorant, and both types are used in combination as polymer C, Examples 2-7 to 2-9, which used anionic polymer CI and betaine polymer CIII in combination, showed the lowest black concentration, followed by Examples 2-10 to 2-11, which used cationic polymer CII-1 and betaine polymer CIII in combination, showing a relatively low black concentration. These examples demonstrate superior opacity and color development. Examples 2-14 to 2-16 and 2-18 to 2-22, which used anionic polymer CI and cationic polymer CII-1 or cationic silicone polymer CII-2 in combination, show superior water resistance. Furthermore, Table 5 shows that Example 2-28, which uses three types of polymer C—anionic polymer CI, cationic silicone polymer CII-2, and betaine polymer CIII—exhibits a relatively low black concentration, has excellent opacity and color development, and is also water-resistant.

[0120] Examples 3-1 to 3-11 (Manufacturing of cosmetic compositions) In the compositions shown in Table 6, Yukaformer SM-dry or Yukaformer SM-dry and cationic silicone polymer 3 were dissolved in anhydrous ethanol or anhydrous isopropanol as solvent A, with polymer C (betaine polymer CIII and cationic silicone polymer CII-2) being used. After confirming that the mixture was clear and free of suspended solids and precipitates, each solvent B shown in Table 6 and water were added, and the mixture was stirred to homogenize it. The mixture was then filtered using a cellulose acetate syringe filter with a pore size of 0.20 μm (manufactured by Advantec Co., Ltd.) to obtain cosmetic compositions Z-1 to Z-11. The amount of polymer C (Yukaformer SM-dry and cationic silicone polymer 3) used in Examples 3-8 to 3-9 that could be dissolved in 100g of each solvent B shown in Table 6 was less than 5g, while the amount that could be dissolved in 100g of solvent A (anhydrous ethanol) was 5g or more.

[0121] (Method of applying cosmetics (manufacturing of cosmetic coatings) and evaluation of opacity and color development) Printed materials having decorative coatings 3-1 to 3-11 were obtained using the same method as in Example 1-1. After obtaining these materials, the image density was measured and the opacity and color development were evaluated. The results are shown in Table 6. In evaluating opacity and color development, the magenta concentration was measured every 5 minutes after stopping the spraying of minute droplets of deionized water. The time required for the magenta concentration to stabilize was measured, and the rate of color development was evaluated. When measuring the magenta concentration, the magenta concentration was considered stable when the difference between the measured magenta concentration and the magenta concentration measured 5 minutes earlier was 0.1 or less. This time was recorded, and the magenta concentration at that point was evaluated. The results are shown in Table 6. The shorter the time it takes for the magenta density to stabilize, the better; a time of 30 minutes or less is practically acceptable in terms of color development speed.

[0122] [Table 6]

[0123] Table 6 shows that Examples 3-1 to 3-11 exhibit excellent color development, with a color development time of 30 minutes or less, low black density, excellent opacity, high magenta density, and a density difference of 0.8 or more between magenta and black density. [Industrial applicability]

[0124] The cosmetic composition of the present invention can produce a good cosmetic film that has excellent opacity and color development, and can be applied to skin, hair, or nails, even without using inorganic pigments.

Claims

1. A cosmetic composition containing solvent A, solvent B, polymer C, and a coloring agent. The solvent A is one or more selected from ethanol, n-propanol, and isopropanol. 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 following formula (1), is 40 or higher. The solvent B is miscible with the solvent A, and the polymer C is soluble in the solvent A and 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. The content of solvent B in the cosmetic composition is 15% by mass or more and 25% by mass or less. Furthermore, it contains a dispersible polymer D, A cosmetic composition comprising the coloring agent dispersed in the dispersible polymer D. Ra=(4×ΔD ２ +ΔP ２ +ΔH ２ ) ０．５ (1) ΔD: Difference in the Hansen solubility parameter of solvent B and water for dispersion components. ΔP: Difference in polarity component in the Hansen solubility parameter between solvent B and water. ΔH: Difference in hydrogen bonding components in the Hansen solubility parameters of 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 dispersible polymer D is soluble in solvent A and insoluble in solvent B.

4. The cosmetic composition according to any one of claims 1 to 3, wherein polymer C contains a polymer comprising at least one selected from an acidic monomer, a basic monomer, and a betaine monomer as a constituent unit.

5. The cosmetic composition according to any one of claims 1 to 4, wherein solvent B is one or more selected from volatile hydrocarbon oils and volatile silicone oils.

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

7. The cosmetic composition according to any one of claims 1 to 6, wherein the polymer C content is 0.5% by mass or more and 15% by mass or less.

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

9. A cosmetic composition for hair, according to any one of claims 1 to 8.

10. A cosmetic coating film formed from the cosmetic composition described in any one of claims 1 to 9.

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