Oil-based solid cosmetic

Abstract

To provide oil-based solid cosmetics that remain stable without surface sweating during storage, offer enhanced removability and easy spread, and achieve a light, thin finish.SOLUTION: Oil-based solid cosmetics comprise following components (A), (B), (C) and (D): (A) a silicone-based oil-based gelator, (B) a hydrocarbon-based wax, (C) a nonvolatile ester oil that is liquid at 25°C, and (D) powder.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an oily solid cosmetic preparation. [Background technology]

[0002] 2. Description of the Related Art Conventionally, oil-based solid cosmetic compositions have been developed that have excellent spreadability and feel when applied, and excellent cosmetic durability. For example, Patent Document 1 describes that an oil-based cosmetic composition containing a specific poly(N-acylalkyleneimine)-modified organopolysiloxane, a non-volatile silicone, a powder, and a solid wax with a penetration of 20 or less not only spreads well when applied, but also suppresses uneven powder distribution after application, provides a glossy finish without a dry or powdery feeling, does not make the skin feel tight even after 3 hours, and has excellent cosmetic durability. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2015-124147 A Summary of the Invention [Problem to be solved by the invention]

[0004] Conventional oil-based solid cosmetics not only suffer from the problem of sweating during storage, which poses stability issues, but also have the problem of being difficult to remove and resulting in a thick finish.

[0005] The present inventors have discovered that an oil-based solid cosmetic preparation, which combines a non-volatile ester oil that is liquid at 25°C with a silicone oil-based gelling agent, a hydrocarbon wax, and a powder, does not cause surface sweating during storage, has excellent stability, has improved removal properties, spreads easily, and provides a thin finish.

[0006] The present invention comprises the following components (A), (B), (C) and (D): (A) a silicone-based oil-based gelling agent, (B) a hydrocarbon wax; (C) a non-volatile ester oil that is liquid at 25°C; (D) Powder The present invention relates to an oil-based solid cosmetic preparation comprising the above-mentioned. The present invention also relates to a method for using the oily solid cosmetic preparation, which comprises applying the preparation to the skin with an applicator having a roller. Effect of the Invention

[0007] The oil-based solid cosmetic of the present invention does not cause sweating on the surface during storage, has excellent stability, is improved in removal properties, has excellent adhesion during application, and provides a thin finish. In addition, it suppresses shine caused by sebum over time, has excellent makeup durability, and does not cause a dry feeling. [Brief description of the drawings]

[0008] [Figure 1] FIG. 1 is a diagram showing an example of an application tool having a roller. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The silicone-based oily gelling agent of component (A) used in the present invention is one that is commonly used in cosmetics, and examples of such agents include poly(N-acylalkyleneimine)-modified organopolysiloxane and dimethicone crosslinked elastomer. Of the components (A), the (A1) poly(N-acylalkyleneimine)-modified organopolysiloxane is an organopolysiloxane segment constituting the main chain, in which at least two of the silicon atoms are linked, via an alkylene group containing a heteroatom, to the following general formula (1);

[0010] [ka]

[0011] (In the formula, R 1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and t represents 2 or 3. An organopolysiloxane comprising poly(N-acylalkyleneimine) segments each having a repeating unit represented by the formula: The number average molecular weight of the poly(N-acylalkyleneimine) segment is 500 to 4000; the mass ratio (a / b) of the organopolysiloxane segment (a) constituting the main chain to the poly(N-acylalkyleneimine) segment (b) is 80 / 20 to 99 / 1; the weight average molecular weight of the organopolysiloxane segment between adjacent poly(N-acylalkyleneimine) segments is 5,000 to 40,000; An organopolysiloxane in which the organopolysiloxane segment constituting the main chain has a weight average molecular weight of 15,000 to 200,000 is preferred, as this provides better stability.

[0012] At least two poly(N-acylalkyleneimine) segments are bonded to any silicon atom constituting the organopolysiloxane segment via an alkylene group containing a heteroatom.Furthermore, it is preferable that the poly(N-acylalkyleneimine) segments are bonded to one or more silicon atoms excluding both ends of the organopolysiloxane segment via the alkylene group, and it is more preferable that the poly(N-acylalkyleneimine) segments are bonded to two or more silicon atoms excluding both ends via the alkylene group. That is, the component (A1) is preferably a graft polymer having, as a side chain, a poly(N-acylalkyleneimine) segment consisting of at least two or more repeating units represented by the above general formula (1).

[0013] The alkylene group containing a heteroatom functions as a linking group for the poly(N-acylalkyleneimine) segment. Examples of such alkylene groups include alkylene groups having 2 to 20 carbon atoms and containing 1 to 3 nitrogen atoms, oxygen atoms, or sulfur atoms. Among these, a group represented by any one of the following formulae (i) to (vii) is preferred, a group represented by the following formulae (i) or (ii) is more preferred, and a group represented by the following formula (i) is even more preferred. In the formulae, An -represents a counter ion of a quaternary ammonium salt, and examples thereof include an ethyl sulfate ion, a methyl sulfate ion, a chloride ion, an iodide ion, a sulfate ion, a p-toluenesulfonate ion, and a perchlorate ion.

[0014] [ka]

[0015] In the N-acylalkyleneimine unit constituting the poly(N-acylalkyleneimine) segment, R 1 In the formula, examples of the alkyl group having 1 to 3 carbon atoms include linear alkyl groups having 1 to 3 carbon atoms, and branched alkyl groups having 3 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

[0016] In the general formula (1), t is the number 2 or 3, and is preferably 2 from the viewpoint of availability of raw materials during the production of organopolysiloxane.

[0017] The mass ratio (a / b) is in the range of 80 / 20 to 99 / 1, and from the viewpoints of excellent adhesion to the skin and excellent uniform removal, is preferably 83 / 17 to 98 / 2, and more preferably 90 / 10 to 97 / 3. In this specification, the mass ratio (a / b) is determined by dissolving 5% by mass of the poly(N-acylalkyleneimine)-modified organopolysiloxane of component (A1) in deuterated chloroform and measuring the mass ratio by nuclear magnetic resonance ( 1 This refers to the value determined from the integral ratio of alkyl or phenyl groups in the organopolysiloxane segment to methylene groups in the poly(N-acylalkyleneimine) segment by H-NMR analysis.

[0018] In the poly(N-acylalkyleneimine)-modified organopolysiloxane of component (A1), the weight average molecular weight (hereinafter also simply referred to as "MWg") of the organopolysiloxane segment between adjacent poly(N-acylalkyleneimine) segments is in the range of 5,000 to 40,000, and from the viewpoint of excellent adhesion to the skin, it is preferably 10,000 to 35,000, and more preferably 15,000 to 32,000.

[0019] In this specification, the term "organopolysiloxane segment between adjacent poly(N-acylalkyleneimine) segments" refers to a portion surrounded by a dashed line between the two points from the bonding point (bonding point A) of the poly(N-acylalkyleneimine) segment to the organopolysiloxane segment to the bonding point (bonding point B) of the adjacent poly(N-acylalkyleneimine) segment, as shown in the following formula (2), and is a region in which one R 2 SiO unit and one R 3 And y+1 (R 2 ) 2 The term "poly(N-acylalkyleneimine) segment" refers to a segment composed of the above R 3 -ZR binds to 4 This refers to.

[0020] [ka]

[0021] In the above general formula (2), R 2 each independently represents an alkyl group having 1 to 22 carbon atoms or a phenyl group; R 3 represents an alkylene group containing a heteroatom, -ZR 4 indicates a poly(N-acylalkyleneimine) segment, and R 4 represents a residue of a polymerization initiator, and y represents a positive number.

[0022] MWg is the molecular weight of the portion enclosed by the dashed line in the above general formula (2), and can be interpreted as the mass (g / mol) of the organopolysiloxane segment per mole of the poly(N-acylalkyleneimine) segment. When the functional groups of the modified organopolysiloxane, which is the raw material compound, are 100% substituted with poly(N-acylalkyleneimine), it coincides with the functional group equivalent (g / mol) of the modified organopolysiloxane.

[0023] The molecular weight of the poly(N-acylalkyleneimine) segment can be calculated from the molecular weight and degree of polymerization of the N-acylalkyleneimine unit, or can be measured by gel permeation chromatography (hereinafter, also simply referred to as "GPC") measurement. In the present invention, it refers to the polystyrene-equivalent number average molecular weight (hereinafter, also simply referred to as "MNox") measured by GPC measurement performed under the measurement conditions described below. From the viewpoint of improving adhesion to the skin and solubility in a solvent, MNox is preferably in the range of 500 to 4000, more preferably 800 to 3500, and even more preferably 1000 to 3000.

[0024] The MWg can be calculated from the content (mass %) of organopolysiloxane segments constituting the main chain (hereinafter, simply referred to as "Csi") according to the following formula (I). MWg=Csi×MNox / (100-Csi) (I)

[0025] The weight average molecular weight (hereinafter, simply referred to as "MWsi") of the organopolysiloxane segment constituting the main chain is 15,000 to 200,000, and preferably 50,000 to 170,000, more preferably 70,000 to 150,000, from the viewpoint of excellent adhesion to the skin and excellent uniformity of removal. In addition, the organopolysiloxane of component (A) can be easily blended into various products by dissolving it in a polar solvent such as water. Since the organopolysiloxane segment constituting the main chain has a common skeleton with the modified organopolysiloxane, which is a raw material compound, the MWsi is approximately the same as the weight average molecular weight of the modified organopolysiloxane, which is a raw material compound. The weight average molecular weight of the modified organopolysiloxane, which is a raw material compound, is measured by GPC under the measurement conditions described below and converted into polystyrene.

[0026] From the viewpoints of excellent adhesion to the skin and excellent uniform removal, the weight average molecular weight (hereinafter also simply referred to as "MWt") of the organopolysiloxane of component (A1) is preferably 15,000 to 200,000, more preferably 50,000 to 170,000, and even more preferably 70,000 to 150,000. MWt is a value measured by gel permeation chromatography (GPC) under the measurement conditions described below, and converted into polystyrene equivalent.

[0027] The organopolysiloxane of component (A1) has a high elastic modulus and a large amount of deformability, and in addition, when heated to a temperature range of 50 to 220°C, its plasticity improves significantly and it becomes soft, and when heating is stopped and the temperature returns to room temperature, it quickly regains its elasticity, which is a characteristic thermoplastic property.

[0028] The organopolysiloxane of component (A1) is, for example, a compound represented by the following general formula (3):

[0029] [ka]

[0030] (In the formula, R 2 has the same meaning as above, R 5 and R6 are R 2 or the following formulae (viii) to (xiii):

[0031] [ka]

[0032] R represents a monovalent group represented by any one of the following: 7 represents a monovalent group represented by the above formulas (viii) to (xiii), d represents a number from 91.5 to 1255.0, and e represents a number from 2.0 to 62.5. and a modified organopolysiloxane represented by the following general formula (4):

[0033] [ka]

[0034] (In the formula, R 1 and t have the same meaning as above) It is produced by reacting a cyclic imino ether represented by the following formula (1) with a terminally reactive poly(N-acylalkyleneimine) obtained by ring-opening polymerization of the cyclic imino ether represented by the following formula (1):

[0035] A polymerization initiator can be used for the ring-opening polymerization of the cyclic imino ether represented by general formula (4) (hereinafter, simply referred to as "cyclic imino ether (4)"). As the polymerization initiator, a compound having strong electrophilic reactivity, for example, an alkyl ester of a strong acid such as an alkyl ester of benzenesulfonate, an alkyl ester of p-toluenesulfonate, an alkyl ester of trifluoromethanesulfonate, an alkyl ester of trifluoroacetate, or a dialkyl sulfate can be used, and among them, a dialkyl sulfate is preferably used.

[0036] Examples of the polymerization solvent that can be used include acetates such as ethyl acetate and propyl acetate, ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone and methyl ethyl ketone, halogenated solvents such as chloroform and methylene chloride, nitrile solvents such as acetonitrile and benzonitrile, and aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide and dimethylsulfoxide, among which acetates are preferably used. The amount of the solvent used is usually 20 to 2000 parts by mass relative to 100 parts by mass of the cyclic iminoether (4).

[0037] The polymerization temperature is usually 30 to 170° C., preferably 40 to 150° C., and the polymerization time varies depending on the polymerization temperature etc., but is usually 1 to 60 hours.

[0038] For example, when 2-substituted-2-oxazoline is used as the cyclic iminoether (4), poly(N-acylethyleneimine) in which t=2 in the above general formula (1) is obtained, and when 2-substituted-dihydro-2-oxazine is used, poly(N-acylpropyleneimine) in which t=3 in the above general formula (1) is obtained.

[0039] The poly(N-acylalkyleneimine) obtained by living polymerization of the cyclic iminoether (4) has a reactive group at the end. Therefore, the organopolysiloxane of component (A) can be obtained by reacting the reactive group at the end of this poly(N-acylalkyleneimine) with the reactive groups (viii) to (xiii) of the modified organopolysiloxane represented by general formula (3).

[0040] The above-mentioned production method by living polymerization is effective in that the degree of polymerization can be easily controlled by the amounts of cyclic iminoether (4) and polymerization initiator used, as shown in the theoretical formula (II) below, and that a substantially monodisperse poly(N-acylalkyleneimine) having a narrower molecular weight distribution than that obtained by conventional radical polymerization can be obtained.

[0041]

number

[0042] The amount of the cyclic imino ether (4) and the amount of the polymerization initiator used are preferably such that MNi in formula (II) is 500-4,000, more preferably 800-3,500, and even more preferably 1,000-3,000.

[0043] The weight average molecular weight of the modified organopolysiloxane represented by general formula (3) is preferably 15,000 to 220,000, more preferably 50,000 to 190,000, and even more preferably 70,000 to 170,000, from the viewpoints of the solubility of the resulting organopolysiloxane in polar solvents such as water and ease of handling after dissolution.

[0044] Furthermore, the functional group equivalent of the modified organopolysiloxane represented by general formula (3) has an upper limit in order to satisfy the mass ratio (a / b) and MWg of the organopolysiloxane of component (A). From this viewpoint and from the viewpoint of imparting appropriate hydrophobicity to the main chain, the functional group equivalent is preferably 50,000 to 40,000, more preferably 10,000 to 35,000, and even more preferably 15,000 to 32,000. Here, the functional group equivalent of the modified organopolysiloxane represented by general formula (3) is the weight average molecular weight of the modified organopolysiloxane represented by general formula (3) divided by the number of R groups that the modified organopolysiloxane has per molecule. 7 This is the value obtained by dividing the number of

[0045] The amounts of the modified organopolysiloxane represented by the general formula (3) and the terminally reactive poly(N-acylalkyleneimine) used are preferably such that the mass ratio (modified organopolysiloxane / terminally reactive poly(N-acylalkyleneimine)) is within a range of 80 / 20 to 99 / 1 from the viewpoints of the elastic modulus and deformability of the resulting organopolysiloxane, and from the viewpoints of excellent adhesion to the skin and excellent uniform removal, the mass ratio is more preferably 83 / 17 to 98 / 2, and even more preferably 90 / 10 to 97 / 3.

[0046] In the present invention, in the synthesis of each organopolysiloxane, various molecular weights were measured according to the following measurement conditions.

[0047] <Measurement Conditions for Weight-Average Molecular Weight of Modified Organopolysiloxane> Column: Super HZ4000 + Super HZ2000 (manufactured by Tosoh Corporation) Eluent: 1 mM triethylamine / THF Flow rate: 0.35 mL / min Column temperature: 40 °C Detector: UV Sample: 50 μL

[0048] <Measurement Conditions for MNox and MWt> Column: Two K-804L (manufactured by Tosoh Corporation) were connected in series and used. Eluent: 1 mM dimethyldodecylamine / chloroform Flow rate: 1.0 mL / min Column temperature: 40 °C Detector: RI Sample: 50 μL

[0049] Also, for calculating the mass ratio (a / b) 1 1H-NMR measurement was performed under the following conditions. < 1 <1H-NMR Measurement Conditions> The composition of the obtained polymer was 1 confirmed by 1H-NMR (400 MHz, manufactured by Varian). A sample of 0.5 g dissolved in 2 g of the measurement solvent (deuterated chloroform) was measured. PULSE SEQUENCE ·Relax.delay: 30 seconds ·Pulse: 45 degrees ·Number of integrations: 8 times Confirmation peak near 0 ppm: Methyl group of polydimethylsiloxane, near 3.4 ppm: Methylene portion of ethyleneimine. The ratio of silicone to poly(N-propionylethyleneimine) was calculated from each integral value.

[0050] Examples of the organopolysiloxane of component (A1) include poly(N-formylethyleneimine)organosiloxane, poly(N-acetylethyleneimine)organosiloxane, and poly(N-propionylethyleneimine)organosiloxane.

[0051] Furthermore, among the components (A), the dimethicone crosslinked elastomer (A2) is preferably a silicone or a derivative thereof having a crosslinked structure obtained by polymerization of a monomer. For example, silicone or a derivative thereof obtained by polymerizing or copolymerizing a monomer selected from dimethicone, vinyl dimethicone, phenyl vinyl dimethicone, lauryl dimethicone, lauryl polydimethylsiloxyethyl dimethicone, etc. is preferable.

[0052] As the dimethicone crosslinked elastomer, from the viewpoints of excellent adhesion to the skin and uniform removal, polymethylsilsesquioxane, (dimethicone / vinyl dimethicone) crosspolymer, (dimethicone / phenyl vinyl dimethicone) crosspolymer, (vinyl dimethicone / lauryl dimethicone) crosspolymer, (vinyl dimethicone / methicone silsesquioxane) crosspolymer, (diphenyl dimethicone / vinyl diphenyl dimethicone / silsesquioxane) crosspolymer, polysilicone-1 crosspolymer, (PEG-15 / lauryl dimethicone) crosspolymer, and (dimethicone PEG-10 / 15) crosspolymer are preferred, and (vinyl dimethicone / methicone silsesquioxane) crosspolymer, (dimethicone / vinyl dimethicone) crosspolymer, (vinyl dimethicone / lauryl dimethicone) crosspolymer, and (PEG-15 / lauryl dimethicone) crosspolymer are more preferred.

[0053] The dimethicone crosslinked elastomer may be used as it is in a solid state, or may be used after being uniformly mixed with water or liquid oil. From the viewpoint of workability during blending, it is preferable to use it as a dispersion mixed with water or liquid oil, and from the viewpoint of good compatibility with the skin, it is more preferable to use it as a dispersion mixed with liquid oil. From the viewpoint of non-sticky feel when used, the liquid oil preferably has a viscosity at 25°C of 100 mPa·s or less, more preferably 50 mPa·s or less, even more preferably 30 mPa·s or less, and even more preferably 10 mPa·s or less. Here, the viscosity is measured using a B-type viscometer (VISCOMETER TVB-10, manufactured by Toki Sangyo Co., Ltd.) with rotor No. 1 at 60 rpm for 1 minute. Furthermore, from the viewpoint of non-sticky feel when used, the liquid oil is preferably at least one selected from silicone oil, hydrocarbon oil, and ester oil, more preferably at least one selected from silicone oil and hydrocarbon oil, even more preferably at least one selected from dimethylpolysiloxane, decamethylcyclopentasiloxane, isododecane, and liquid paraffin, and even more preferably at least one selected from dimethylpolysiloxane, decamethylcyclopentasiloxane, and isododecane.

[0054] The (dimethicone / vinyl dimethicone) crosspolymer may be directly incorporated into the composition, or may be incorporated as an aqueous dispersion in which it is dispersed in water, or as an oil dispersion in which it is dispersed in oil, specifically liquid oil. Examples of the solid crosspolymer include Trefil E-506S (solid content 100% by mass) (manufactured by Dow Corning Toray Co., Ltd.). Examples of the oil dispersion include KSG-15 (solid content 7% by mass), which is a mixture with decamethylcyclopentasiloxane (KF-995), KSG-16 (solid content 25% by mass), which is a mixture with dimethylpolysiloxane (KF-96A-6cs) (both manufactured by Shin-Etsu Chemical Co., Ltd.), and Trefil E-508 (solid content 70%), which is a mixture with dimethicone. Examples of the aqueous dispersion include commercially available products such as BY29-119 (solid content 63% by mass) and BY29-129 (solid content 63% by mass) (both manufactured by Dow Corning Toray Co., Ltd.).

[0055] The (dimethicone / phenylvinyldimethicone) crosspolymer may be blended directly into the composition, or may be blended as an oil dispersion in which it is dispersed in oil, specifically liquid oil. As the oil dispersion, a commercially available product such as KSG-18A (solid content 15% by mass) (manufactured by Shin-Etsu Chemical Co., Ltd.), which is a mixture with diphenylsiloxyphenyl trimethicone (KF-56A), can be used.

[0056] In addition, the (vinyl dimethicone / lauryl dimethicone) crosspolymer may be blended into the composition as it is, or may be blended as an oil dispersion in which it is dispersed in oil, specifically liquid oil. As the oil dispersion, commercially available products such as KSG-41A (solid content 25% by mass), which is a mixture with liquid paraffin, KSG-42A (solid content 20% by mass), which is a mixture with light isoparaffin (isododecane), KSG-43 (solid content 30% by mass), which is a mixture with glyceryl tri-2-ethylhexanoate, and KSG-44 (solid content 30% by mass), which is a mixture with squalane (all manufactured by Shin-Etsu Chemical Co., Ltd.), can be used. As the (vinyl dimethicone / methicone silsesquioxane) crosspolymer, commercially available solid products such as KSP-100 (solid content 100% by mass), KSP-101 (solid content 100% by mass), KSP-102 (solid content 100% by mass), and KSP-105 (solid content 100% by mass) (manufactured by Shin-Etsu Chemical Co., Ltd.) can be used.

[0057] The (dimethicone PEG-10 / 15) crosspolymer may be blended directly into the composition, or may be blended as an oil dispersion in which it is dispersed in oil, specifically liquid oil. As the oil dispersion, a commercially available product such as KSG-210 (solid content 25% by mass) (manufactured by Shin-Etsu Chemical Co., Ltd.), which is a mixture with dimethylpolysiloxane (KF-96A-6cs), can be used. The (PEG-15 / lauryl dimethicone) crosspolymer may be blended directly into the composition, or may be blended as an oil dispersion in which it is dispersed in oil, specifically liquid oil. As the oil dispersion, commercially available products such as KSG-310 (solid content 30% by mass), which is a mixture with liquid paraffin, KSG-320 (solid content 25% by mass), which is a mixture with light isoparaffin (isododecane), and KSG-330 (solid content 20% by mass), which is a mixture with glyceryl tri-2-ethylhexanoate (all manufactured by Shin-Etsu Chemical Co., Ltd.), can be used.

[0058] As component (A), from the viewpoints of improving removability, providing excellent adhesion during application, providing a thin finish, providing excellent makeup durability, and suppressing dryness, poly(N-acylalkyleneimine)-modified organopolysiloxane is preferred.

[0059] One or more kinds of component (A) can be used, and the content is preferably 0.1% by mass or more in the total composition, more preferably 0.4% by mass or more, even more preferably 1% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less, from the viewpoints of excellent shape retention of the oil-based solid cosmetic, forming a uniform coating film when applied, obtaining a thin finish, and suppressing dryness. The content of component (A) is preferably 0.1 to 10% by mass in the total composition, more preferably 0.4 to 8% by mass, and even more preferably 1 to 5% by mass.

[0060] The hydrocarbon wax of component (B) is one that is commonly used in cosmetics, and examples thereof include paraffin wax, ceresin, synthetic hydrocarbon wax, Fischer-Tropsch wax, microcrystalline wax, and polyethylene wax.

[0061] Component (B) preferably contains (B1) a hydrocarbon wax having a penetration number at 25°C of more than 20 and 110 or less. The penetration of (B1) at 25° C. is more preferably 25 to 80. Here, the penetration rate is measured by measuring the length that a specified needle (needle mass 2.5±0.02g, needle holder mass 47.5±0.02g, weight mass 50±0.05g) penetrates into a wax sample kept at 25±0.1°C in 5 seconds, and multiplying this penetration distance (mm) by 10 to obtain the penetration rate, and is a value measured in accordance with JIS K-2235-5.4 (1991). (B1) Examples of the hydrocarbon wax having a penetration at 25° C. of more than 20 and not more than 110 include microcrystalline wax and paraffin wax, with microcrystalline wax being preferred. These waxes can be commercially available products. For example, microcrystalline waxes include Multiwax W-445, W-835 (all manufactured by SONNEBORN), Hi-Mic-1045, 1070, 2045 (all manufactured by Nippon Seiro), refined microcrystalline wax (manufactured by Nikko Rica Corporation), and 155° Microwax (manufactured by Nippon Oil Corporation).

[0062] One or more kinds of component (B1) can be used, and the content is preferably 0.05% by mass or more in the total composition, more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 8% by mass or less, from the viewpoints of suppressing sweating on the surface of the oil-based solid cosmetic during storage, providing excellent stability, improving removal, providing excellent adhesion during application, and providing a thin finish. The content of component (B1) is preferably 0.05 to 15% by mass, more preferably 0.1 to 10% by mass, and even more preferably 0.2 to 8% by mass in the total composition.

[0063] The mass ratio (B1) / (B) of component (B1) to component (B) is preferably 0.05 or more, more preferably 0.07 or more, even more preferably 0.08 or more, and preferably 0.5 or less, more preferably 0.4 or less, and even more preferably 0.35 or less, from the viewpoints of suppressing sweating on the surface of the oil-based solid cosmetic during storage, providing excellent stability, further improving removal, providing excellent adhesion during application, providing a thin finish, and suppressing shine and dryness caused by sebum over time. The mass ratio (B1) / (B) of component (B1) to component (B) is preferably 0.05 to 0.5, more preferably 0.07 to 0.4, and even more preferably 0.08 to 0.35.

[0064] One or more types of component (B) may be used, and the content is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 4% by mass or more, preferably 15% by mass or less, more preferably 13% by mass or less, and even more preferably 10% by mass or less, based on the overall composition, from the viewpoint of excellent shape retention of the oil-based solid cosmetic preparation. The content of component (B) is preferably 1 to 15% by mass, more preferably 2 to 13% by mass, and even more preferably 4 to 10% by mass, based on the overall composition.

[0065] Component (C) is a non-volatile ester oil that is liquid at 25°C. In the present invention, the term "liquid" refers to something that has fluidity, and includes cream and paste forms. Non-volatile oil is defined as oil that loses less than 1% in weight after 1 g of oil is spread on a 48 mm diameter glass petri dish and left at 25°C and normal pressure for 24 hours.

[0066] The ester oils of component (C) are those commonly used in cosmetics, and examples thereof include monoester oils such as cetyl 2-ethylhexanoate, isononyl isononanoate, isotridecyl isononanoate, isopropyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, and stearyl stearate; diester oils such as diisostearyl malate, neopentyl glycol dicaprate, glyceryl diisostearate, and neopentyl glycol diethylhexanoate; and triester oils such as glyceryl tri(caprylic acid / capric acid) and glyceryl tri(2-ethylhexanoate).

[0067] Among these, from the viewpoints of suppressing sweating on the surface of the oil-based solid cosmetic during storage and providing excellent stability, further improving removability, providing excellent adhesion during application, providing a thin finish, and suppressing shine and dryness caused by sebum over time, triester oils are preferred, fatty acid triglyceride oils are more preferred, and tri-2-ethylhexanoate is even more preferred.

[0068] One or more kinds of component (C) can be used, and the content is preferably 1% by mass or more in the total composition, more preferably 2% by mass or more, even more preferably 4% by mass or more, preferably 12% by mass or less, more preferably 10% by mass or less, and even more preferably 8% by mass or less, from the viewpoints of suppressing sweating on the surface of the oil-based solid cosmetic during storage, providing excellent stability, further improving removal, providing excellent adhesion during application, providing a thin finish, and suppressing shine and dryness caused by sebum over time. The content of component (C) is preferably 1 to 12% by mass in the total composition, more preferably 2 to 10% by mass, and even more preferably 4 to 8% by mass.

[0069] In the present invention, the mass ratio (B) / (C) of component (B) to component (C) is preferably 0.2 or more, more preferably 0.3 or more, even more preferably 0.6 or more, preferably 5 or less, more preferably 4 or less, and even more preferably 2 or less, from the viewpoints of suppressing sweating on the surface of the oily solid cosmetic during storage, providing excellent stability, further improving removability, providing excellent adhesion during application, providing a thin finish, and suppressing shine and dryness caused by sebum over time. The mass ratio (B) / (C) of component (B) to component (C) is preferably 0.2 to 5, more preferably 0.3 to 4, and even more preferably 0.6 to 2.

[0070] There are no limitations on the powder of component (D) so long as it is one that is commonly used in cosmetics, and examples of the powder that can be used include extender pigments, color pigments, and luster pigments. Examples of the extender pigment include inorganic pigments such as silicic acid, silicic anhydride, magnesium silicate, talc, sericite, boron nitride, mica, synthetic mica, glass flakes, synthetic phlogopite, kaolin, clay, bentonite, bismuth oxychloride, zirconium oxide, magnesium oxide, aluminum oxide, calcium sulfate, barium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, aluminum silicate, magnesium silicate, silica, alumina, and composite pigments thereof. Specific examples of composite pigments include titanium oxide-coated mica, zinc oxide-coated mica, titanium oxide-zinc oxide-coated mica, iron oxide-coated mica, iron oxide-coated mica titanium, barium sulfate-titanium oxide-coated mica, iron oxide-coated synthetic phlogopite, chromium oxide-coated mica titanium, titanium oxide-coated glass powder, iron oxide-coated glass powder, titanium oxide-containing glass powder, and iron oxide-containing glass powder.

[0071] Examples of color pigments include metal oxides such as titanium oxide, zinc oxide, yellow iron oxide, red iron oxide, black iron oxide, Prussian blue, ultramarine blue, chromium oxide, and chromium hydroxide; metal complexes such as manganese violet and cobalt titanate; inorganic pigments such as carbon black; synthetic organic pigments such as Red No. 3, Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 227, Red No. 228, Red No. 230, Red No. 401, Red No. 405, Red No. 505, Orange No. 203, Orange No. 204, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 401, Blue No. 1, and Blue 404; and natural organic pigments such as β-carotene, caramel, and paprika color.

[0072] Luster pigments that can be used include plate-like powders such as mica, synthetic phlogopite, glass, silica, alumina, etc., the surface of which is coated with colorants such as titanium oxide, iron oxide, silicon oxide, Prussian blue, chromium oxide, tin oxide, chromium hydroxide, gold, silver, carmine, organic pigments, etc., as well as film rolls cut into any shape such as polyethylene terephthalate-polymethyl methacrylate laminated powder, polyethylene terephthalate-aluminum vapor-deposited powder, and polyethylene terephthalate-gold vapor-deposited laminated powder.

[0073] These powders can be used after being hydrophobized. The hydrophobization treatment is not limited to any treatment that is applied to ordinary cosmetic powders, and examples of the hydrophobization treatment include silicone treatment, fatty acid treatment, lauroyl lysine treatment, lecithin treatment, amino acid treatment such as N-acyl amino acid treatment, metal soap treatment, etc. Among these, silicone treatment and amino acid treatment are preferred, silicone, stearoyl glutamic acid, and lauroyl aspartic acid are more preferred, and at least silicone treatment is even more preferred.

[0074] One or more kinds of component (D) can be used, and the content is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 25% by mass or more, and is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 60% by mass or less, in terms of realizing excellent covering power, finish, and excellent aesthetics, based on the total composition. The content of component (D) is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 25 to 60% by mass, based on the total composition.

[0075] The oily solid cosmetic preparation of the present invention may further contain a non-volatile silicone oil that is liquid at 25°C. Examples of non-volatile silicone oils include those used in ordinary cosmetics, such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and modified silicone oils such as polyether-modified silicone, alkyl-modified silicone, higher fatty acid ester-modified silicone, higher alkoxy-modified silicone, and fluorine-modified silicone. Of these, from the viewpoints of providing excellent shape retention of an oil-based solid cosmetic composition, excellent adhesion during application, and a thin finish, dimethylpolysiloxane and methylphenylpolysiloxane are preferred, and dimethylpolysiloxane and methylphenylpolysiloxane having a viscosity of 5 mPa s or more at 25°C are more preferred.

[0076] One or more kinds of non-volatile silicone oils can be used, and the content is preferably 10% by mass or more in the total composition, more preferably 20% by mass or more, even more preferably 30% by mass or more, preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 50% by mass or less, from the viewpoint of obtaining excellent shape retention of the oil-based solid cosmetic, excellent adhesion during application, and a thin finish. The content of the non-volatile silicone oil is preferably 10 to 60% by mass in the total composition, more preferably 20 to 55% by mass, and even more preferably 30 to 50% by mass.

[0077] The oily solid cosmetic preparation of the present invention may further contain oily components other than those mentioned above. In the present invention, the content of volatile oil is preferably 1% by mass or less in the total composition from the viewpoint of stability, and more preferably is substantially free of volatile oil.

[0078] In the present invention, the water content is preferably 1% by mass or less in the total composition from the viewpoint of stability, and more preferably is substantially free of water.

[0079] In addition to the above-mentioned components, the oil-based solid cosmetic preparation of the present invention may contain components used in ordinary cosmetics, such as surfactants, water-soluble and oil-soluble polymers, ethanol, polyhydric alcohols, preservatives, antioxidants, colorants, thickeners, pH adjusters, fragrances, ultraviolet absorbing agents, ultraviolet scattering agents, moisturizing agents, blood circulation promoters, cooling agents, antiperspirants, germicides, skin activators, etc.

[0080] The oily solid cosmetic preparation of the present invention can be produced by a conventional method, for example, by heating, dissolving and mixing the ingredients, filling the mixture into a container such as a metal dish, and then cooling the mixture. The oily solid cosmetic preparation of the present invention preferably has a penetration hardness at 30° C. using a 2 mmφ jig of 25 to 120 g, more preferably 30 to 100 g. The penetration hardness is measured using a rheometer COMPAC-100II manufactured by Sun Scientific Corporation at 30° C. with a tool diameter of 2 mm and a table speed of 3.0 cm / min, and the maximum load (g) is measured when the tool penetrates to a depth of 2 mm.

[0081] The oil-based solid cosmetic composition of the present invention can be produced according to a conventional method and can be used as a makeup cosmetic composition such as a makeup base, foundation, lipstick, blusher, eye shadow, etc., and is preferably used as a foundation.

[0082] The oil-based solid cosmetic preparation of the present invention can be applied by applying an appropriate amount to the hand or sponge and gently gliding it onto the skin in a conventional manner. It can also be applied to the skin using an application tool having a roller, for example, as shown in Figure 1. In this case, the cosmetic preparation can be applied by rolling the roller back and forth on the cosmetic preparation to apply an appropriate amount, and rolling the roller back and forth on the skin with a comfortable strength. As a result, the cosmetic preparation can be applied more evenly to the skin with improved removability. EXAMPLES

[0083] Synthesis Example 1 3.63 g (0.036 mol) of 2-ethyl-2-oxazoline and 8.46 g of ethyl acetate were mixed, and the mixture was dehydrated with 0.6 g of molecular sieves (Zeorum A-4, manufactured by Tosoh Corporation) at 28° C. for 15 hours. In addition, 100 g of side chain primary aminopropyl modified polydimethylsiloxane (KF-8015, Shin-Etsu Silicones, weight average molecular weight 100,000, amine equivalent 20,000) was mixed with 203 g of ethyl acetate, and the mixture was dehydrated with 15.2 g of molecular sieves at 28°C for 15 hours. To the above-mentioned dehydrated 2-ethyl-2-oxazoline in ethyl acetate solution, 0.54 g (0.0035 mol) of diethyl sulfate was added, and the mixture was heated under reflux at 80°C for 8 hours under a nitrogen atmosphere to synthesize terminal-reactive poly(N-propionylethyleneimine). The number average molecular weight measured by GPC was 1200. This terminally reactive poly(N-propionylethyleneimine) solution was added all at once to the above dehydrated side chain primary aminopropyl modified polydimethylsiloxane solution, and the mixture was heated to reflux at 80° C. for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain N-propionylethyleneimine-dimethylsiloxane copolymer as a white rubbery solid (102 g). The mass ratio of the organopolysiloxane segment in the final product was 0.96, and the weight average molecular weight of the final product was 104,000.

[0084] [Table 1]

[0085] Examples 1 to 8, Comparative Example 1 An oil-based solid cosmetic (foundation) with the composition shown in Table 2 was manufactured and its needle penetration hardness at 30°C was measured, and it was also evaluated for stability (whether or not it caused sweating), whether the cosmetic was evenly removed, how well it adhered during application, the thin finish, whether it was shiny due to sebum after 6 hours, whether it felt dry after 6 hours, and whether it could be evenly applied to the skin using a roller. The results are also shown in Table 2.

[0086] (Manufacturing method) The oil phase components including components (A), (B), and (C) were mixed and dissolved by heating at 90° C. Furthermore, the powder phase components including component (D) that had been mixed separately in a grinder were added, and the mixture was thoroughly mixed and stirred until homogenous while maintaining the temperature at 85° C. This mixture was filled into a metal dish and cooled to room temperature to obtain an oil-based solid cosmetic product (foundation).

[0087] (Evaluation method) (1) Penetration hardness at 30°C: For each oil-based solid cosmetic product (foundation), a COMPAC-100II rheometer manufactured by Sun Scientific Corporation was used to measure the maximum load (g) when the jig penetrated to a depth of 2 mm at 30°C with a jig diameter of 2 mm and a table speed of 3.0 cm / min, and this was taken as the penetration hardness.

[0088] (2) Stability (whether or not sweating occurs): Each oil-based solid cosmetic preparation (foundation) was stored at 40° C. for 1 hour, and then the surface properties were visually evaluated according to the following criteria. 5: No sweating is observed on the surface. 4: Slight sweating is observed on some parts of the surface. 3: Sweating is observed over the entire surface, producing small oil droplets. 2: Sweating is observed over the entire surface, producing large oil droplets. 1: Sweating is observed over the entire surface, producing an oily film and a glossy appearance.

[0089] (3) Cosmetics are applied evenly: Five expert panelists applied an appropriate amount of each oil-based solid cosmetic product (foundation) to a sponge and evaluated the degree of removal according to the following criteria. The results were shown as the total score given by the five panelists. 5; It can be applied very evenly. 4;Can be applied evenly. 3: Can be applied fairly evenly. 2; It is not very evenly applied. 1: It cannot be applied evenly.

[0090] (4) Adhesion during application: Five expert panelists took an appropriate amount of each oil-based solid cosmetic product (foundation) onto a sponge, spread it onto the skin, and sensory evaluated the adhesion according to the following criteria. The results were shown as the total score given by the five panelists. 5;Adheres firmly to the skin. 4;Fits closely to the skin. 3;Fits slightly close to the skin. 2;It doesn't adhere very well to the skin. 1;Does not adhere to the skin.

[0091] (5) Thin finish: Five expert panelists applied an appropriate amount of each oil-based solid cosmetic product (foundation) to a sponge, spread it on the skin, and then sensory evaluated the naturalness of the finish (thin finish) according to the following criteria. The results were shown as the total score of the five panelists. 5;A fairly thin finish is achieved. 4: A thin finish is achieved. 3: A slightly thin finish is achieved. 2; The finish is not very thin. 1: The finish is not thin.

[0092] (6) No shine caused by sebum after 6 hours: Five expert panelists applied an appropriate amount of each oil-based solid cosmetic product (foundation) to a sponge, spread it on the skin, and then evaluated the durability of the finish after six hours (the lack of shine caused by sebum) according to the following criteria. The results were shown as the total score of the five panelists. 5. No greasiness caused by sebum at all. 4. No shine caused by sebum. 3. Not much greasiness due to sebum. 2: There is some shine due to sebum. 1: There is shine due to sebum.

[0093] (7) Lack of dryness after 6 hours: Five expert panelists applied an appropriate amount of each oil-based solid cosmetic product (foundation) to a sponge, spread it on the skin, and then evaluated the lack of dryness after six hours using the following criteria. The results were shown as the total score of the five panelists. 5. No dryness at all. 4;No dry feeling. 3;It doesn't feel too dry. 2: Feels slightly dry. 1: Feels dry.

[0094] (8) Use a roller to apply evenly to the skin: A specialist panelist performed a sensory evaluation of the degree of removal of each oil-based solid cosmetic product (foundation) when the roller shown in FIG. 1 was moved back and forth therethrough, according to the following criteria. 5; It can be applied very evenly. 4;Can be applied evenly. 3: Can be applied fairly evenly. 2; It is not very evenly applied. 1: It cannot be applied evenly.

[0095] [Table 2]

Claims

1. The following components (A), (B), (C) and (D): (A) A silicone-based oily gelling agent, (B) A hydrocarbon-based wax, (C) A non-volatile ester oil that is liquid at 25°C, (D) Powder An oily solid cosmetic containing the same.

2. The oily solid cosmetic according to Claim 1, wherein the mass ratio (B) / (C) of component (B) to component (C) is 0.2 to 5.

3. The oily solid cosmetic according to Claim 1, wherein the penetration hardness at 30°C with a 2 mmφ tool is 25 to 120 g.

4. The oily solid cosmetic according to Claim 1 or 2, wherein the content of component (A) is 0.1 to 10% by mass, the content of component (B) is 1 to 15% by mass, and the content of component (C) is 1 to 12% by mass.

5. A method for using the oily solid cosmetic according to Claim 1 or 2, which is applied to the skin with an applicator having a roller.