Oil-based cosmetic material

Abstract

Provided is an oil-based cosmetic material that excels in preventing smudging and has excellent firmness (elasticity), abrasion resistance (makeup longevity), and sustained moisturizing effect. The present invention is an oil-based cosmetic material containing the following components (A) to (D): (A) a non-volatile oil that is liquid at 25°C, (B) a semi-solid oil that is semi-solid at 25°C, (C) an oil-based gelling agent, and (D) a polyorganosiloxane having a specific block structure.

Description

Oil-based cosmetics

[0001] This invention relates to oil-based cosmetics.

[0002] Makeup cosmetics such as lipstick, blush, and eyeshadow are items that add color to areas such as the lips, cheeks, and eyelids, creating a glamorous finish. These are often provided as oil-based cosmetics due to their vivid color and long-lasting wear. In recent years, with the diversification of market trends, the finish and feel of the makeup film that consumers demand have also diversified. However, a makeup film that does not smudge and has excellent abrasion resistance remains an important quality that is in demand regardless of trends. Furthermore, in recent years, many consumers are seeking skincare elements in makeup cosmetics, and there is a tendency to prefer makeup films that provide elasticity that gives a plump and firm feeling, and that provide long-lasting moisture. Various studies have been conducted to realize a makeup film with excellent abrasion resistance (long-lasting wear).

[0003] For example, a technology has been proposed that creates an oil-based cosmetic that, when applied to the skin, does not have the stickiness characteristic of oil, has a smooth and excellent feel, adheres well to the skin, and makes pores less noticeable, by containing a specific amount of liquid oil excluding volatile silicone oil, a film-forming agent, and a hydrophobic surface-treated powder (see, for example, Patent Document 1).

[0004] Furthermore, technologies for reducing the feeling of dryness over time in lip cosmetics are known. For example, a technology has been proposed that contains an oil gelling agent, a paste oil with a specific melting point, a liquid oil, and a powder, and after examining the amount of each component, it is possible to apply it thinly without unevenness, obtain a transparent matte finish, and reduce the feeling of dryness over time (see, for example, Patent Document 2).

[0005] Japanese Patent Publication No. 2024-085999 Japanese Patent Publication No. 2021-031427

[0006] However, while the technology described in Patent Document 1 offered excellent makeup longevity, the liquid oil tended to cause the makeup film to bleed easily, and the volatile oils tended to cause a feeling of dryness as they evaporated, resulting in a short-lived moisturizing effect. Similarly, while the technology described in Patent Document 2 offered excellent long-lasting moisturizing effects, the paste oil and liquid oil tended to cause the makeup film to be easily damaged by friction. Therefore, it has been difficult to develop oil-based cosmetics that offer excellent resistance to bleeding, firmness (elasticity), abrasion resistance (makeup longevity), and moisturizing effects using conventional technologies.

[0007] Therefore, the present invention aims to develop an oil-based cosmetic that is excellent in terms of resistance to bleeding, firmness (elasticity), abrasion resistance (makeup longevity), and sustained moisturizing effect.

[0008] In view of the above circumstances, the inventors conducted diligent studies and found that by combining a non-volatile oil that is liquid at 25°C, an oil that is semi-solid at 25°C, an oily gelling agent, and a polyorganosiloxane having a specific block structure, an oily cosmetic composition with excellent resistance to bleeding, firmness (elasticity), abrasion resistance (makeup longevity), and sustained moisturizing effect can be obtained, thus completing the present invention.

[0009] In other words, the present invention includes the following: [1] The following components (A) to (D): (A) A non-volatile oil that is liquid at 25°C (B) A semi-solid oil that is semi-solid at 25°C (C) An oily gelling agent (D) A polyorganosiloxane having a block structure, represented by the following general formula (1), having a weight-average molecular weight of 500,000 or more, being solid at room temperature, and having a softening point of 50°C or higher (In the formula, R １ , R ２ , R ３ , R ４ and R ５A is an oily cosmetic containing a ) which is an oily cosmetic containing a ) which is an oily cosmetic containing a ) which is an oily cosmetic containing a ) which is an oily cosmetic containing a ) which is an oily cosmetic containing a ) which is an oily cosmetic containing a ) which is an oily cosmetic containing a ) which is an oily cosmetic containing a ) which is an oily cosmetic containing a ) which is an oily cosmetic according to [1] which is an oily cosmetic according to [1] which is an oily cosmetic containing a ) [3] The oily cosmetic composition according to [1] or [2], wherein component (C) is one or more selected from the group consisting of organically modified clay minerals, dextrin fatty acid esters, waxes, amino acid-based gelling agents, fuming silica, and fatty acids or their salts (excluding component (A)). [4] The oily cosmetic composition according to [1] or [2], wherein component (A) is one or more selected from the group consisting of ester oils, silicone oils, hydrocarbon oils, higher alcohols, and fatty acids. [5] The oily cosmetic composition according to [1] or [2], wherein component (B) is hydrocarbon oil and / or ester oil. [6] The oily cosmetic composition according to [1] or [2], wherein the mass ratio (A) / (D) of component (A) to component (D) is 0.1 to 15. [7] The oily cosmetic composition according to [1] or [2], wherein the mass ratio (B) / (D) of component (B) to component (D) is 0.1 to 10. [8] The oily cosmetic composition according to [1] or [2], further containing component (E) a polyhydric alcohol. [9] The oily cosmetic composition according to [1] or [2], which is a lip cosmetic composition.

[0010] The present invention provides an oil-based cosmetic composition that is excellent in terms of resistance to bleeding, firmness (elasticity), abrasion resistance (makeup longevity), and sustained moisturizing effect.

[0011] The present invention will now be described in detail. However, the present invention is not limited to the following embodiments and can be freely modified within the scope of the present invention. In this specification, percentages are expressed in mass unless otherwise specified. In this specification, when a numerical range is expressed using "~", the range includes the values ​​at both ends. In this invention, "viscosity" refers to the value obtained by measurement using a B-type viscometer (manufactured by Shibaura Systems Co., Ltd.) at 25°C.

[0012] Component (A) used in the present invention is a non-volatile oil that is liquid at 25°C. In the present invention, "liquid at 25°C" means an oil that is fluid at 25°C and 1 atmosphere. Furthermore, in the present invention, a non-volatile oil at 25°C means an oil with a boiling point of 260°C or higher at 1 atmosphere.

[0013] Component (A) in the present invention is not particularly limited as long as it is commonly used in cosmetics, for example, hydrocarbon oils such as polybutene, hydrogenated polyisobutene, α-olefin oligomer, liquid paraffin, and heavy liquid isoparaffin; triglycerides such as glyceryl tri-2-ethylhexanoate and caprylic / capric triglyceride; polyglyceryl-2 triisostearate (diglyceryl triisostearate), polyglyceryl-2 tetraisostearate (diglyceryl tetraisostearate), polyglyceryl-2 diisostearate Polyglycerin fatty acid esters such as diglyceryl diisostearate, polyglyceryl-2 monoisostearate (diglyceryl monoisostearate), polyglyceryl-10 pentaisostearate (decaglyceryl pentaisostearate), polyglyceryl-10 nonaisostearate (decaglyceryl nonaisostearate), polyglyceryl-10 decaisostearate (decaglyceryl decaisostearate), polyglyceryl-10 decaisooctanoate (decaglyceryl decaisooctanoate), diisostearyl malate, (vinyl phosphate Roridone / Hexadecene copolymer, propylene glycol dicaprate, neopentyl glycol dioctanoate, isopropyl myristate, C12-15 alkyl benzoate, isopropyl sebacate, isononyl isononanoate, cetyl ethylhexanoate, isotridecyl isononanoate, tridecyl trimellitate, pentaerythrityl tetraisostearate, pentaerythrityl tetraethylhexanoate, sucrose tetraisostearate, sucrose hexatetraisostearate, and other sugar fatty acid ester oils; castor oil, Examples of vegetable oils include avocado oil, almond oil, perilla oil, olive oil, safflower oil, sesame oil, rice bran oil, soybean oil, corn oil, palm oil, sunflower oil, and jojoba oil; silicone oils such as phenyl-modified silicones like dimethylpolysiloxane, diphenylsiloxyphenyl trimethicone, phenyl trimethicone, diphenyl dimethicone, and trimethylpentaphenyltrisiloxane; higher alcohols such as oleyl alcohol, octyldodecanol, and decyltetradecanol; and fatty acids such as isostearic acid, oleic acid, linoleic acid, and linolenic acid.

[0014] In the present invention, component (A) is preferably one or more selected from the group consisting of ester oils, silicone oils, hydrocarbon oils, higher alcohols, and fatty acids, more preferably one or more selected from the group consisting of ester oils, silicone oils, and hydrocarbon oils, and even more preferably one or more selected from the group consisting of ester oils and silicone oils.

[0015] The viscosity of component (A) used in the present invention at 25°C is not particularly limited. For example, from the viewpoint of no bleeding, it is preferably 5 mPa·s or more, more preferably 10 mPa·s or more, even more preferably 20 mPa·s or more, even more preferably 30 mPa·s or more, especially more preferably 40 mPa·s or more, and most preferably 50 mPa·s or more. Furthermore, from the viewpoint of abrasion resistance, it is preferably 30,000 mPa·s or less, more preferably 25,000 mPa·s or less, even more preferably 20,000 mPa·s or less, even more preferably 15,000 mPa·s or less, especially more preferably 10,000 mPa·s or less, and most preferably 5,000 mPa·s or less. A pressure of 5 to 30,000 mPa·s is preferred, 10 to 25,000 mPa·s is more preferred, 20 to 20,000 mPa·s is even more preferred, 30 to 15,000 mPa·s is even more preferred, 40 to 10,000 mPa·s is particularly preferred, and 50 to 5,000 mPa·s is most preferred. Within this range, it is more preferable because it is superior in terms of lack of bleeding and abrasion resistance (cosmetic longevity).

[0016] Commercially available products include hydrogenated polyisobutenes such as Pearlream 18, Pearlream 24, and Pearlream 46 (all manufactured by NOF Corporation), and polybutenes such as refined polybutene HV-100F (SB) (manufactured by Nippon Natural Products Co., Ltd.), Nisseki Polybutene HV-35, Nisseki Polybutene HV-100, Nisseki Polybutene 300F, and Nisseki Polybutene. 1900F (manufactured by JX Nikko Nippon Oil & Energy Corporation), Nomcoat HP100 (manufactured by Nisshin Oillio Group), as polyglyceryl-2 triisostearate, Cosmol 43V, as polyglyceryl-2 tetraisostearate, Cosmol 44V (both manufactured by Nisshin Oillio Group), as polyglyceryl-10 pentaisostearate, IS-1005P, as polyglyceryl-10 decaisostearate, IS-1009P (both manufactured by Sakamoto Pharmaceutical Co., Ltd.), as (VP / hexadecene) copolymer, ANTARON V216 (manufactured by ISP Japan), as tridecyl trimellitate, LIPONATE TDTM (manufactured by LIPO CHEMICALS), DOCADIT TM-13N (manufactured by Nisshin Oillio Group), as dimethylpolysiloxane, KF-96A-1000CS, KF-96-5000CS, KF-96-10000CS, KF-96-10000CS, KF-56, KF-54, KF-54HV, FL-100-100CS, FL-100-450CS, FL-100-1000CS, FL-100-10000CS (all of the above, Examples include SH556 (manufactured by Toray Dow Corning) as phenyl trimethicone, KF-56A as diphenylsiloxy phenyl trimethicone, and KF-50, KF-53, and KF-54 (all manufactured by Shin-Etsu Chemical Co., Ltd.) as diphenyl dimethicone. These can be used without particular restriction, and one or more types can be used in combination.

[0017] The content of component (A) used in the present invention is not particularly limited, but is preferably 1% by mass or more (hereinafter simply abbreviated as "%)" in the oily cosmetic composition, more preferably 5% or more, and even more preferably 8% or more. Also, 60% or less is preferred, 50% or less is more preferred, and 40% or less is even more preferred. Also, 1 to 60% is preferred, 5 to 50% is more preferred, and 8 to 40% is even more preferred. Within this range, it is more preferable because it is superior in terms of lack of bleeding, firmness (elasticity), and abrasion resistance (makeup longevity).

[0018] Component (B) used in the present invention is a semi-solid oil at 25°C. In the present invention, "semi-solid at 25°C" refers to a state that lies between liquid and solid at 25°C and 1 atmosphere, and is distinguished from liquid oil and solid oil. It refers to a state in which there is no fluidity at 25°C and it can be freely deformed by external force. The semi-solid oil at 25°C is preferably an oil having a melting point of 30 to 65°C at 1 atmosphere, and more preferably an oil having a melting point of 35 to 60°C. Here, "solid at 25°C" refers to a substance that is solid at 25°C and 1 atmosphere. The melting point of component (B) used in the present invention is the value measured by the second method of melting point measurement listed in the Japanese Pharmacopoeia. However, the value for petrolatum is the value measured by the third method.

[0019] Component (B) is not particularly limited as long as it is commonly used in cosmetics, and examples include hydrocarbon oils, dimer acid esters, triglycerides, fatty acid dipentaerythrityl esters, acyl amino acid esters, fatty acid hydrogenated castor oil, vegetable oils, animal oils, fatty acid cholesterol esters, fatty acid phytosterol esters, and other ester oils. Specifically, these include hydrocarbon oils such as petrolatum and paraffin, dimer acid esters such as dimer dilinoleyl (phytosteryl / isostearyl / cetyl / stearyl / behenyl) and dimer dilinoleyl bis(behenyl / isostearyl / phytosteryl) dimer dilinoleate, triglycerides such as (caprylic / caprin / myristic / stearic acid) triglyceride, fatty acid dipentaerythrityl such as hexa(hydroxystearate / isostearate) dipentaerythrityl and hexa(hydroxystearate / stearic acid / rosinic acid) dipentaerythrityl Examples include erythrityl esters, acyl amino acid esters such as di(octyldodecyl / phytosteryl / behenyl) lauroyl glutamate, di(cholesteryl / behenyl / octyldodecyl) lauroyl glutamate, hydrogenated castor oil such as hydrogenated castor oil stearate, cocoa butter, shea butter, jojoba esters, vegetable fats such as mango butter, animal fats such as beeswax, fatty acid phytosterol esters such as macadamia nut oil fatty acid phytosteryl, and bis-diglyceryl polyacyladipate-2, which can be used individually or in combination of two or more.

[0020] In the present invention, from the viewpoint of not bleeding, abrasion resistance (makeup longevity), and sustained moisturizing effect, hydrocarbon oils and / or ester oils are preferred, one or more selected from the group consisting of petrolatum, dimer acid esters, fatty acid dipentaerythrityl esters, acyl amino acid esters, fatty acid cholesterol esters, and fatty acid phytosterol esters are more preferred, one or more selected from the group consisting of petrolatum, dimer acid esters, fatty acid dipentaerythrityl esters, and acyl amino acid esters are even more preferred, and one or more selected from the group consisting of petrolatum, dimer acid esters, and fatty acid dipentaerythrityl esters are particularly preferred.

[0021] Commercially available products include, for example, Snowwhite Special (melting point 53°C) (manufactured by Sonneborn) as petrolatum, Cosmol 168EV as hexa(hydroxystearate / isostearate) dipentaerythrityl, Cosmol 168ARV (melting point 37°C) as hexa(hydroxystearate / stearate / rosinate) dipentaerythrityl (both manufactured by Nisshin Oillio Co., Ltd.), and PLANDOOL-MA as macadamia nut fatty acid phytosteryl. S (melting point 45°C), dimer dilinoleate (phytosteryl / isostearyl / cetyl / stearyl / behenyl), PLANDOOL-S, PLANDOOL-H (both melting point 40°C), dimer dilinoleyl bis(behenyl / isostearyl / phytosteryl), PLANDOOL-G (melting point 40°C) (all manufactured by Nippon Seika Co., Ltd.), bis-diglyceryl polyacyladipate-2, SOFTISAN649 (melting point 35°C) (IOI Examples include Eldew PS-304 (melting point 47°C) (manufactured by Ajinomoto Co., Ltd.) as lauroyl glutamate di(octyldodecyl / phytosteryl / behenyl), and Castride MS (melting point 44°C) (manufactured by National Mimatsu Co., Ltd.) as hydrogenated castor oil stearate.

[0022] The content of component (B) used in the present invention is not particularly limited, but is preferably 1% or more, more preferably 5% or more, and even more preferably 8% or more in an oily cosmetic composition. Also, 30% or less is preferred, 20% or less is more preferred, and 15% or less is even more preferred. Also, 1 to 30% is preferred, 5 to 20% is more preferred, and 8 to 15% is even more preferred. Within this range, it is more preferable because it provides superior firmness (elasticity), abrasion resistance (makeup longevity), and sustained moisturizing effect.

[0023] Component (C) used in the present invention is an oil gelling agent. In the present invention, an oil gelling agent generally solidifies or gels an oily component. The oil gelling agent is not particularly limited as long as it is usually used in cosmetics, and can be appropriately selected and used according to the properties of the cosmetics to be used, such as solid, semi-solid, liquid, etc. For example, waxes such as hydrocarbon wax, silicone wax, fats and oils, dextrin fatty acid ester, sucrose fatty acid ester, inulin fatty acid ester, 12-hydroxystearic acid, fatty acids or their salts (except for the component (A)), fumed silica, fatty acid glycerin ester, crosslinked silicone polymer, organically modified clay mineral, amino acid-based gelling agent, oil-soluble polyurethane, etc. can be mentioned, and these can be used alone or in combination of two or more kinds.

[0024] The organically modified clay mineral is obtained by ion-exchanging a water-swelling clay mineral with a cationic surfactant such as an alkyl quaternary ammonium salt. In the present invention, those exchanged with benzyl dimethyl stearyl ammonium ions and those exchanged with dimethyl distearyl ammonium ions are particularly preferred. The water-swelling clay mineral is one kind of colloidal hydrated aluminum silicate having a three-layer structure, and generally has the following general formula (2): (X, Y) ２３ (Si, Al) ４ O １０ (OH) ２ Z・nH ２O (where X is Al, Fe, Mn or Cr; Y is Mg, Fe, Ni, Zn or Li; Z is K, Na or Ca; and n is a number of 0 or more). Specifically, montmorillonite groups such as natural or synthetic (in this case, those in which (OH) in the general formula is substituted with fluorine) montmorillonite, laponite and hectorite, and synthetic mica known as sodium silicic mica, sodium or lithium teniolite, etc. are included. As the water-swellable clay mineral, montmorillonite and hectorite are particularly preferable. Further, as the organically modified clay mineral, dimethyldistearylammonium hectorite and benzyldimethylstearylammonium hectorite are preferable. Examples of commercially available products of organically modified clay minerals include Benton 27V, Benton 38V (manufactured by ELEMENTIS), etc.

[0025] Examples of the sugar fatty acid ester include dextrin fatty acid ester, inulin fatty acid ester, etc. Examples of the dextrin fatty acid ester include dextrin palmitate, dextrin stearate, dextrin isostearate, dextrin myristate, (palmitic acid / 2-ethylhexanoic acid) dextrin, etc. Examples of the inulin fatty acid ester include inulin stearate, etc. In the present invention, dextrin fatty acid ester is preferable, and dextrin palmitate and (palmitic acid / 2-ethylhexanoic acid) dextrin are more preferable. Examples of commercially available products include, as dextrin palmitate, Leopal KL2, Leopal TL2; as dextrin myristate, Leopal MKL2; as (palmitic acid / 2-ethylhexanoic acid) dextrin, Leopal TT2; as (palmitic acid / hexyl decanoic acid) dextrin, Leopal WX (all manufactured by Chiba Flour Milling Co., Ltd.). Examples of the inulin fatty acid ester include inulin stearate, etc. Examples of commercially available products include, as inulin stearate, Leopal ISL2, Leopal ISK2 (both manufactured by Chiba Flour Milling Co., Ltd.).

[0026] Examples of the wax include hydrocarbon waxes, silicone waxes, ester waxes, etc. Specifically, examples thereof include hydrocarbon waxes such as paraffin wax, ceresin wax, montan wax, microcrystalline wax, synthetic wax, ethylene-propylene copolymer, polyethylene wax, Fischer-Tropsch wax, silicone waxes such as stearyldimethicone, and ester waxes such as candelilla wax, carnauba wax, beeswax, rice wax, sunflower wax, Chinese vegetable tallow, and rice bran wax. In the present invention, hydrocarbon waxes are preferred, and microcrystalline wax, synthetic wax, ethylene-propylene copolymer, polyethylene wax, and Fischer-Tropsch wax are more preferred.

[0027] Examples of the amino acid-based gelling agent include dibutyllauroylglutamide, dibutylethylhexanoylglutamide, etc. Commercially available products include amino acid-based oil gelling agent GP-1 as dibutyllauroylglutamide, and amino acid-based oil gelling agent EB-21 as dibutylethylhexanoylglutamide.

[0028] Fumed silica is fine amorphous silica having a particle size of 100 nm or less. Further, fumed silica may be used after being hydrophobically treated. Examples of the hydrophobization method include trimethylsilylation treatment with trimethylsilyl chloride or hexamethyldisilazane, octylsilanization treatment, coating baking treatment using methylhydrogenpolysiloxane, coating with metal soap, etc. In the present invention, hydrophobically treated fumed silica such as dimethylsilylated silica is preferred.

[0029] The fatty acid or its salt is other than the component (A), and examples thereof include stearic acid, zinc stearate, magnesium stearate, aluminum stearate, zinc myristate, zinc laurate, etc.

[0030] Examples of fatty acid glycerol esters include (behenate / eicosanedioic acid) glyceryl and tribehenate glyceryl. Examples of commercially available products include (behenate / eicosanedioic acid) glyceryl such as Nomucoat HK-G (manufactured by Nisshin Oillio Co., Ltd.) and tribehenate glyceryl such as SYNCROWAX HRC (manufactured by Croda Japan Co., Ltd.).

[0031] Examples of cross-linked silicone polymers include (dimethicone / vinyl dimethicone) crosspolymer, dimethicone crosspolymer, polysilicone-11, (vinyl dimethicone / lauryl dimethicone) crosspolymer, (dimethicone / phenyl vinyl dimethicone) crosspolymer, (dimethicone / (PEG-10 / 15)) crosspolymer, (PEG-15 / lauryl dimethicone) crosspolymer, and (dimethicone / polyglycerin-3) crosspolymer. Commercially available products include KSG-15, KSG-16, KSG-18, KSG-43, KSG-210, KSG-310, KSG-710, and KSG-810 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0032] Oil-soluble polyurethanes are polymers having lipophilic urethane bonds. Examples of oil-soluble polyurethanes include (hydrogenated porobutadiene / glycol / HDI) copolymer, polyurethane-79, (HDI / trimethylol hexyllactone) crosspolymer, and mixtures of hydrogenated poly(C6-20 olefin) and tri(caprylic / capric acid) glyceryl. Examples of commercially available products include OILKEMIA 5S CC POLYMER (manufactured by Lubrizol).

[0033] In the present invention, component (C) is preferably one or more selected from the group consisting of organically modified clay minerals, dextrin fatty acid esters, waxes, amino acid-based gelling agents, fuzzy silica, and fatty acids or their salts (excluding component (A)) from the viewpoint of not bleeding and firmness (elasticity), more preferably one or more selected from the group consisting of organically modified clay minerals, dextrin fatty acid esters, waxes, amino acid-based gelling agents, and fuzzy silica, and even more preferably one or more selected from the group consisting of organically modified clay minerals, dextrin fatty acid esters, and waxes.

[0034] In particular, in one embodiment of the present invention, for example, when the oily cosmetic is solid, using wax as component (C) is preferable in terms of non-bleeding, scratch resistance (cosmetic longevity), and shape retention of the oily cosmetic. In another embodiment, when the oily cosmetic is paste-like or liquid, using organically modified clay mineral as component (C) is preferable in terms of improved usability, such as firmness (elasticity), sustained moisturizing effect, and non-stickiness. In particular, using organically modified clay mineral and wax in combination is even more preferable because it provides superior non-bleeding and firmness.

[0035] The content of component (C) used in the present invention is not particularly limited and can be appropriately adjusted according to the properties of the oily cosmetic. For example, it is preferably 0.5% or more, more preferably 2% or more, and even more preferably 5% or more in the oily cosmetic. Also, it is preferably 25% or less, more preferably 20% or less, and even more preferably 15% or less. Also, it is preferably 0.5 to 25%, more preferably 2 to 20%, and even more preferably 5 to 15%. Within this range, it is more preferable because it is superior in terms of lack of bleeding, firmness (elasticity), and sustained moisturizing effect.

[0036] Component (D) in the present invention is a polyorganosiloxane having a block structure, represented by the following formula (1), having a weight-average molecular weight of 500,000 or more, being a solid at room temperature, and having a softening point of 50°C or higher (hereinafter also referred to as "polyorganosiloxane having a block structure"). The above-mentioned properties at room temperature and softening point of the polyorganosiloxane refer to the properties and softening point in a solvent-free state. In this specification, room temperature refers to 25°C.

[0037] In the formula, R １ , R ２ , R ３ , R ４ and R ５ Each of these is independently a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, which may have a hydrogen atom or a substituent. m represents the number of repeating diorganosiloxy units, where 50 ≥ m ≥ 0. a, b, c, d, and e represent the molar ratios of their respective siloxane units, where 0.3 ≥ a ≥ 0, 0.3 ≥ b > 0, 0.5 ≥ c ≥ 0, 0.95 ≥ d > 0.5, 0.3 ≥ e ≥ 0, and a + b × (2 + m) + c + d + e = 1. x and y represent the number of hydroxyl or alkoxy groups bonded to 1 mole of Si atoms in the siloxane units a to e, respectively, where 0.1 ≥ x > 0 and 0.1 ≥ y > 0.

[0038] R １ , R ２ , R ３ , R ４ and R ５Each of these is a hydrocarbon group having 1 to 20 carbon atoms, which may independently have a hydrogen atom or a substituent. The hydrocarbon group preferably has 1 to 10 carbon atoms and may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, or a combination thereof. The aliphatic hydrocarbon group may be either saturated or unsaturated and may be linear, branched, or cyclic. Examples of aliphatic hydrocarbon groups include alkyl groups, alkenyl groups, and cycloalkyl groups. Examples of alkyl groups include alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl groups. Examples of alkenyl groups include alkenyl groups having 2 to 10 carbon atoms, such as vinyl, allyl, hexenyl, and octylenyl groups. Examples of cycloalkyl groups include cycloalkyl groups having 3 to 10 carbon atoms, such as cyclopentyl and cyclohexyl groups. Examples of aromatic hydrocarbon groups include aromatic hydrocarbon groups having 6 to 10 carbon atoms, such as the phenyl group and the naphthyl group.

[0039] Examples of substituents include halogen atoms, alkoxy groups, (meth)acryloxy groups, mercapto groups, and glycidyloxy groups. A chlorine atom is preferred as the halogen atom. For the alkyl portion of the alkoxy group, the examples and preferred examples of alkyl groups described above apply. Examples of alkoxy groups include methoxy groups and ethoxy groups.

[0040] Specific examples of C1-C20 hydrocarbon groups that may have substituents include methyl group, chloromethyl group, methoxymethyl group, ethyl group, ethoxyethyl group, vinyl group, propyl group, (meth)acryloxypropyl group, mercaptopropyl group, chloropropyl group, glycidyloxypropyl group, epoxycyclohexylethyl group, allyl group, butyl group, pentyl group, cyclopentyl group, hexyl group, hexenyl group, cyclohexyl group, phenyl group, heptyl group, octyl group, octylenyl group, (meth)acryloxyoctyl group, mercaptooctyl group, chloroctyl group, glycidyloxyoctyl group, decyl group, and the like.

[0041] R １ , R ２ , R ３ and R ４ Regarding this, methyl groups, ethyl groups, propyl groups, and phenyl groups are preferred, methyl groups and ethyl groups are more preferred, and methyl groups are even more preferred. ５ For this, saturated hydrocarbon groups having 1 to 4 carbon atoms are preferred, with examples including methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, and t-butyl groups, and more preferably n-butyl, s-butyl, and i-butyl groups.

[0042] a, b, c, d, and e represent the molar ratios of each siloxane unit, with 0.3≧a≧0, 0.3≧b>0, 0.5≧c≧0, 0.95≧d>0.5, 0.3≧e≧0, and a+b×(2+m)+c+d+e=1. x and y represent the number of hydroxyl groups or alkoxy groups bonded to 1 mole of Si atoms in the siloxane units a to e, respectively, with 0.1≧x>0 and 0.1≧y>0.

[0043] With respect to the hydroxyl or alkoxy groups bonded to the Si atoms of a polydiorganosiloxane having a block structure, it is preferable from the viewpoint of polymer stability that x and y are 0.05 ≥ x > 0 and 0.05 ≥ y > 0, respectively. When x = y = 0, it does not contain structural groups that undergo dehydration, dealcoholization, condensation, and crosslinking. Although the polymer stability is excellent, it becomes a component that does not cure, which is undesirable as it reduces the durability of the coating film. On the other hand, when x or y is greater than 0.1, while the aforementioned curability is excellent, there is a high possibility that the polymer stability will decrease, and in particular when x > 0.1, the stability will be low, which is undesirable.

[0044] Regarding the ratio of siloxane units in the polydiorganosiloxane having a block structure of the present invention, from the viewpoint of polymer stability, high degree of polymerization, and film flexibility, it is preferable that at least one of the following conditions be met: 40 > m > 10, 0.05 ≥ a > 0, 0.3 ≥ b > 0, 0.3 ≥ c > 0, and 0.05 ≥ e ≥ 0, more preferably two or more, and even more preferably all of them. Furthermore, in addition to the above, it is even more preferable that 0.9 ≥ d > 0.7.

[0045] The polydiorganosiloxane having a block structure has a weight-average molecular weight of 500,000 or more, preferably 1,000,000 or more, more preferably 1,200,000 or more, and even more preferably 2,000,000 or more, from the viewpoint of film-forming properties, film continuity, and lack of stickiness of the coating film. There is no particular upper limit to the weight-average molecular weight, but from the viewpoint of suppressing gelation, for example, the weight-average molecular weight is preferably 16,000,000 or less, more preferably 10,000,000 or less, and even more preferably 8,000,000 or less. As a range that balances the performance of the coating film and the stability of the siloxane polymer, 500,000 to 16,000,000 is preferred, 1,000,000 to 10,000,000 is more preferred, 1,200,000 to 10,000,000 is even more preferred, and 2,000,000 to 8,000,000 is even more preferred.

[0046] The weight-average molecular weight in this invention is a value obtained by converting a polystyrene with a known molecular weight to a standard substance using gel permeation chromatography (GPC) measured under the conditions shown below. [Measurement conditions] Flow rate: 0.5 mL / min Detector: Differential refractive index detector (RI) Column: Two of the following columns are used in direct connection. TSKgel GMHHR-H(30) (7.8 mm I.D. × 30 cm × 1) (Tosoh Corporation) Column temperature: 40°C Sample injection volume: 200 μL (THF solution with a concentration of 20 g / L)

[0047] Polydiorganosiloxanes with a block structure are preferably introduced with a linear polydiorganosiloxane structure from the viewpoint of non-stickiness of the coating film and film flexibility. As an indicator of the state in which such a structure is introduced while being maintained ２９One method is signal analysis using Si-NMR, specifically, it is possible to distinguish by detecting signals belonging to polydiorganosiloxanes that fall within a predetermined range of chemical shifts. Generally, these are detected in the range of -10 to -50 ppm, but the polydiorganosiloxanes having a block structure contained in the cosmetic composition of the present invention are ２９ The present invention is characterized in that the chemical shift of the signal attributed to the diorganosiloxane unit in Si-NMR is detected in the range of -15 to -25 ppm, and the detection width of the signal peak (the difference between the chemical shift at the detection start point and the chemical shift at the detection end point) is 3 to 7 ppm. The narrower the detection width of the signal peak, the more it indicates that the linear siloxane structure is maintained while being introduced into the polymer. If the detection width is greater than 10 ppm, it means that the linear structure is practically absent from the polymer, making it difficult to obtain the desired coating film properties. In the present invention, ２９ Si-NMR was performed using a 300MHz-NMR analyzer manufactured by JEOL Ltd., and a solution sample with a sample concentration of 20 wt% was measured under conditions of 25°C.

[0048] In the present invention, it is preferable to control the pH of the extracted water in the composition obtained by dissolving the block-structured polyorganosiloxane in an organic solvent so that it exhibits acidity between 3.5 and 6. Generally, it is known that the pH of the extracted water in a liquid obtained by dissolving polyorganosiloxane in an organic solvent is neutral unless the solvent itself is acidic or basic. By controlling the pH within the aforementioned range, it is possible to obtain a stable solution without causing gelation or other problems over a long period of time, even with high molecular weight polyorganosiloxanes like those in the present invention. Methods for controlling the pH of the extracted water include the use of acids and buffers, but it is preferable to incorporate an acid, and more preferably to incorporate an organic carboxylic acid.

[0049] Examples of acids include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, as well as organic carboxylic acids such as formic acid, acetic acid, propionic acid, citric acid, succinic acid, maleic acid, methanesulfonic acid, and trifluoromethanesulfonic acid, but are not limited to those exemplified here.

[0050] In the present invention, a composition in which a polyorganosiloxane having a block structure is dissolved in an organic solvent preferably contains an organic solvent that is not an aromatic hydrocarbon. This is because aromatic hydrocarbons, such as benzene, toluene, and xylene, are organic solvents that have a significant environmental impact.

[0051] The polyorganosiloxane having a block structure contained in the cosmetic composition of the present invention can be produced, for example, by the following steps 1 to 3. Step 1: A silane monomer capable of constituting a siloxane unit of formula (1) above, having a chlorosilyl group or an alkoxysilyl group having 1 to 2 carbon atoms as a hydrolyzable group, and a polydiorganosiloxane having hydrolyzable silyl groups at both ends are dropped into a mixed medium layer consisting of water, a hydrophilic organic solvent with a water solubility of 50 to 1000 g / L at 25°C, and a hydrophobic organic solvent with a water solubility of 1 g / L or less at 25°C, and a polydiorganosiloxane having hydrolyzable silyl groups at both ends are dropped and hydrolyzed and condensed. Step 2: After removing the generated hydrogen chloride and alcohol, condensation polymerization is carried out under strongly acidic conditions with a pH of 3 or less until the weight-average molecular weight is 500,000 or more. Step 3: The acid is neutralized or removed and the pH of the extracted water is adjusted to 3.5 to 6.

[0052] Examples of hydrophilic organic solvents with a water solubility of 50 to 1000 g / L at 25°C include alcohols, ketones, esters, and ether compounds. Specifically, examples include n-propanol, isopropanol, n-butanol, secondary butanol, isobutanol, tertiary butanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, methyl ethyl ketone, and cyclohexanone. Among these, n-propanol, isopropanol, n-butanol, and isobutanol are preferred from the viewpoint of controlling the reaction during hydrolysis condensation and suppressing the formation of insoluble substances.

[0053] Examples of hydrophobic organic solvents with a water solubility of 1 g / L or less at 25°C include aliphatic hydrocarbon solvents such as hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, decane, isododecane, and isoparaffin compounds derived from olefin gases, as well as aromatic hydrocarbon solvents such as toluene and xylene. Among these, hexane, heptane, octane, cyclohexane, methylcyclohexane, and ethylcyclohexane are preferred from the viewpoint of reaction control during hydrolysis condensation, maintenance of block structure, and solubility of the resulting resin, and hexane, heptane, and ethylcyclohexane are more preferred.

[0054] The preferred weight ratio of a mixed medium consisting of water, a hydrophilic organic solvent with a water solubility of 50 to 1000 g / L at 25°C, and a hydrophobic organic solvent with a water solubility of 1 g / L or less at 25°C is 10 to 30 parts hydrophilic organic solvent and 10 to 30 parts hydrophobic organic solvent, with water being 100 parts. Exceeding this upper limit reduces productivity because it requires the use of more organic solvent than necessary. On the other hand, if it falls below this lower limit, it becomes difficult to control the reaction during hydrolysis condensation, and solvent-insoluble substances are generated.

[0055] As the silane and siloxane materials to be hydrolyzed and condensed, it is preferable to use silane monomers that can constitute the siloxane unit of formula (1) having a chlorosilyl group or an alkoxysilyl group having 1 to 2 carbon atoms as a hydrolyzable group, and polydiorganosiloxanes having hydrolyzable silyl groups at both ends. In particular, for polydiorganosiloxanes having hydrolyzable silyl groups at both ends, α,ω-dimethylchlorosiloxypolydimethylsiloxane, shown in formula (2) below, is preferred from the viewpoint of reactivity during hydrolysis. Furthermore, regarding the silane monomer, it is more preferable from the viewpoint of reaction control and production efficiency that the compound has only a chlorosilyl group as a hydrolyzable group.

[0056] (In the equation, 50 ≥ m ≥ 0.)

[0057] During the hydrolysis condensation reaction, the weight concentration of the reactive silane and siloxane material is preferably 10 to 30% by weight relative to the total amount of the mixed medium including water and the reactive silane and siloxane material. If this upper limit is exceeded, it becomes difficult to control the reaction during hydrolysis condensation, and insoluble matter is generated in the solvent. On the other hand, if it falls below this lower limit, it is undesirable because it reduces productivity due to the use of more organic solvent than necessary.

[0058] The temperature during the hydrolysis condensation reaction is preferably between 0 and 40°C. If the temperature is higher than 40°C, it becomes difficult to control the reaction during hydrolysis condensation, and there is a risk of generating solvent-insoluble substances. If the temperature is below 0°C, the aforementioned reaction control effect becomes excessive, and it becomes inefficient in terms of the cooling energy required for temperature control.

[0059] In a method for producing polyorganosiloxanes having a block structure, after removing the generated hydrogen chloride and alcohol, condensation polymerization is carried out under strongly acidic conditions with a pH of 3 or less until the weight-average molecular weight reaches 500,000 or more. From the viewpoint of reaction control, the reaction temperature is preferably in the range of 10 to 80°C. Furthermore, from the viewpoint of reaction control, the pH is preferably between 1 and 3. If the reaction temperature is higher than the upper limit of the range and the pH is lower than the lower limit of the range, the condensation polymerization proceeds excessively quickly and becomes difficult to control. On the other hand, if the reaction temperature is lower than the lower limit of the range and the pH is higher than the upper limit, the polymerization rate decreases significantly, and productivity deteriorates.

[0060] Component (D) in the present invention can be dissolved in any oil and can also be provided as a dissolved product. When the oil is a volatile oil, the volatilization of the oil enables the formation of a film, thus exhibiting the effect of a film-forming agent. As for the volatile oil, it is preferable to use one that forms a film early after application of the cosmetic and exhibits a film-forming effect, and from this point of view, it is preferable to use one dissolved in a volatile oil with a boiling point of 260°C or lower. Examples of volatile oils include silicone oils such as decamethylpentasiloxane, dimethicone, octamethylcyclotetrasiloxane, dodecamethylcyclohexasiloxane, methyltrimethicone, decamethyltetrasiloxane, and ethyltrisiloxane, as well as volatile hydrocarbon oils such as light liquid isoparaffin, isohexadecane, and isododecane. Decamethylpentasiloxane, dimethicone, and isododecane are particularly preferred.

[0061] The content of component (D) used in the present invention is not particularly limited, but in an oily cosmetic composition, for example, it is preferably 0.5% or more as solid content, more preferably 1% or more, and even more preferably 2% or more. Also, it is preferably 15% or less, more preferably 12% or less, and even more preferably 10% or less. Also, it is preferably 0.5 to 15%, more preferably 1 to 12%, and even more preferably 2 to 10%. Within this range, it is more preferable because it is superior in terms of lack of bleeding, abrasion resistance (makeup longevity), and sustained moisturizing effect.

[0062] The mass ratio (A) / (D) of component (A) to component (D) in the present invention is not particularly limited. For example, from the viewpoint of firmness (elasticity), it is preferably 0.1 or more, more preferably 0.5 or more, and still more preferably 1 or more. Also, it is preferably 15 or less, more preferably 12 or less, still more preferably 10 or less, and still more preferably 7 or less. Also, it is preferably 0.1 to 15, more preferably 0.5 to 12, still more preferably 1 to 10, and still more preferably 1 to 7. Within this range, it is more preferable because it provides better resistance to bleeding and abrasion (makeup longevity).

[0063] The mass ratio (B) / (D) of component (B) to component (D) in the present invention is not particularly limited. For example, from the viewpoint of sustained moisturizing effect, it is preferably 0.1 or higher, more preferably 0.3 or higher, and even more preferably 0.5 or higher. Also, from the viewpoint of no bleeding, firmness (elasticity), and abrasion resistance (makeup longevity), it is preferably 10 or lower, more preferably 8 or lower, even more preferably 6 or lower, and even more preferably 4 or lower. Furthermore, it is between 0.1 and 10, more preferably 0.3 to 8, even more preferably 0.5 to 6, and even more preferably 0.5 to 4. Within this range, it is more preferable because it provides better resistance to bleeding and sustained moisturizing effect.

[0064] In the present invention, the present invention may further contain a polyhydric alcohol as component (E). The polyhydric alcohol is not particularly limited as long as it is commonly used in cosmetics, and examples include sugar alcohols such as propylene glycol, 1,3-butylene glycol, dipropylene glycol, tripropylene glycol, glycerin, diglycerin, polyethylene glycol, sorbitol, and maltitol. In particular, the inclusion of 1,3-butylene glycol, dipropylene glycol, tripropylene glycol, etc. is more preferable because it does not easily inhibit the film-forming properties of component (D), improves preservative power, and provides superior sustained moisturizing effect.

[0065] In the present invention, the content of component (E) is not particularly limited, but is preferably 0.05% or more, more preferably 0.1% or more, and even more preferably 0.3% or more in the oily cosmetic composition. Also, it is preferably 10% or less, more preferably 8% or less, and even more preferably 5% or less. Furthermore, it is preferably 0.05 to 10%, more preferably 0.1 to 8%, and even more preferably 0.3 to 5%. Within this range, it is more preferable because it is superior in terms of not bleeding and the duration of moisturizing effect.

[0066] In addition to the above components (A) to (E), the oily cosmetic composition of the present invention may appropriately incorporate other components commonly used in cosmetics, as long as they do not interfere with the effects of the present invention. Examples include oils other than components (A) and (B), film-forming agents other than component (D), powders, preservatives, antioxidants, surfactants, medicinal components, UV absorbers, fragrances, aqueous components other than component (E), and humectants.

[0067] As for the powder, there are generally no particular restrictions as long as it can be used in cosmetics, and any particle shape, particle size, and particle surface condition can be used. There are no particular limitations in terms of shape such as plate-like, spindle-like, needle-like, particle size such as aerosol, fine particles, or pigment-grade, and particle structure such as porous or non-porous, and examples include inorganic powders, luminous powders, organic powders, and composite powders.For example, white body powders such as muscovite, phlogopite, red mica, biotite, synthetic mica, sericite, synthetic sericite, kaolin, silicon carbide, bentonite, smectite, silica, aluminum oxide, magnesium oxide, zirconium oxide, diatomaceous earth, aluminum silicate, magnesium aluminum metasilicate, calcium silicate, barium silicate, magnesium silicate, calcium carbonate, magnesium carbonate, hydroxyapatite, boron nitride, polyamide resins, polyethylene resins, polyacrylic resins, polyester resins, and fluorine resins. Lipids, cellulose resins, polystyrene resins, copolymer resins such as styrene-acrylic copolymer resins, organic polymer resin powders such as polypropylene resins and urethane resins, low molecular weight organic powders such as zinc stearate and N-acyllysine, natural organic powders such as silk powder and cellulose powder, fibers such as nylon, polyester, rayon, and cellulose, titanium dioxide, red iron oxide, yellow iron oxide, black iron oxide, ultramarine, Prussian blue titanium dioxide, black titanium dioxide, ultramarine, chromium oxide, chromium hydroxide, carbon black, titanium / titanium oxide sintered products, zinc oxide, aluminum oxide Inorganic powders such as um, cerium oxide, zirconium oxide, etc., inorganic powders such as bismuth oxychloride, organic pigment powders such as Red 201, Red 202, Red 205, Red 226, Red 228, Orange 203, Orange 204, Blue 404, Yellow 401, etc., organic pigment powders such as zirconium, barium, or aluminum lake, Red 3, Red 104, Red 106, Orange 205, Yellow 4, Yellow 5, Green 3, Blue 1, etc., titanium mica, iron oxide treated mica, iron oxide treated titanium mica, organic pigment treated titanium mica, titanium oxide treated glass powder, iron oxide Examples include titanium dioxide-treated glass powder, lustrous powders such as aluminum powder, pigment powders such as organic lake pigments, composite powders such as fine-particle titanium dioxide-coated titanium mica, fine-particle zinc oxide-coated titanium mica, barium sulfate-coated titanium mica, titanium dioxide-containing silicon dioxide, and zinc oxide-containing silicon dioxide, as well as polyethylene terephthalate-aluminum-epoxy laminated powder, polyethylene terephthalate-polyolefin laminated film powder, and polyethylene terephthalate-polymethyl methacrylate laminated film powder, and one or more of these can be used.Furthermore, these powders may be used individually or as a composite of two or more. These may be surface-treated with fluorine compounds, silicone compounds, metal soaps, lecithin, hydrogenated lecithin, collagen, hydrocarbons, higher fatty acids, higher alcohols, esters, waxes, waxes, surfactants, etc., as long as they do not interfere with the effects of the present invention. One or more of these may be used as needed.

[0068] Examples of preservatives include parahydroxybenzoic acid esters, phenoxyethanol, and 1,2-pentadiol; examples of antioxidants include tocopherol and ascorbic acid; and examples of cosmetic ingredients include vitamins, anti-inflammatory agents, and herbal medicines.

[0069] Examples of UV absorbers include anthranyl-based, dibenzoylmethane-based (such as butyl methoxydibenzoylmethane and isopropyl dibenzoylmethane), cinnamic acid-based (such as ethylhexyl methoxycinnamate, isopropyl methoxycinnamate, and 2-ethoxyethyl 4-methoxycinnamate), salicylic acid-based (such as ethylhexyl salicylate), camphor-based, benzophenone-based (such as benzophenone-3), triazine-based (such as bis-ethylhexyloxyphenol methoxyphenyl triazine and ethylhexyl triazone), benzotriazole, benzalmalonate-based, benzimidazole-based, bis-benzoazolyl-based, p-aminobenzoic acid-based, diphenyl acrylate-based (such as octocrerin), and urocanic acid-based. Examples of moisturizers include proteins, mucopolysaccharides, collagen, elastin, and keratin.

[0070] The oil-based cosmetic composition of the present invention has oil as a continuous phase and is substantially water-free. In the present invention, "substantially water-free" means either completely free of water or present in an amount that does not affect the present invention, and the water content is preferably 5% or less, more preferably 1% or less.

[0071] The oily cosmetic composition of the present invention is not particularly limited, but can be manufactured using conventional methods. For example, it can be obtained by dissolving and mixing components (A) to (C) at 70 to 110°C, adding component (D), and optionally component (E) and other components, and mixing and dispersing them.

[0072] The oily cosmetic composition of the present invention is not particularly limited in its properties and may be liquid, semi-solid, gel, cream, or solid. Among these, liquid, semi-solid, and solid forms are preferred.

[0073] The oily cosmetic composition of the present invention is not particularly limited and can include, for example, base makeup cosmetics such as cosmetic oil, sunscreen, foundation, primer, and concealer; eye cosmetics such as mascara, eyeshadow, eyebrow pencil, and eyeliner; lip cosmetics such as blush, lipstick, lip gloss, lip balm, and lip essence; and hair cosmetics such as hair oil, hair colorant, and hair styling product. Makeup cosmetics are particularly preferred, lip cosmetics are even more preferred, and lipstick, lip gloss, lip balm, and lip essence are even more preferred.

[0074] The present invention may also take the following configuration: [1] The following components (A) to (D): (A) A non-volatile oil that is liquid at 25°C (B) A semi-solid oil that is semi-solid at 25°C (C) An oily gelling agent (D) A polyorganosiloxane having a block structure, represented by the following general formula (1), having a weight-average molecular weight of 500,000 or more, being solid at room temperature, and having a softening point of 50°C or higher (In the formula, R １ , R ２ , R ３ , R ４ and R ５A is an oily cosmetic containing a ) which is an oily cosmetic containing a ) which is an oily cosmetic containing a ) which is an oily cosmetic containing a ) which is an oily cosmetic containing a ) which is an oily cosmetic containing a ) which is an oily cosmetic containing a ) which is an oily cosmetic containing a ) which is an oily cosmetic containing a ) which is an oily cosmetic containing a ) which is an oily cosmetic according to [1] which is an oily cosmetic according to [1] which is an oily cosmetic containing a ) [3] The oily cosmetic composition according to [1] or [2], wherein component (C) is one or more selected from the group consisting of organically modified clay minerals, dextrin fatty acid esters, waxes, amino acid-based gelling agents, fuming silica, and fatty acids or their salts (excluding component (A)). [4] The oily cosmetic composition according to any one of [1] to [3], wherein component (A) is one or more selected from the group consisting of ester oils, silicone oils, hydrocarbon oils, higher alcohols, and fatty acids. [5] The oily cosmetic composition according to any one of [1] to [4], wherein component (B) is hydrocarbon oil and / or ester oil. [6] The oily cosmetic composition according to any one of [1] to [5], wherein the mass ratio (A) / (D) of component (A) to component (D) is 0.1 to 15. [7] An oily cosmetic composition according to any one of [1] to [6], wherein the mass ratio (B) / (D) of component (B) to component (D) is 0.1 to 10. [8] An oily cosmetic composition according to any one of [1] to [7], further containing component (E) a polyhydric alcohol. [9] An oily cosmetic composition according to any one of [1] to [8], which is a lip cosmetic composition.

[0075] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0076] (1) GPC measurement conditions Instrument: HLC-8320GPC manufactured by Tosoh Corporation Developing solvent: Tetrahydrofuran (THF) Flow rate: 0.5 mL / min Detector: Differential refractive index detector (RI) Column: Two of the following columns are used in direct connection. TSKgel GMHHR-H(30) (7.8 mm I.D. × 30 cm × 1) (manufactured by Tosoh Corporation) Column temperature: 40°C Sample injection volume: 200 μL (THF solution with a concentration of 20 g / L) Standard: Monodisperse polystyrene (2) Silicon nuclear magnetic resonance spectrum ( ２９ Si-NMR) Measurement conditions Equipment: 300MHz-NMR manufactured by JEOL Ltd. Solvent: CDCl ３ Sample concentration: 20% Internal standard: Tetramethylsilane (TMS)

[0077] In the following, the kinematic viscosity of the product was measured at 25°C using a Cannon-Fenske viscometer according to the method described in JIS Z 8803:2011, and the content of silanol hydroxyl groups in the product (mass%), hereinafter referred to as silanol content, was quantified from the amount of methane gas generated when the product was reacted with a Grignard reagent (methylmagnesium iodide).

[0078] Manufacturing Example 1 [Synthesis of Polyorganosiloxane with Block Structure] 2700 g of deionized water, 400 g of isobutanol, and 300 g of heptane were charged into a 5 L three-necked flask equipped with a stirrer, condenser, dropping funnel, and thermometer, and stirred. A mixture of 650 g (4.3 mol) of methyltrichlorosilane, 70 g (0.9 mol Si equivalent) of α,ω-dimethylchlorosiloxypolydimethylsiloxane (formula 3) below, and 300 g of heptane (at 25°C) was added dropwise over 2 hours while controlling the temperature so that the internal temperature did not exceed 40°C. After the addition was complete, the hydrochloric acid aqueous phase, in which hydrogen chloride generated by the hydrolysis of the chlorosilyl group dissolved in the deionized water, was separated from the organic phase. This organic phase was washed multiple times with saline solution until the water-washed phase became neutral. The resulting organic phase had a kinematic viscosity of 2.7 mm. ２Under drying conditions of 0.5°C for 3 hours at 105°C, the non-volatile residue was 33%, and the organic solution contained an organosiloxane with a molecular weight of approximately 7600 as determined by GPC. 20 g of concentrated hydrochloric acid was added to this organic solution, and a condensation polymerization reaction was carried out by heating at 60°C for 3 hours. Subsequently, heptane was added to adjust the concentration so that the drying residue was 20%, and after washing multiple times with saline solution until the water washing phase was neutral, 0.03% citric acid was added to the organic solution and dissolved to obtain an organic solution in which the polyorganosiloxane having the desired block structure was dissolved in an organic solvent. The kinematic viscosity of this organic solution was 14.4 mm². ２ Under drying conditions of 105°C for 3 hours at s, the non-volatile residue was 21%, and the molecular weight was approximately 1.43 million according to GPC. ２９ Si-NMR measurements revealed signals attributed to diorganosiloxane units (D units) in the range of -16 to -23 ppm, with a detection width of 5 ppm for the main signal peak. Furthermore, it was confirmed that the polyorganosiloxane having the above block structure is solid at room temperature without solvent, and that its softening point is above 50°C. It was also confirmed that the polyorganosiloxane having the above block structure satisfies the above general formula (1).

[0079]

[0080] Production Example 2 [Synthesis of Polyorganosiloxane Having a Block Structure] A polyorganosiloxane having a block structure with a weight-average molecular weight of 3.1 million was obtained in the same manner as in Production Example 1, except that the condensation polymerization reaction conditions were changed to 60°C for 4 hours. It was confirmed that the above polyorganosiloxane having a block structure is solid at room temperature in the absence of solvent, and that its softening point is 50°C or higher. It was also confirmed that the above polyorganosiloxane having a block structure satisfies the above general formula (1).

[0081] Production Example 3 [Synthesis of Polyorganosiloxane Having a Block Structure] A polyorganosiloxane having a block structure with a weight-average molecular weight of 590,000 was obtained in the same manner as in Production Example 1, except that the condensation polymerization reaction conditions were changed to 60°C for 2 hours. It was confirmed that the above polyorganosiloxane having a block structure is solid at room temperature in the absence of solvent, and that its softening point is 50°C or higher. It was also confirmed that the above polyorganosiloxane having a block structure satisfies the above general formula (1).

[0082] Production Example 4 [Synthesis of Polyorganosiloxane with Block Structure] 500 g of the polysiloxane solution with a 20% dry residue obtained in Production Example 1 was mixed with 16 g (0.16 mol) of triethylamine and 13 g (0.12 mol) of trimethylchlorosilane. The mixture was then heated at 60°C for 3 hours to carry out the trimethylsiloxylation reaction of the silanol in the polysiloxane. Subsequently, the mixture was washed multiple times with saline solution until the water washing phase became neutral to obtain an organic solution in which a polyorganosiloxane with a weight-average molecular weight of 1.56 million, trimethylsiloxy-blocked and block structure, was dissolved in an organic solvent. It was confirmed that the above polyorganosiloxane with block structure was solid at room temperature in the absence of solvent, and that its softening point was 50°C or higher. It was also confirmed that the above polyorganosiloxane with block structure satisfies the above general formula (1).

[0083] Examples 1-22 and Comparative Examples 1-6 Oil-based lipstick (applicator container) Oil-based lipsticks with the compositions shown in Tables 1-3 were prepared by the following method, and each item of "no bleeding," "firmness (elasticity)," "scratchy resistance (makeup longevity)," and "persistence of moisturizing effect" was evaluated and judged according to the evaluation method and judgment criteria shown below. The results are shown in Tables 1-3.

[0084] *1: Saracos 5408 (viscosity 66 mPa / s at 25°C) (manufactured by Nisshin Oillio Co., Ltd.) *2: Cosmol 43V (viscosity 350 mPa / s at 25°C) (manufactured by Nisshin Oillio Co., Ltd.) *3: KF-54 (viscosity 400 mPa / s at 25°C) (manufactured by Shin-Etsu Chemical Co., Ltd.) *4: High Malate DIS (viscosity 2700 mPa / s at 25°C) (manufactured by Higher Alcohol Industry Co., Ltd.) *5: Pearlream 18 (viscosity 26700 mPa / s at 25°C) (manufactured by NOF Corporation) *6: ISODODECANE (manufactured by IMCD Corporation) *7: Snowwhite Special (melting point 53°C) (manufactured by Sonneborn Co., Ltd.) *8: PLANDOOL-S (melting point 40°C) (manufactured by Nippon Seika Co., Ltd.) *9: Cosmoll 168ARV (melting point 37°C) (manufactured by Nisshin Oillio Co., Ltd.) *10: BENTONE 38V BC (manufactured by ELEMENTIS Co., Ltd.) *11: Leopal KL2 (manufactured by Chiba Flour Milling Co., Ltd.) *12: EPS Wax (melting point 90-99°C) (manufactured by Nippon Natural Products Co., Ltd.) *13: KSG-016F (manufactured by Shin-Etsu Chemical Co., Ltd.) *14: SR1000 (manufactured by Momentive Performance Materials Japan Co., Ltd.)

[0085]

[0086]

[0087] (Manufacturing Method) A: Heat and dissolve ingredients (7) to (9) and (11) to (12) at 100°C and mix. B: Add ingredients (10) and some of (18) to (22) and (1) to (5) to A and disperse uniformly with a roller. C: Add the remaining ingredients (6), (13) to (17) and (1) to (5) to B and mix at 35 to 70°C. D: Fill C into a container with an applicator and cool to 25°C to obtain an oily lipstick.

[0088] (Evaluation Method 1) A panel of 20 cosmetic evaluation specialists was asked to use the oil-based lipsticks of the above-mentioned examples and comparative examples, and a sensory evaluation was conducted. For "lack of bleeding," the panel evaluated whether the makeup film did not bleed from immediately after application until the finished result; for "firmness (elasticity)," they evaluated whether the makeup film was elastic upon application and gave the lips a feeling of firmness; and for "persistence of moisturizing effect," they evaluated whether the moisturizing effect of the makeup film was felt one hour after using the oil-based lipstick. Each panelist made an absolute evaluation according to the following criteria, and the average score of all panelists was then judged according to the following criteria. <Absolute Evaluation Criteria> (Score): (Evaluation) 5: Very good 4: Fairly good 3: Neutral 2: Fairly bad 1: Very bad <Judgment Criteria> (Judgment): (Average score) A: 4.5 or higher B: 3.5 or higher and less than 4.5 C: 2.5 or higher and less than 3.5 D: Less than 2.5

[0089] (Evaluation Method 2) Immediately after preparation, each sample was taken with a finger or applicator and 0.1 g was applied to a 2 cm x 2 cm piece of artificial leather. After 1 hour, the artificial leather with the sample applied was rubbed five times with a tissue and the condition of the sample on the tissue was observed. The degree of abrasion resistance of each sample was judged according to the following criteria. <Judgment Criteria> (Judgment): (Condition on tissue) A: Not transferred to the tissue at all B: Slightly transferred to the tissue C: Quite a lot transferred to the tissue D: Almost entirely transferred to the tissue

[0090] As shown in the results in Tables 1 to 3, Examples 1 to 22 of the present invention were excellent in all items. On the other hand, Comparative Example 1, which did not contain ingredient (A), was not satisfactory in terms of firmness (elasticity) and the duration of moisturizing effect, and Comparative Example 2, which did not contain ingredient (B), was not satisfactory in terms of firmness (elasticity) and the duration of moisturizing effect. Furthermore, Comparative Example 3, which did not contain ingredient (C), was not satisfactory in terms of lack of bleeding, firmness (elasticity), and abrasion resistance (makeup longevity). Comparative Example 4, which did not contain ingredient (D), was not satisfactory in terms of lack of bleeding, abrasion resistance (makeup longevity), and the duration of moisturizing effect. Comparative Example 5, which contained (dimethicone / vinyl dimethicone) crosspolymer instead of ingredient (D), was not satisfactory in terms of abrasion resistance (makeup longevity) and the duration of moisturizing effect. Comparative Example 6, which contained trimethylsiloxysilicate instead of ingredient (D), was not satisfactory in terms of firmness (elasticity), abrasion resistance (makeup longevity), and the duration of moisturizing effect.

[0091] Example 23: Lipstick components (%) (1) Synthetic wax (melting point 91-96°C) *15 6.5 (2) Candelilla wax (melting point 72°C) *16 2 (3) Mineral oil (viscosity 55 mPa·s at 25°C) *17 10 (4) Polyglyceryl-2 triisostearate *2 15 (5) Petrolatum *7 10 (6) Dilauroyl glutamate (octyldodecyl / phytosteryl / behenyl) (melting point 47°C) *18 4 (7) Polyorganosiloxane (solids) having the block structure of Production Example 4 15 (8) Isododecane *6 Remaining amount (9) Fuzzy silylated silica *19 2 (10) 1,3-Butylene glycol 0.4 (11) Jojoba oil (viscosity 40 mPa·s at 25°C) 0.05 (12) Lecithin 0.5 (13) Mica (average particle size 15 μm) 3 (14) Cellulose (average particle size 8.5 μm) 10 (15) Red No. 202 1 (16) Yellow No. 4 1.5 (17) Polyglyceryl-2 tetraisostearate 2% treated iron oxide 0.1 (18) Polyglyceryl-2 tetraisostearate 2% treated titanium dioxide 0.5 (19) Polyglyceryl-2 tetraisostearate 2% treated black iron oxide 0.1 (20) Purified water 0.01 (21) Sodium hyaluronate 0.1 *15: CIREWAX 90 (manufactured by CIREBELLE) *16: Refined Candelilla Wax SR-3 (manufactured by Nippon Natural Products Co., Ltd.) *17: Klearol White Mineral Oil (manufactured by Sonneborn, LLC) *18: Eldew PS-304 (manufactured by Ajinomoto Co., Ltd.) *19: Aerosil R976S (manufactured by Nippon Aerosil Co., Ltd.)

[0092] A. Dissolve components (1) to (6) uniformly at 100°C. B. Add (9), (11) to (21) to A and mix and disperse uniformly using a roll mill. C. Add components (7), (8), and (10) to B and mix uniformly. D. Heat C to 100°C and fill into a rubber mold (12Φ) container while stirring. E. Cool D to -10°C and insert into a refill container to obtain lipstick.

[0093] The lipstick of Example 23 exhibited excellent resistance to smudging, firmness (elasticity), abrasion resistance (makeup longevity), and sustained moisturizing effect.

[0094] Example 24: Lip Gloss Ingredients (%) (1) Dextrin Palmitate*11 10 (2) Dextrin Palmitate / Ethylhexanoate*20 5 (3) Polyglyceryl-2 Triisostearate*2 25 (4) Diphenyl Dimethicone*3 10 (5) Dimer Dilinoleate (Phytosteryl / Isostearyl / Cetyl / Stearyl / Behenyl)*8 10 (6) Polyorganosiloxane (Solid Content) Having the Block Structure of Production Example 4 10 (7) Isododecane*6 Remainder (8) Fuzzy Silylated Silica*19 1 (9) Polymethylsilsesquioxane Resin*21 6 (10) Methyl Methacrylate Crosspolymer (Average Particle Size 6.5 μm) 4 (11) Synthetic Fluorphlogopite (Average Particle Size 25 μm) 7 (12) Red No. 202 1 (13) Red No. 104 1 (14) Yellow No. 4 0.5 (15) Lecithin 0.5% treated titanium dioxide 1 (16) Lauroyl lysine 2% treated black iron oxide 0.1 (17) 1,3-Butylene glycol 0.5 (18) Fragrance 0.1 (19) Menthol 0.05 (20) Damask rose extract 0.03 (21) Tocopherol acetate 0.005 (22) Astaxanthin solution 0.002 (23) Jojoba oil (viscosity 40 mPa·s at 25℃) 0.02 *20: Leopard TT2 (manufactured by Chiba Flour Milling Co., Ltd.) *21: TOSPEARL 150KA (manufactured by Momentive Performance Materials Japan Co., Ltd.)

[0095] (Manufacturing method) A: Heat ingredients (1) to (5) to 100°C and dissolve uniformly. B: Add ingredients (8) to (23) to A and mix and disperse uniformly using a roll mill. C: Add ingredients (6) and (7) to B and mix uniformly. D: Fill C into an applicator container while stirring at 90°C or higher to obtain lip gloss.

[0096] The lip gloss of Example 24 exhibited excellent resistance to smudging, firmness (elasticity), abrasion resistance (makeup longevity), and sustained moisturizing effect.

[0097] Example 25: Lip Balm (Solid) Ingredients (%) (1) Polyethylene (melting point 94°C) 5 (2) Microcrystalline wax (melting point 82.2°C) 6 (3) Paraffin wax (melting point 63°C) 2 (4) Lauroyl glutamate di(octyldodecyl / phytosteryl / behenyl) *18 14 (5) Petrolatum *7 5 (6) Polyglyceryl-2 triisostearate *2 Remaining amount (7) Octyldodecanol (viscosity 50 mPa·s at 25°C) 5 (8) Hydrogenated polyisobutene *5 10 (9) Polyorganosiloxane having the block structure of Production Example 4 (solid content) 10 (10) Lecithin 0.5 (11) Phytosteryl oleate (melting point 30°C) 0.01 (12) Ethyl linoleate 0.01 (13) Linoleic acid 0.01 (14) Spherical cellulose powder (average particle size 20 μm) 3 (15) (Vinyl dimethicone / lauryl dimethicone) crosspolymer *22 20 (16) 1,2-pentanediol 0.2 (17) Dipropylene glycol 0.3 (18) Fragrance 0.02 (19) Ascorbyl palmitate 0.05 (20) Vanillyl butyl 0.1 (21) Ascorbic acid 0.01 *22: KSG-43 (solvent: glyceryl tri-2-ethylhexanoate, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0098] (Manufacturing method) A: Heat ingredients (1) to (8) to 110°C and dissolve them uniformly. B: Add ingredients (9) to (21) to A and disperse them uniformly. C: Pour B into a jar container and cool to room temperature to solidify and obtain lip balm (solid).

[0099] The lip balm (solid) of Example 25 exhibited excellent resistance to smudging, firmness (elasticity), abrasion resistance (makeup longevity), and sustained moisturizing effect.

[0100] Example 26: Oil-based concealer ingredients (%) (1) Synthetic wax (melting point 80-85°C) *23 5 (2) Microcrystalline wax (melting point 82.2°C) 6 (3) Petrolatum *7 5 (4) Pentaerythrityl tetraethylhexanoate *1 20 (5) Octyldodecanol (viscosity 50 mPa / s at 25°C) 5 (6) Diisostearyl malate *4 10 (7) Isododecane *6 Remaining amount (8) Polyorganosiloxane (solids) having the block structure of Production Example 2 10 (9) Rose fruit oil 1 (10) Distearaldimonium hectorite *13 0.8 (11) Dimethylsilylated silica 0.5 (12) Camellia sinensis flower extract 0.1 (13) Olive squalane (viscosity 30 mPa / s at 25°C) 0.1 (14) Jojoba oil (viscosity 40 mPa·s at 25°C) 1 (15) Lauroyl lysine 2% treated red iron oxide 2 (16) Lauroyl lysine 2% treated yellow iron oxide 3 (17) Lauroyl lysine 2% treated black iron oxide 2 (18) Lauroyl lysine 2% treated titanium dioxide 18 (19) Silica (spherical, average particle size 10 μm) 1 (20) Dipropylene glycol 0.4 *23: CIREWAX 80 (manufactured by CIREBELLE) *24: WHITE BEES WAX (manufactured by Miki Chemical)

[0101] A. Dissolve components (1) to (6) uniformly at 100°C. B. Add components (9) to (19) to A and mix and disperse uniformly using a roll mill. C. Add components (7), (8), and (20) to B and mix. D. Fill C into a metal dish container while stirring at over 100°C. E. Cool D to -10°C to obtain an oil-based concealer.

[0102] The oil-based concealer of Example 26 exhibited excellent resistance to smudging, firmness (elasticity), abrasion resistance (makeup longevity), and sustained moisturizing effect.

[0103] Example 27: Lip Essence Ingredients (%) (1) Stearic Acid 0.5 (2) Bis-Diglyceryl Polyacyladipate-2 6 (3) Petrolatum*7 10 (4) Pentaerythrityl Tetraethylhexanoate*1 20 (5) Octyldodecanol (viscosity 50 mPa / s at 25°C) 5 (6) Diisostearyl Malate*4 Remainder (7) Isododecane*6 20 (8) Polyorganosiloxane (solids) having the block structure of Production Example 3 5 (9) Distearaldimonium Hectorite*13 2 (10) Dimethylpolysiloxane (kinematic viscosity 10 CS at 25°C) 3 (11) Dimethylsilylated Silica 2.5 (12) Hydrolyzed Collagen 0.01 (13) Sodium Hyaluronate 0.01 (14) Hydrolyzed hyaluronic acid 0.01 (15) Astaxanthin solution 0.001 (16) Niacinamide 0.8 (17) Rose water 1.5 (18) Olive squalane (viscosity 30 mPa / s at 25°C) 0.1 (19) Silica (porous spherical, average particle size 10 μm) 1 (20) Dipropylene glycol 0.3 (21) Fragrance 0.05

[0104] A. Dissolve components (1) to (6) uniformly at 80°C. B. Add components (9) to (20) to A and mix and disperse uniformly using a roll mill. C. Add components (7), (8), and (21) to B and mix. D. Fill C into a tube container at 80°C. E. Cool D to 25°C to obtain lip essence.

[0105] The lip essence of Example 27 exhibited excellent properties in terms of non-smudging, firmness (elasticity), abrasion resistance (makeup longevity), and sustained moisturizing effect.

Claims

1. The following components (A) to (D): (A) Non-volatile oil that is liquid at 25°C (B) Semi-solid oil that is semi-solid at 25°C (C) Oily gelling agent (D) Polyorganosiloxane having a block structure, represented by the following general formula (1), having a weight-average molecular weight of 500,000 or more, being solid at room temperature, and having a softening point of 50°C or higher (In the formula, R １ , R ２ , R ３ , R ４ and R ５ A saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, which may each have a hydrogen atom or substituents, m represents the number of repeating diorganosiloxy units, where 50 ≥ m ≥ 0, a, b, c, d, and e represent the molar ratios of each siloxane unit, where 0.3 ≥ a ≥ 0, 0.3 ≥ b > 0, 0.5 ≥ c ≥ 0, 0.95 ≥ d > 0.5, 0.3 ≥ e ≥ 0, and a + b × (2 + m) + c + d + e = 1, and x and y represent the number of hydroxyl groups or alkoxy groups bonded to 1 mole of Si atoms in the siloxane units a to e, respectively, where 0.1 ≥ x > 0 and 0.1 ≥ y > 0.

2. The oily cosmetic composition according to claim 1, wherein the viscosity of component (A) at 25°C is 30,000 mPa·s or less.

3. The oily cosmetic composition according to claim 1 or 2, wherein component (C) is one or more selected from the group consisting of organically modified clay minerals, dextrin fatty acid esters, waxes, amino acid-based gelling agents, fuzzy silica, and fatty acids or their salts (excluding component (A)).

4. The oily cosmetic composition according to claim 1 or 2, wherein component (A) is one or more selected from the group consisting of ester oils, silicone oils, hydrocarbon oils, higher alcohols, and fatty acids.

5. The oily cosmetic composition according to claim 1 or 2, wherein component (B) is a hydrocarbon oil and / or an ester oil.

6. The oily cosmetic composition according to claim 1 or 2, wherein the mass ratio (A) / (D) of component (A) to component (D) is 0.1 to 15.

7. The oily cosmetic composition according to claim 1 or 2, wherein the mass ratio (B) / (D) of component (B) to component (D) is 0.1 to 10.

8. The oily cosmetic composition according to claim 1 or 2, further comprising component (E) a polyhydric alcohol.

9. The oily cosmetic composition according to claim 1 or 2, which is a lip cosmetic composition.

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