JP2019172598A - Oily eyeliner cosmetics - Google Patents

Abstract

To provide oily eyeliner cosmetics that have smooth feeling of use, have excellent properties without bleeding of a makeup film nor lack of a makeup film, and are easy to remove a makeup film.SOLUTION: Provided is an oily eyeliner cosmetic containing (a) a specific copolymer into which one or more hydroxyalkyl (meth) acrylates are introduced, and (b) Hydrophobized powder. Furthermore, it can contain fumed silicic acid anhydride as a component (c).SELECTED DRAWING: None

Description

  The present invention relates to an oily eyeliner cosmetic containing a specific copolymer and a hydrophobized powder, and more specifically, excellent smooth use feeling and no blurring of the cosmetic film or lack of the cosmetic film, The present invention relates to an oily eyeliner cosmetic that easily removes a cosmetic film.

  Eyeliner cosmetics make your eyes look bigger by putting lines with good color on the eye contours. In addition, due to the usage method of drawing on the outline of the eye, there is a demand for a makeup sustainability effect that allows easy drawing of lines, bleeding by tears and sebum, and lack of makeup film due to continuous movement of wrinkles. Recently, makeup that emphasizes the eyes has become popular, and in order to further emphasize the eyes, eyeliner cosmetics are layered on top of each other to draw thin lines and thick lines, and to draw dark and clear eye lines. In addition to usability, emphasis has been placed on ease of removal of the cosmetic film (ease of removal) and lack of burden.

  In addition, efforts to improve various functions have been made in order to meet such market demands. For example, it contains acrylic-silicone-based graft copolymer, spherical fine particle powder, and low boiling point silicone oil in order to obtain a smooth feeling of use, which is a quality required for eyeliner cosmetics. There have been techniques such as liquid makeup cosmetics (see Patent Document 1) having good ductility and excellent usability.

JP 2002-047140 A

  However, although the cosmetics obtained by the technique of Patent Document 1 can provide a long-lasting effect such as water resistance and sebum resistance and a light feeling of use, the cosmetic film is hard and is easy to remove and has no burden. I didn't get a satisfactory one.

  Accordingly, it has been difficult to obtain an eyeliner cosmetic that is excellent in smooth use feeling, non-bleeding of the cosmetic film, and lack of omission of the cosmetic film, and is easy to remove the cosmetic film.

  Under such circumstances, the present inventors have conducted intensive studies, and as a result, the following components (a), (b), (a) specific copolymers into which one or more hydroxyalkyl (meth) acrylates have been introduced. (B) In the oil-based eyeliner cosmetic containing the hydrophobized powder, it is possible to produce a smooth feeling of use, no blur, no missing cosmetic film, and ease of removing the cosmetic film. The headline and the present invention were completed.

That is, the present invention comprises the following components (a) and (b):
A copolymer having a weight average molecular weight of 700 to 300,000 comprising the following monomer units (I) to (IV) as essential components:
Monomer unit (I): silicone macromonomer represented by the following formula (1); 15 to 50% by mass,
[In the above formula (1), X is a divalent aromatic group having 6 to 12 carbon atoms or —COOR ³ —, wherein R ³ is an aliphatic group bonded to Si, and R ¹ is hydrogen. An atom or a methyl group, R ² is the same or different from each other, a fluorine-substituted or unsubstituted monovalent alkyl group having 1 to 30 carbon atoms or an aryl group, and n represents an integer of 1 to 100 . ]
Monomer unit (II): a condensation reaction between an alcohol compound or amine compound having 12 or more carbon atoms and one or more of (meth) acrylic acid, (meth) acrylic acid glycidyl compound, and (meth) acrylic acid halogen compound (Meth) acrylate monomer or (meth) acrylamide monomer obtained from 15 to 50% by mass,
Monomer unit (III): a hydrophilic monomer having a radical polymerizable group which is one or more hydroxyalkyl (meth) acrylates; 0.1 to 25% by mass;
Monomer unit (IV): radically polymerizable hydrophobic monomer having a hydrocarbon group having 10 or less carbon atoms; 10 to 60% by mass
(B) It relates to an oily eyeliner cosmetic containing a hydrophobized powder.

The oily eyeliner cosmetic according to the above, wherein the hydroxyalkyl (meth) acrylate of the monomer unit (III) of the component (a) is either 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate. It is about.

The component (b) relates to the oily eyeliner cosmetic described above, which is a hydrophobized powder treated with at least one selected from a fluorine compound and a silicone compound.

Furthermore, it is related with the said oil-based eyeliner cosmetic containing the fumed silicic acid anhydride as a component (c).

  The oil-based eyeliner cosmetic of the present invention is excellent in a smooth feeling of use, no blur, no missing cosmetic film, and ease of removing the cosmetic film.

  Hereinafter, the present invention will be described in detail. In the present specification, “to” means a range including numerical values before and after.

The copolymer of component (a) used in the present invention is a copolymer having a weight average molecular weight of 700 to 300,000 (hereinafter referred to as “copolymer”) comprising the following monomer units (I) to (IV) as essential components. Polymer (a) ”).
Monomer unit (I): silicone macromonomer represented by the following formula (1); 15 to 50% by mass,
[In the above formula (1), X is a divalent aromatic group having 6 to 12 carbon atoms or —COOR ³ —, wherein R ³ is an aliphatic group bonded to Si, and R ¹ is hydrogen. An atom or a methyl group, R ² is the same or different from each other, a fluorine-substituted or unsubstituted monovalent alkyl group having 1 to 30 carbon atoms or an aryl group, and n represents an integer of 1 to 100 . ]
Monomer unit (II): a condensation reaction between an alcohol compound or amine compound having 12 or more carbon atoms and one or more of (meth) acrylic acid, (meth) acrylic acid glycidyl compound, and (meth) acrylic acid halogen compound (Meth) acrylate monomer or (meth) acrylamide monomer obtained from 15 to 50% by mass,
Monomer unit (III): a hydrophilic monomer having a radical polymerizable group which is one or more hydroxyalkyl (meth) acrylates; 0.1 to 25% by mass;
Monomer unit (IV): radically polymerizable hydrophobic monomer having a hydrocarbon group having 10 or less carbon atoms; 10 to 60% by mass.

Monomer unit (I): Silicone macromonomer The monomer unit (I) for constituting the copolymer (a) is a silicone macromonomer represented by the above formula (1).

R ^{1 of the} silicone macromonomer represented by the above formula (1) is a hydrogen atom or a methyl group, preferably a methyl group.

R ² is the same or different from each other, and is a fluorine-substituted or unsubstituted monovalent alkyl group having 1 to 30 carbon atoms or an aryl group, and more preferable for the skin is fluorine-substituted, Or an unsubstituted monovalent alkyl group having 1 to 6 carbon atoms or an aryl group, more preferably a methyl group, a phenyl group or a trifluoropropyl group from the viewpoint of hypoallergenicity and slipperiness to the skin, and most preferred. Is a methyl group.

X is a C 6-12 divalent aromatic group or —COOR ³ —, and preferably a C 6-8 divalent aromatic group or —COOR ³ —. Examples of the divalent aromatic group include a phenylene group, a tolylene group, a xylylene group, a mesitylene group, and the like, and preferably a phenylene group. In —COOR ³ —, R ³ is an aliphatic group bonded to Si, and the carbonyl group is bonded to a carbon atom of the copolymer main chain. R3 is for example - _{(CH 2) a} - a, where a is an integer from 1 to 9, preferably 2-7 integer, more preferably 3 to 5 integer. Examples where X is a divalent aromatic group or —COOR ³ — are shown in the following general formulas (2) and (3). In these silicone macromonomers, R ^{1 to} R ³ and a, n are the same as those already described.

  n is an integer of 1 to 100, preferably an integer of 3 to 80, and more preferably an integer of 5 to 65. When n exceeds the upper limit value 100, the reactivity of the polymerization reaction may be reduced during the production of the copolymer (a). Moreover, the adhesiveness of the obtained copolymer (a) falls. Furthermore, when a hydrocarbon-based oil agent is blended in cosmetics, the compatibility between the oil agent and the copolymer may deteriorate. On the other hand, when n is 0, the slipperiness is insufficient or the stickiness is increased.

  The silicone macromonomer represented by the general formulas (1), (2), and (3) is typically obtained by dehydrochlorination by a conventional method by obtaining a (meth) acrylate-substituted chlorosilane compound and a carbinol-modified silicone. However, the synthesis method is not limited to this.

Monomer unit (II): (meth) acrylate monomer or (meth) acrylamide monomer The monomer unit (II) for constituting the copolymer (a) comprises an alcohol compound or amine compound having 12 or more carbon atoms, and (meth) It is a (meth) acrylate monomer or a (meth) acrylamide monomer obtained by a condensation reaction of any one or more of acrylic acid, a (meth) acrylic acid glycidyl compound, and a (meth) acrylic acid halogen compound. Since the copolymer (a) becomes a copolymer having a side chain having 12 or more carbon atoms by including a structural unit derived from the (meth) acrylate monomer or (meth) acrylamide monomer of the monomer unit (II), A copolymer (a) showing good compatibility with the oil is obtained. The monomer unit (II) (meth) acrylate monomer or (meth) acrylamide monomer is, for example, an alcohol or amine having 12 or more carbon atoms, (meth) acrylic acid, (glycidyl) (meth) acrylate, or (meth) acrylic acid halide. Can be easily produced by subjecting to a condensation reaction to ester or acid amide. Of the (meth) acrylate monomer or (meth) acrylamide monomer used as the monomer unit (II), specific examples of those particularly preferably used include lauryl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth). In addition to acrylate and behenyl (methacrylate), those represented by the following chemical formula may be mentioned.
_{CH 2 = CHCOOCH 2 CH (OH} ) CH 2 O (CH 2) 17 CH 3
_{CH 2 = C (CH 3)} COOCH 2 CH (OH) CH 2 O (CH 2) 29 CH 3
_{CH 2 = C (CH 3)} CONH (CH 2) 17 CH 3
_{CH 2 = CHCONH (CH 2)} 21 CH 3
_{CH 2 = C (CH 3)} COO (CH 2) 15 CH 3
_{CH 2 = CHCOO (CH 2)} 15 CH 3

Monomer unit (III): hydrophilic monomer The monomer unit (III) for constituting the copolymer (a) is a hydrophilic monomer having a radical polymerizable group. As the hydrophilic monomer having a radically polymerizable group of the monomer unit (III), one or more kinds of (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2 -Hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylate, (meth) acrylamide, (meth) acrylate alcohols, polyoxyalkylene mono (meth) acrylate, (poly) glycerin mono (meth) acrylate are exemplified . In particular, in order to form a film with less odor, it is preferable to use one or more hydroxyalkyl (meth) acrylates. Although not particularly limited, the hydroxyalkyl (meth) acrylate may be 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (2-hydroxypropyl) in view of obtaining a copolymer with good usability and less odor. It is preferable to use one or more of (meth) acrylates.

Monomer unit (IV): radical polymerizable hydrophobic monomer The monomer unit (IV) for constituting the copolymer (a) is a radical polymerizable monomer having a hydrocarbon group having 10 or less carbon atoms. By including a structural unit derived from a radical polymerizable monomer having a hydrocarbon group having 10 or less carbon atoms, the copolymer (a) can be adjusted in strength and flexibility of the coating. The hydrocarbon group having 10 or less carbon atoms contained in the radically polymerizable monomer of the monomer unit (IV) may be any of chain, cyclic and aromatic. For example, one or more kinds of methyl (meth) acrylate, ethyl ( (Meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isodecyl (meth) acrylate, cyclohexyl ( Examples include meth) acrylate, benzyl (meth) acrylate, and isopornyl (meth) acrylate. The radically polymerizable monomer of the monomer unit (IV) is particularly preferably selected from two or more of these. In addition, since these often contribute to the strength and flexibility of the film, they are preferably radically polymerizable monomers that increase Tg when polymerized, such as methyl (meth) acrylate and isoponyl (meth) acrylate. Furthermore, it is more preferable to combine with a radically polymerizable monomer having a low Tg for flexibility.

  The monomer unit (I) for constituting the copolymer (a) is 15 to 50% by mass, preferably 15 to 40% by mass, and more preferably 18 to 38% by mass. When it is less than 15% by mass, the properties as a silicone polymer are lowered, and the compatibility with silicone oil is lowered. Moreover, water resistance also falls and sufficient water repellency cannot be provided to a film. When the amount is more than 50% by mass, the compatibility with the organic oil is lowered, and a viscous film is formed, resulting in poor usability.

  Moreover, although monomer unit (II) for comprising a copolymer (a) is 15-50 mass%, Preferably it is 20-40 mass%, More preferably, it is 28-38 mass%. If it is less than 15% by mass, the compatibility with the organic oil is lowered. If it is more than 50% by mass, it becomes difficult to form a flexible film, so that the feeling in use becomes worse.

  Further, the ratio of the monomer units (I) and (II) for constituting the copolymer (a) depends on the kind of the selected substance, but is 3 as monomer units (I) / monomer units (II). / 1 to 1/3 (mass ratio), particularly preferably 1.2 / 1 to 1 / 1.2 (mass ratio). When the ratio of the monomer units (I) and (II) is 3/1 to 1/3 (mass ratio), a copolymer (a) that is more excellent in compatibility with both silicone oil and polar oil can be obtained. Therefore, it is preferable.

  Moreover, although monomer unit (III) for comprising a copolymer (a) is 0.1-25 mass%, Preferably it is 1-20 mass%, More preferably, it is 5-18 mass%. If it is less than 0.1% by mass, the adhesion is lowered and the sustainability of the cosmetic is lowered. On the other hand, when the content is more than 25% by mass, the compatibility with the coexisting oil is lowered. Moreover, although monomer unit (IV) for comprising a copolymer (a) is 10-60 mass%, Preferably it is 15-50 mass%, More preferably, it is 20-50 mass%. If it is lower than 10% by mass, the strength and flexibility of the film become insufficient, so that the feeling of use becomes worse. If it is higher than 60% by mass, the strength becomes too strong or the flexibility is too low, and the feeling of use becomes worse. Furthermore, the strength and flexibility of the film can be adjusted by the blending balance of the monomer units (III) and (IV), and the component (III) also contributes to imparting hydrophilicity.

  The sum of the mass% of the monomer units (I) to (IV) for constituting the copolymer (a) is adjusted to 100 mass%.

  The copolymer (a) is polymerized in the presence of the monomer of the monomer units (I) to (IV) and a radical polymerization initiator such as benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile. As the polymerization method, any of a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, and a bulk polymerization method can be applied. Among these, the solution polymerization method is preferable because it is easy to appropriately prepare the dispersion of the graph of gel permeation chromatography (GPC) when examining the obtained weight average molecular weight and the weight average molecular weight of the copolymer. Is the method. As the solvent used in the polymerization, aliphatic organic solvents such as pentane, hexane, decane, dodecane, hexadecane, and octadecane, aromatic organic solvents such as benzene, toluene, xylene, methanol, ethanol, propanol, butanol, The polymerization reaction may be carried out in an alcoholic organic solvent such as hexanol or decanol, a halogenated organic solvent such as chloroform or carbon tetrachloride, or a ketone organic solvent such as acetone or methyl ethyl ketone. However, from the viewpoint of use as a cosmetic application, it is preferable to use no solvent or ethanol or isopropanol as a solvent.

  The weight average molecular weight in terms of polystyrene in GPC of the copolymer (a) thus produced is 700 to 300,000, preferably 2000 to 200,000, more preferably 3000 to 100,000. It is. When the weight average molecular weight is larger than 300,000, compatibility with various oil agents is lowered. On the other hand, when the weight average molecular weight is less than 700, the feeling of use as a film agent, thickener, surfactant, and / or dispersant is lowered.

  Commercially available products of the copolymer of component (a) used in the present invention include those listed as Polyacrylate-44 (polyacrylate-44) under the INCI name (International Nomenclature Cosmetic Labeling Names). X-22-8338E (solid content: 30%, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

  The content of the component (a) in the present invention is not particularly limited, but is 0.5 to 20% by mass (from the viewpoints of excellent blurring, lack of makeup film loss, and ease of removal of the makeup film). Hereinafter, it is preferably simply%), more preferably 1 to 15%, and particularly preferably 3 to 12%.

  The hydrophobized powder of component (b) used in the present invention is obtained by coating part or all of the surface of the powder with a hydrophobizing agent in order to impart hydrophobicity. If it is used for, it can use without being specifically limited. By treating the powder surface, the adhesion of the powder surface is weakened and the aggregation of the powders is reduced. Therefore, when combined with the component (a), a more uniform decorative film is formed. Effects such as lack of film loss can be obtained. Examples of the hydrophobizing agent used in the hydrophobizing powder of component (b) include fluorine compounds, silicone compounds, oil agents, gelling agents, emulsion polymers, and the like. A fluorine compound and a silicon compound are more preferable, and a fluorine compound is particularly preferable in terms of excellent ease of dropping.

  Examples of the fluorine compound used in the hydrophobized powder of component (b) used in the present invention include perfluoroalkyl phosphate diethanolamine salt, perfluorooctyltriethoxysilane, and perfluoropolyether. More preferably, fluorooctyltriethoxysilane is used.

  If the powder used as the base of the hydrophobized powder of component (b) used in the present invention is usually used in cosmetics, it has a spherical, plate-like, needle-like shape, fine particles, pigment grade, etc. There are no particular restrictions on the particle size, porous, non-porous particle structure, etc., and inorganic powders, glitter powders, organic powders, pigment powders, metal powders, composite powders And the like. Specifically, white inorganic pigments such as titanium oxide, zinc oxide, cerium oxide and barium sulfate, colored inorganics such as iron oxide, carbon black, titanium / titanium oxide sintered product, chromium oxide, chromium hydroxide, bitumen and ultramarine blue Pigment, silica, talc, muscovite, phlogopite, saucite, biotite, synthetic mica, sericite, sericite, kaolin, silicon carbide, bentonite, smectite, aluminum oxide, magnesium oxide, zirconium oxide, Antimony oxide, diatomaceous earth, aluminum silicate, magnesium aluminum silicate, calcium silicate, barium silicate, magnesium silicate, calcium carbonate, magnesium carbonate, hydroxyapatite, boron nitride, etc. white powder, titanium oxide coated mica , Titanium oxide coated bismuth oxychloride, iron oxide mica Bright powder such as Tungsten, Bituminized Mica Titanium, Carmine Treated Mica Titanium, Bismuth Oxychloride, Fish Scale Foil, Polyethylene Terephthalate / Aluminum / Epoxy Laminated Powder, Polyethylene Terephthalate / Polyolefin Laminated Film Powder, Polyethylene Terephthalate / Polymethylmethacrylate Laminated Film Powder Body, polyamide resin, polyethylene resin, polyacrylic resin, polyester resin, fluorine resin, cellulose resin, polystyrene resin, copolymer resin such as styrene-acrylic copolymer resin, polypropylene resin, urethane resin, etc. Organic polymer resin powder, organic low molecular weight powder such as zinc stearate, N-acyl lysine, natural organic powder such as silk powder, cellulose powder, dextrin powder, red 201, red 202, red 2 No. 5, Red No. 226, Red No. 228, Orange No. 203, Orange No. 204, Blue No. 404, Yellow No. 401, Red No. 3, Red No. 104, Red No. 106, Orange No. 205, Yellow No. 4, Yellow No. 5 , Organic pigment powder such as zirconium, barium or aluminum lake such as green No. 3, blue No. 1 or metal powder such as aluminum powder, gold powder, silver powder, fine titanium oxide coated mica titanium, fine zinc oxide coated mica titanium, Examples thereof include composite powders such as barium sulfate-coated mica titanium, titanium oxide-containing silicon dioxide, and zinc oxide-containing silicon dioxide, and fibers such as nylon, polyester, rayon, and cellulose.

  The treatment amount of the hydrophobizing agent of the hydrophobizing powder of component (b) used in the present invention is not particularly limited, but is preferably 0.1 to 10%, more preferably 1 to 5%.

  The content of the component (b) in the present invention is not particularly limited, but is preferably 0.1 to 50% from the viewpoints of smooth use feeling, lack of a decorative film and ease of removal. 1 to 40% is more preferable, and 10 to 40% is particularly preferable.

  The content mass ratio of the component (a) and the component (b) in the present invention is not particularly limited, but the component (a) / (b) is from the viewpoint of being more excellent in the lack of a decorative film and ease of removal. = 0.01 to 200 is preferable, 0.05 to 15 is more preferable, and 0.1 to 1 is particularly preferable.

The oily eyeliner cosmetic composition of the present invention further contains fumed silicic acid as component (c), so that the cosmetic film becomes stronger and the cosmetic film is not partially missing and does not bleed. Effects such as ease of removing the decorative film can be obtained.
The component (c) fumed silicic anhydride in the present invention is fine amorphous silicic anhydride, and examples thereof include those obtained by hydrolyzing silicon tetrachloride in hydrogen and an oxygen flame. The fumed silicic acid may be surface-treated. Examples of the treatment method include trimethylsiloxy treatment, dimethylsilylation treatment, octylsilanization treatment, methylhydrogenation with trimethylsilyl chloride or hexamethyldisilazane. Examples thereof include a coating baking process using polysiloxane and a coating with metal soap. Among these, dimethylsilylation treatment is preferable from the standpoint of superior lack of partial omission of the decorative film. Moreover, the average particle diameter of the primary particles of these fumed silicic anhydride is not particularly limited, but is preferably 50 nm or less, more preferably 5 to 50 nm, and particularly preferably 5 to 20 nm.
Commercially available products include AEROSIL 200, AEROSIL 300, AEROSIL 380, AEROSIL R-972, AEROSIL R-974, AEROSIL R-976 (manufactured by Nippon Aerosil Co., Ltd.), Talanox 500 (manufactured by Tarco), Cabozil TS-530 ( Can be used, and one or more of these can be used.

  The content of the component (c) in the present invention is not particularly limited, but is preferably 0.1 to 10% from the viewpoint that the decorative film becomes stronger and is more excellent in the absence of partial omission of the decorative film, More preferably, it is 1 to 5%.

  The oily eyeliner cosmetics of the present invention include, in addition to the above components (a) to (c), powders such as components usually used in cosmetics, oily components, inorganic pigments, organic pigments and dyes, and surface activity. Agents, fibers, polyhydric alcohols, water-soluble polymers, water-soluble film-forming resins, aqueous components such as humectants, sugars, UV absorbers, anti-fading agents, antioxidants, antifoaming agents, cosmetic ingredients, preservatives Further, a fragrance or the like can be contained within a range not impeding the effects of the present invention.

  The oil component is other than the component (a), and can be used without particular limitation as long as it is an oil that is usually used in cosmetics. The origin of animal oil, vegetable oil, synthetic oil, semi-solid oil, liquid oil, etc. Regardless of properties such as volatile oil, hydrocarbons, fats and oils, ester oils, fatty acids, higher alcohols, fluorine-based oils and the like can be used. Specifically, hydrocarbons such as liquid paraffin, squalane, polyisobutylene, light liquid isoparaffin, isododecane, petrolatum, polyethylene, microcrystalline wax, Fischer-Tropsch wax, ceresin wax, olive oil, mink oil, macadamian nut oil, etc. Fats and oils, cetyl isooctanoate, isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, neopentyl glycol dioctanoate, glyceryl tri (caprylate / caprate), jojoba oil, glyceryl tri-2-ethylhexanoate, diacid malate Esters such as isostearyl, fatty acids such as isostearic acid and oleic acid, higher alcohols such as oleyl alcohol, isostearyl alcohol and 2-decyltetradecanol S, perfluorodecane, perfluorooctane, fluorine-based oils such perfluoropolyether or the like, oil-soluble cosmetic ingredients, and the like.

  As the powder component, other than the components (b) and (c), if the powder is used as a powder generally used in cosmetics, a spherical shape, a plate shape, a needle shape, fine particles, It is not particularly limited by particle size such as pigment class, particle structure such as porous and nonporous, etc., inorganic powders, glitter powders, organic powders, pigment powders, metal powders, Examples include composite powders. Specifically, white inorganic pigments such as titanium oxide, zinc oxide, cerium oxide, barium sulfate, iron oxide, carbon black, titanium / titanium oxide sintered product, chromium oxide, chromium hydroxide, bitumen, ultramarine blue, etc. Colored inorganic pigments, talc, muscovite, phlogopite, saucite, biotite, synthetic mica, sericite, sericite, kaolin, silicon carbide, bentonite, smectite, aluminum oxide, magnesium oxide, zirconium oxide, Antimony oxide, diatomaceous earth, aluminum silicate, magnesium aluminum silicate, calcium silicate, barium silicate, magnesium silicate, calcium carbonate, magnesium carbonate, hydroxyapatite, boron nitride, etc. white powder, titanium oxide coated mica , Titanium oxide coated bismuth oxychloride, iron oxide mica Bright powder such as Tungsten, Bituminized Mica Titanium, Carmine Treated Mica Titanium, Bismuth Oxychloride, Fish Scale Foil, Polyethylene Terephthalate / Aluminum / Epoxy Laminated Powder, Polyethylene Terephthalate / Polyolefin Laminated Film Powder, Polyethylene Terephthalate / Polymethylmethacrylate Laminated Film Powder Body, polyamide resin, polyethylene resin, polyacrylic resin, polyester resin, fluorine resin, cellulose resin, polystyrene resin, copolymer resin such as styrene-acrylic copolymer resin, polypropylene resin, urethane resin, etc. Organic polymer resin powder, organic low molecular weight powder such as zinc stearate, N-acyl lysine, natural organic powder such as silk powder, cellulose powder, dextrin powder, red 201, red 202, red 2 No. 5, Red No. 226, Red No. 228, Orange No. 203, Orange No. 204, Blue No. 404, Yellow No. 401, Red No. 3, Red No. 104, Red No. 106, Orange No. 205, Yellow No. 4, Yellow Organic pigment powders such as zirconium, barium or aluminum lakes such as No. 5, Green No. 3 and Blue No. 1 or metal powders such as aluminum powder, gold powder and silver powder, fine titanium oxide coated mica titanium, fine zinc oxide coated mica Examples thereof include composite powders such as titanium, barium sulfate-coated mica titanium, titanium oxide-containing silicon dioxide, and zinc oxide-containing silicon dioxide, and fibers such as nylon, polyester, rayon, and cellulose.

As the surfactant, any surfactant that is generally used in cosmetics can be used. Nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, etc. Is mentioned. Although not particularly limited, it is preferable to use an amphoteric surfactant from the viewpoint that the effects of the present invention can be remarkably exhibited, and it is particularly difficult to use lecithin.
The aqueous component may be any component that is soluble in water. In addition to water, for example, propylene glycol, 1,3-butylene glycol, dipropylene glycol, glycerin, diglycerin, polyglycerin, aloe vera, witch. Plant extracts such as hazel, hamamelis, cucumber, lemon, lavender, rose water and the like can be mentioned.
Examples of the ultraviolet absorber include benzophenone-based, PABA-based, cinnamic acid-based, salicylic acid-based, such as 4-tert-butyl-4'-methoxydibenzoylmethane, oxybenzone, 2-methoxyhexyl paramethoxycinnamate 2, 4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine, hexyl diethylaminohydroxybenzoylbenzoate, bisethylhexyloxyphenol methoxyphenyl triazine and the like can be mentioned.
Examples of the antioxidant include tocopherol and ascorbic acid, examples of the beauty component include vitamins, anti-inflammatory agents, herbal medicines, and examples of the antiseptic include paraoxybenzoate, phenoxyethanol, 1,2-pentadiol, and the like. .

  The oily eyeliner cosmetics of the present invention may be in any form such as liquid, gel, cream, solid, etc., and may have a dosage form such as oily, water-in-oil type using oil as a continuous phase. From the standpoint that the effects of the present invention can be obtained particularly remarkably, the water content is preferably 1% or less, more preferably 0.5% or less, and no water is contained. Particularly preferred.

  Hereinafter, the synthesis example of the copolymer (a) and the examples and comparative examples of the oily eyeliner cosmetics of the present invention will be shown to specifically explain the present invention. However, the present invention is limited to the following examples. It is not something. Unless otherwise specified, “%” described below means “mass%” and represents the mass% of each component with the total mass of each example as 100%.

Synthesis examples (1) to (4)
In a glass flask equipped with a stirrer, a thermometer, and a reflux condenser, 140.0 g of isopropanol, each monomer shown in Table 1 below, and 4.0 g of t-butylperoxy-2-ethylhexanoate were placed under a nitrogen stream. The mixture was heated to reflux with stirring. After polymerization for 5 hours, volatile components were distilled off under reduced pressure to obtain silicone copolymers (Synthesis Examples (1) to (4)). The weight average molecular weight (in terms of polystyrene) was determined by GPC.

Examples 1 to 9 and Comparative Examples 1 to 4: Oily eyeliner cosmetic (gel)
Oily solid eyeliner cosmetics having the formulations shown in Table 2 below were prepared and evaluated for smooth use feeling, no blur, lack of cosmetic film, and ease of removal by the following methods. The results are also shown in Table 2.

(Manufacturing method)
A. Ingredients (1) to (8) are uniformly dissolved by heating at 110 ° C.
B. Add components (9) to (17) to A and mix uniformly.
C. B was filled in a container to obtain an oily eyeliner cosmetic (gel).

(Evaluation methods)
The following evaluation items were evaluated by the following methods.
(Evaluation item)
I. Smooth use feeling b. No blurring. Ease of removal of missing cosmetic film d. Ease of dropping

With respect to the items (i) to (d), a use test was conducted by 20 specialist panels for each sample. Each sample was applied to the skin and evaluated for i) immediately after use, and for b) and c) after 6 hours from use, whether it was blotted with sweat or tears, and whether there was no omission of a cosmetic film was evaluated. Thereafter, an appropriate amount of the remover shown below was included in the cotton, and the ease of dropping was evaluated. About each item, each panel person evaluated in seven grades by the following absolute evaluation criteria, gave a score, the average value was calculated from the total score of all the panels, and judged by the following four-step judgment criteria.

Absolute Evaluation Criteria (Score): (Evaluation)
6: Very good 5: Good 4: Somewhat good 3: Normal 2: Somewhat bad 1: Bad 0: Very bad

4-step criteria (judgment): (average score)
: Over 5 points
○: Over 3.5 points and 5 points or less △: Over 1 point and 3.5 points or less ×: 1 point or less

Remover for evaluation (component)
(1) Liquid paraffin 4
(2) Isododecane 8
(3) Purified water remaining amount (4) Carboxymethylcellulose 0.8
(5) Triethanolamine 1.8
(6) Methyl paraoxybenzoate 0.3
(7) Phenoxyethanol 0.5
(8) Glycerin 2
(Manufacturing method)
A. Ingredients (1) to (2) are uniformly dispersed.
B. Components (3) to (8) are mixed uniformly.
C. Add A to B and emulsify at room temperature.
D. C was filled in a container to obtain an evaluation remover.

As is apparent from the results in Table 2, the oily eyeliner cosmetics (gel form) of Examples 1 to 9 of the present invention have a smoother feeling of use and blurring than the oily eyeliner cosmetics of Comparative Examples 1 to 4. It was excellent in lack of makeup, lack of makeup film, and ease of removal.
On the other hand, in Comparative Example 1 without component (a), the makeup film was not firm, and satisfactory results were not obtained in terms of smooth use feeling, no bleeding, and lack of the makeup film. Further, in Comparative Example 2 containing an (acrylates / dimethicone) copolymer instead of the component (a), the adhesion of the decorative film was high, and a satisfactory one was not obtained in terms of ease of makeup removal. Further, in Comparative Example 3 containing a copolymer of (acrylates / stearyl acrylate / dimethicone methacrylate) instead of component (a), the cosmetic film bleeds into sebum, which is satisfactory in terms of bleed. I couldn't. Further, in Comparative Example 4 which does not contain the hydrophobized powder of component (b), the cosmetic film bleeds into sebum and is peeled off, which is satisfactory in terms of no bleed and lack of cosmetic film. I couldn't get anything.

Example 10: Water-in-oil eyeliner cosmetic (liquid)
(Ingredient) (%)
(1) (palmitic acid / octanoic acid) dextrin 2
(2) Polyethylene * 5 2
(3) Fischer-Tropsch wax * 9 2
(4) 2-decyltetradecanol * 10 1
(5) Light liquid isoparaffin * 11 Residual amount (6) Polyisobutylene * 12 5
(7) Copolymer (a) of Synthesis Example (2) 7
(8) Dimethyl distearyl ammonium hectorite * 13 3
(9) Silylated silica anhydride * 8 0.5
(10) Methylsiloxane network polymer * 14 3
(11) Bengala * 15 0.5
(12) Red No. 226 * 6 0.5
(13) Carbon black 4
(14) Purified water 10
(15) Edetate disodium 0.01
(16) 1,2-pentanediol 1
(17) Sorbitan sesquioleate 0.5
(18) Methyl paraoxybenzoate 0.5
(19) Fragrance 0.1
* 9: CIREBELLE108 (CIREBELLE)
* 10: NJCOAL 240A (manufactured by Shin Nippon Chemical Co., Ltd.)
* 11: IP solvent 1620MU (made by Idemitsu Kosan Co., Ltd.)
* 12: Opanol B-100 (manufactured by BASF)
* 13: Lucentite SAN (Coop Chemical)
* 14: Tospearl 145A (Momentive Performance Materials Japan)
* 15: 2% methyl hydrogen polysiloxane treatment

(Manufacturing method)
A. Components (1) to (7) are heated and dissolved at 100 ° C., and components (8) to (13) are uniformly mixed.
B. Add components (14) to (19) to A and emulsify.
C. B was filled in a container with an applied body to obtain a water-in-oil eyeliner cosmetic (liquid).

  The water-in-oil eyeliner cosmetic of Example 10 was excellent in smooth use feeling, no blur, no missing cosmetic film, and easy removal.

Example 11: Oily eyeliner cosmetic (solid)
(Ingredient) (%)
(1) Dextrin palmitate * 16 1
(2) Ceresin wax 10
(3) Trimethylsiloxysilicate * 17 14
(4) Methacryl-modified methylpolysiloxane * 18 5
(5) Dimethiconol 2.5
(6) Light liquid isoparaffin * 11 Residual amount (7) Decamethylcyclopentasiloxane 20
(8) Phenyl glycol 1
(9) Glyceryl tri-2-ethylhexanoate 5
(10) Copolymer (a) 3 of Synthesis Example (3)
(11) Black iron oxide * 19 10
(12) Polyethylene terephthalate / aluminum
・ Epoxy laminated powder 1
(13) Silicic anhydride * 20 2
(14) Titanium oxide coated synthetic phlogopite * 21 2
(15) Tocopherol acetate 0.5
* 16: Leopard KL2 (Chiba Flour Mills)
* 17: Silicon KF-7312J (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 18: Silicon KP-545 (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 19: 2% dimethicone treatment
* 20: AEROSIL380S (Nippon Aerosil Co., Ltd.)
* 21: HELIOS R100S (Topy Industries) 1% liquid paraffin treatment

(Manufacturing method)
A. Components (1) to (10) are dissolved by heating at 90 ° C.
B. Add components (11) to (15) to A and mix uniformly.
C. B was filled in a metal pan at 90 ° C. to obtain an oily eyeliner cosmetic (solid).

  The oil-based eyeliner cosmetic (solid) of Example 11 was excellent in smooth use feeling, no blur, no missing cosmetic film, and easy removal.

Example 12: Oily eyeliner cosmetic (pencil shape)
(Ingredient) (%)
(1) Owl 20
(2) Sunflower seed wax 10
(3) Trimethylsiloxysilicate * 17 10
(4) Decamethylcyclopentasiloxane 5
(5) 2-decyltetradecanol 15
(6) Liquid paraffin remaining amount (7) Phenyl glycol 1
(8) Copolymer (a) of Synthesis Example (4) 9
(9) Methylsiloxane network polymer * 14 5
(10) Carbon black * 22 10
(11) Sericite * 6 10
(12) Silylated silicic acid * 8 1
(13) Natural vitamin E 0.1
* 22: 2% lecithin treatment (production method)
A. Components (1) to (8) are heated and dissolved at 90 ° C.
B. Add components (9) to (13) to A and mix uniformly.
C. B was filled in a mold and charged in a container to obtain an oily eyeliner cosmetic (pencil shape).

The oily eyeliner cosmetic (pencil-like) of Example 12 was excellent in smooth use feeling, no blur, no missing cosmetic film, and easy removal.

Claims (4)

The following components (a) and (b);
(A) a copolymer having a weight average molecular weight of 700 to 300,000 comprising the following monomer units (I) to (IV) as essential components;
Monomer unit (I): silicone macromonomer represented by the following formula (1); 15 to 50% by mass,
[In the above formula (1), X is a divalent aromatic group having 6 to 12 carbon atoms or —COOR ³ —, wherein R ³ is an aliphatic group bonded to Si, and R ¹ is hydrogen. An atom or a methyl group, R ² is the same or different from each other, a fluorine-substituted or unsubstituted monovalent alkyl group having 1 to 30 carbon atoms or an aryl group, and n represents an integer of 1 to 100 . ]
Monomer unit (II): a condensation reaction between an alcohol compound or amine compound having 12 or more carbon atoms and one or more of (meth) acrylic acid, (meth) acrylic acid glycidyl compound, and (meth) acrylic acid halogen compound (Meth) acrylate monomer or (meth) acrylamide monomer obtained from 15 to 50% by mass,
Monomer unit (III): a hydrophilic monomer having a radical polymerizable group which is one or more hydroxyalkyl (meth) acrylates; 0.1 to 25% by mass;
Monomer unit (IV): radically polymerizable hydrophobic monomer having a hydrocarbon group having 10 or less carbon atoms; 10 to 60% by mass
(B) An oily eyeliner cosmetic containing a hydrophobized powder. The hydroxyalkyl (meth) acrylate of the monomer unit (III) of the component (a) is one or more selected from 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. 2. The oily eyeliner cosmetic according to 1. The oily eyeliner cosmetic according to claim 1 or 2, wherein the component (b) is a hydrophobized powder treated with one or more selected from fluorine compounds and silicone compounds. Furthermore, the oil-based eyeliner cosmetics in any one of Claims 1-3 which contain fumed silicic acid anhydride as a component (c).