JP6849986B2 - Hair mascara composition - Google Patents

Description

The present invention relates to a hair mascara composition.

The hair mascara composition is generally easy to use, and has the advantage that hair can be dyed speedily simply by applying it to a target site. Therefore, for example, it is suitable for use when quickly dyeing gray hair before going out. In addition, the hair mascara composition can often be washed off with shampoo, which is convenient when you are dissatisfied with the dyed color or want to change to another color. In addition, the hair mascara composition generally causes less damage to the hair as compared to ordinary hair dyes. Therefore, the market demand for hair mascara compositions is high.

In the conventional hair mascara composition, the set resin is often used as a hair fixing agent, and the hair is stiff, although the fixing force and the coloring property are excellent.
As an example of improving the stiffness of hair, for example, Patent Document 1 discloses a hair styling composition using solid oils and fats as a hair fixing agent. However, the hair styling composition has a drawback that it has a good feel when applied to hair, but has low quick-drying property, and easily adheres to hands and clothes. Further, in the hair styling composition, the dispersibility of the decorative material is poor, and it is difficult to uniformly disperse and spread the decorative material on the hair, so that the uniformity of coloring is not sufficient. Further, Patent Document 2 discloses a composition for hair application containing a water-soluble thickener. However, the hair coating composition has a drawback that it dries quickly and does not have sufficient fixing force, so that it easily adheres to hands and clothes.

The hair mascara composition can improve the stiffness of the hair by reducing the content of the set resin, but the fixing force is weakened, and as a result, problems such as color transfer have occurred. In addition, by reducing the content of the set resin, the viscosity is lowered, the liquid is scattered, the liquid drips, etc., which deteriorates the operability, and the dispersibility of the pigment is lowered, so that the hair cannot be uniformly applied. There was a problem. Patent Document 3 discloses a hair mascara containing water, ethanol, and hydroxypropylmethylcellulose, which is a thickener, in order to prevent the liquid from splashing, but the quick-drying property is insufficient and the color is easily transferred.

Attempts have been made to soften the film formed by the hair fixing agent and reduce the stiffness of the hair, but the texture is improved, but the fixing force is weak and the color is easily transferred (for example, Patent Documents 4 and 5). Further, although there is an example in which the feel is improved by combining the set resin with a gelling agent and a silicone-modified polymer (Patent Document 6), the fixing force is not sufficient and there is still a problem of color transfer.

Eyelash mascara is consistent with the hair mascara composition in that it adds color to the keratin fibers, but with a very different purpose. The purpose of the eyelash mascara is to have a long rush effect (effect of making the hair look thick and long) and a curl keeping effect (effect of curling and fixing the hair) (for example, Patent Document 7), but the hair mascara composition. The purpose of the object is to apply only the color while keeping the hair natural. Therefore, when the eyelash mascara is used as the hair mascara composition, it becomes stiff, and it is difficult to apply the eyelash mascara to the hair mascara composition.

Japanese Unexamined Patent Publication No. 2004-10540 Japanese Patent No. 4714076 Japanese Patent No. 5117654 Japanese Unexamined Patent Publication No. 6-100418 Japanese Unexamined Patent Publication No. 11-10012 Japanese Unexamined Patent Publication No. 2005-239626 Japanese Unexamined Patent Publication No. 2001-55310

It is an object of the present invention to provide a hair mascara composition having operability, quick-drying property, uniform coating force, abrasion resistance and water resistance which are resistant to color transfer, and having a good touch. And.

The present inventors have diligently studied to solve the above problems. As a result, they have found that the above-mentioned problems can be solved by a hair mascara composition having the following constitution, and have completed the present invention.
The present invention is, for example, the following [1] to [5].

[1] In 100% by mass of the hair mascara composition, at least one component (A) of 0.1 to 30% by mass selected from the silicone copolymer and its saponification product, and 0.5 of hydroxypropyl cellulose (B). The silicone copolymer contains ~ 5% by mass and the pigment (C), and the silicone copolymer has 2 or more polymerizable groups in 0.1 to 50 parts by mass of (a1) silicone (however, 100% by mass of silicone (a1)). A mixture containing (a2) 0.5 to 14 parts by mass of a hydrophilic monomer and (a3) 30 to 99.4 parts by mass of a hydrophobic monomer (provided that the entire mixture contains 100 parts by mass). A hair mascara composition which is a polymer of

[2] The hair mascara composition according to [1], wherein the silicone having two or more polymerizable groups contained in the silicone (a1) is represented by the formula (2).
(R ¹ ) (R ² ) ₂ SiO (Si (R ² ) ₂ O) _n Si (R ² ) ₂ (R ¹ ) (2)
[In the formula (2), R ¹ there are a plurality of, each independently represent a polymerizable group, the R ² s each independently represent a linear, branched or cyclic, hydrocarbon having 1 to 18 carbon atoms It represents a group or an alkoxy group, and the hydrocarbon group and the alkoxy group may have a substituent, and n represents an integer of 10 to 1,000. ]

[3] The hair mascara composition according to [1] or [2], wherein the hydrophilic monomer (a2) has a carboxyl group.

[4] The method according to any one of [1] to [3], wherein the hydrophobic monomer (a3) is a linear or branched vinyl ester of an alkylcarboxylic acid having an alkyl group having 1 to 15 carbon atoms. Hair mascara composition.

[5] The hair mascara composition according to any one of [1] to [4], which further comprises an oil agent (D).

According to the present invention, a hair mascara composition having operability that does not easily cause liquid splashing and dripping, quick-drying, uniform covering power, abrasion resistance and water resistance that do not easily transfer colors, and a good touch. Can be provided.

Hereinafter, the hair mascara composition of the present invention will be described. Hereinafter, the hair mascara composition of the present invention is also simply referred to as a "composition". In this specification, acrylic and methacrylic are also collectively referred to as "(meth) acrylic".

[Hair mascara composition]
The composition of the present invention comprises at least one component (A) (hereinafter also referred to as “component (A)”) selected from the silicone copolymer and its saponification product, which will be described below, and hydroxypropyl cellulose (B). , And the pigment (C). The composition preferably further contains an oil agent (D). Further, the composition may contain a resin (E) or other components (F), if necessary.

<Ingredient (A)>
The composition of the present invention contains at least one component (A) selected from the silicone copolymer and its saponification product. The silicone copolymer is a polymer of a mixture containing silicone (a1), a hydrophilic monomer (a2) and a hydrophobic monomer (a3). The mixture may contain compounds other than the above (a1) to (a3), if necessary.

<Silicone (a1)>
Silicone (a1) has a siloxane bond. The silicone (a1) is preferably a linear or branched silicone having a main chain having an atomic number of 10 to 2,100.

The silicone (a1) is preferably a silicone represented by the formula (1).
(R ¹ ) _a (R ² ) _3-a SiO (Si (R ² ) ₂ O) _n Si (R ² ) _3-a' (R ¹ ) _a' (1)
In the formula (1), a plurality of R ¹ each independently represent a polymerizable group, the R ² s each independently represent a linear, branched or cyclic, hydrocarbon group having 1 to 18 carbon atoms Alternatively, it represents an alkoxy group, and the hydrocarbon group and the alkoxy group may have a substituent. n represents an integer of 10 to 1,000, a represents 0 or 1, and a'represents 0 or 1.

Examples of R ¹ include an organic group having a double bond and having 2 to 8 carbon atoms, and specific examples thereof include a vinyl group, an allyl group, a butenyl group, and a (meth) acryloyloxyalkyl group. The alkylene group contained in the (meth) acryloyloxyalkyl group preferably has 1 to 4 carbon atoms. As R ¹ , vinyl group, 3- (meth) acryloyloxypropyl group and (meth) acryloyloxymethyl group are preferable.

Examples of the hydrocarbon group having 1 to 18 carbon atoms of R ² include a methyl group, an ethyl group, an N-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group and an n-pentyl group. Examples thereof include an isopentyl group, a neopentyl group, a t-pentyl group, and a hexyl group.

Examples of the alkoxy group having 1 to 18 carbon atoms of R ² include a methoxy group, an ethoxy group, a propoxy group, and an n-butyloxy group.
The R ² may be a group having a substituent in which a part of the alkyl group having 1 to 18 carbon atoms and the alkoxy group is substituted, and examples of the substituent include a halogen group and a mercapto group. Examples thereof include a carboxyl group, a keto group, an enamine group, an amino group, an aminoethylamino group, an aryloxy group, an aryl group, an alkoxysilyl group and a hydroxyl group.

Examples of the silicone represented by the formula (1) include α, ω-divinyl-polydimethylsiloxane, α, ω-di- (3- (meth) acryloyloxypropyl) -polydimethylsiloxane, and α-monovinyl-poly. Examples thereof include dimethylsiloxane, α-mono-(3- (meth) acryloyloxypropyl) -polydimethylsiloxane, and α-mono-((meth) acrylicoxymethyl) -polydimethylsiloxane.

The mixture forming the component (A) contains 10% by mass or more, preferably 50% by mass or more of silicone having 2 or more polymerizable groups in 100% by mass of the silicone (a1) contained in the mixture. Specifically, the silicone having two or more polymerizable groups is preferably a silicone represented by the following formula (2).

(R ¹ ) (R ² ) ₂ SiO (Si (R ² ) ₂ O) _n Si (R ² ) ₂ (R ¹ ) (2)
In the formula (2), R ^1, R ² and n have the same meanings as R ^1, R ² and n in formula (1).
Examples of the silicone represented by the formula (2) include α, ω-divinyl-polydimethylsiloxane and α, ω-di- (3- (meth) acryloyloxypropyl) -polydimethylsiloxane.

Examples of commercially available silicone products having two or more polymerizable groups include α, ω-divinyl-polydimethylsiloxane manufactured by Polymer PTS-P1000 (Wacker Chemie AG (Munich, Germany), trade name).

The silicone (a1) may be used alone or in combination of two or more.
The blending amount of the silicone (a1) in 100 parts by mass of the mixture is 0.1 to 50 parts by mass, preferably 0.1 to 40 parts by mass.

<Hydrophilic monomer (a2)>
The hydrophilic monomer (a2) has a polymerizable group and is hydrophilic. The hydrophilic monomer (a2) is a monomer other than the silicone (a1). The hydrophilic monomer (a2) preferably has a hydrophilic group, and examples of the hydrophilic group include a carboxyl group, an acid anhydride group, an amide group, a sulfonic acid group, a nitrile group, and an amino group. May be formed. Examples of the polymerizable group include organic groups having 1 to 8 carbon atoms having a double bond or a triple bond. The hydrophilic group and the polymerizable group may be the same group, and examples of the group in which the hydrophilic group and the polymerizable group are the same include a nitrile group.

Examples of the hydrophilic monomer (a2) include unsaturated organic monocarboxylic acids such as (meth) acrylic acid and crotonic acid; unsaturated organic dicarboxylic acids such as maleic acid and fumaric acid; and unsaturated organic acids such as maleic anhydride. Anhydrous; unsaturated carboxylic acid amides such as (meth) acrylamide; unsaturated sulfonic acids such as vinyl sulfonic acid and 2- (meth) acrylamide-2-methylpropanesulfonic acid and salts thereof; such as carbonitrile and acrylic nitrile. Nitriles; amino group-containing monomers such as diallyldimethylammonium chloride (DADMAC), 3-trimethylammonium propyl (meth) acrylamide chloride (MAPTAC) and 2-trimethylammonium ethyl (meth) acrylate chloride.

The hydrophilic monomer (a2) preferably has a carboxyl group, and the hydrophilic monomer (a2) is preferably crotonic acid and (meth) acrylic acid.
The hydrophilic monomer (a2) may be used alone or in combination of two or more.

From the viewpoint of obtaining a hair mascara composition that imparts flexibility when applied to hair and has a good feel, the amount of the hydrophilic monomer (a2) in 100 parts by mass of the mixture is preferably 0.5 to 14 parts by mass. Is 0.5 to 10 parts by mass, more preferably 3 to 6 parts by mass.

<Hydrophobic monomer (a3)>
The hydrophobic monomer (a3) has a polymerizable group and is hydrophobic. The hydrophobic monomer (a3) is a monomer other than the silicone (a1) and the hydrophilic monomer (a2). Examples of the hydrophobic monomer (a3) include vinyl ester, (meth) acrylic acid ester, and unsaturated hydrocarbon.

Examples of the vinyl ester include vinyl esters of linear or branched alkylcarboxylic acids having 1 to 15 carbon atoms, and specifically, vinyl acetate (hereinafter, also referred to as “VA”) and vinyl propionate. , Vinyl butyrate, vinyl-2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate, vinyl pivalate, VeoVa9 and VeoVa10 (Hexion Specialty Chemicals (Columbus, Ohio, USA), trade name) and the like. Examples thereof include vinyl esters of 5 to 12 branched alkylcarboxylic acids.

Examples of the (meth) acrylic acid ester include an ester of (meth) acrylic acid and a linear, branched or cyclic alcohol having 1 to 15 carbon atoms, and specifically, methyl (meth) acrylate. , Ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, norbornyl (meth) acrylate And so on.

Examples of unsaturated hydrocarbons include ethene, propene, butene, and isobutene.
The hydrophobic monomer (a3) may be a diester of fumaric acid or maleic acid, and specific examples thereof include a diester of fumaric acid or maleic acid and ethyl propanol or isopropanol.

The hydrophobic monomer (a3) is preferably a vinyl ester, and more preferably a vinyl ester of a linear or branched alkylcarboxylic acid having 1 to 15 carbon atoms. The hydrophobic monomer (a3) is preferably a vinyl acetate and a vinyl ester of a branched alkylcarboxylic acid having 5 to 12 carbon atoms, preferably 8 to 12 carbon atoms.

The hydrophobic monomer (a3) may be used alone or in combination of two or more.
The amount of the hydrophobic monomer (a3) in 100 parts by mass of the mixture is 30 to 99.4 parts by mass, preferably 36 to 99.4 parts by mass, more preferably 50 to 99.4 parts by mass, still more preferably 54. ~ 96.9 parts by mass.

<Manufacturing method, physical properties and blending amount of component (A)>
The component (A) is at least one selected from a silicone copolymer which is a polymer of a mixture containing a silicone (a1), a hydrophilic monomer (a2) and a hydrophobic monomer (a3), and a saponification product thereof. The component (A) has the effect of forming a soft film and giving a soft touch when the composition of the present invention is applied to hair, and is excellent in water resistance and abrasion resistance.

Silicone copolymers are synthesized, for example, by radical solution polymerization of the mixture in a solvent that has good dissolving properties in the mixture and at the same time acts as a molecular weight modifier.

The weight average molecular weight (Mw) of the silicone copolymer is preferably 30,000 to 90,000, more preferably 35,000 to 60,000. Mw can be measured, for example, by gel permeation chromatography.

The saponification product of the silicone copolymer can be produced, for example, by saponifying the silicone copolymer in a solvent using a method known to those skilled in the art. At this time, it is preferable to use an acid catalyst or a base catalyst.

Examples of the solvent include aliphatic alcohols having 1 to 6 carbon atoms, and specific examples thereof include methanol and ethanol. The solvent may be a mixture of water and an aliphatic alcohol. The solvent may be used alone or in combination of two or more.

Examples of the acid catalyst include inorganic strong acids such as hydrochloric acid and sulfuric acid; and organic strong acids such as aliphatic or aromatic sulfonic acids.
Base catalysts include, for example, hydroxides, alcoholates and carbonates of alkali metals or alkaline earth metals.

The catalyst is preferably a base catalyst. Further, it is desirable that the catalyst is used in the state of an aqueous solution or an alcohol solution. The catalyst may be used alone or in combination of two or more.

The amount of the catalyst used is preferably 0.2 to 20.0 mol with respect to 1 mol of the silicone copolymer.
In general, saponification is preferably carried out under the conditions of 20 to 70 ° C, more preferably 30 to 60 ° C. For example, the transesterification reaction is initiated by adding a catalytic solution to a solution containing a silicone copolymer. Generally, the transesterification reaction is interrupted when 40 to 100 mol% of the ester contained in the silicone copolymer is hydrolyzed. The transesterification reaction is interrupted by adding a basic reagent when the transesterification reaction is carried out using an acid catalyst, and when the transesterification reaction is carried out using a basic catalyst, a carboxylic acid or an inorganic acid. Etc. is added to the acid reagent. Then, for example, the saponification product is obtained by separating by centrifugation, filtration or the like.

The component (A) is preferably a silicone copolymer among the silicone copolymer and its saponification product.
Examples of commercially available products of the component (A) include silicone copolymers contained in BEALSIL P1101 (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.).

The silicone copolymer contained in BELSIL P1101 is silicone (a1) (containing 50% by mass or more of α, ω-divinyl-polydimethylsiloxane, which is a silicone represented by the formula (2), in 100% by mass of silicone (a1)). It is a polymer of a mixture containing crotonic acid, vinyl acetate, and a vinyl ester of a branched alkylcarboxylic acid having 8 to 12 carbon atoms. The silicone copolymer contained in BELSIL P1101 contains 0.1 to 40 parts by mass of silicone (a1), 3 to 6 parts by mass of hydrophilic monomer (a2), and 54 to 96.9 parts by mass of hydrophobic monomer (a3). It corresponds to a polymer of a mixture (provided that the entire mixture is 100 parts by mass). Further, the Mw measured by the gel permeation chromatography method of the silicone copolymer contained in BELSIL P1101 is in the range of 35,000 to 60,000.

The blending amount of the component (A) in 100% by mass of the composition of the present invention is 0.1 to 30% by mass, preferably 0.3 to 20% by mass, and more preferably 0.5 to 10% by mass. When the blending amount of the component (A) is at least the above lower limit value, the hair has a smooth and flexible feel when the composition is applied to the hair, and is excellent in water resistance and abrasion resistance. Therefore, it is preferable that the blending amount of the component (A) is not more than the upper limit value, because the composition can be uniformly coated on the hair and can be easily washed off.

<Hydroxypropyl cellulose (B)>
The composition of the present invention comprises hydroxypropyl cellulose (B). Since hydroxypropyl cellulose (B) acts as a thickener, by containing an appropriate amount of hydroxypropyl cellulose (B), the composition is less likely to cause liquid scattering and dripping, and is excellent in operability. Further, by using the component (A) and the hydroxypropyl cellulose (B) together, the pigment (C) can be uniformly dispersed, and the covering power, quick-drying property, abrasion resistance and water resistance are good. Composition can be obtained.

The viscosity of hydroxypropyl cellulose (B) is not particularly limited, but the viscosity of a 2% by mass aqueous solution of hydroxypropyl cellulose (B) at 20 ° C. is preferably 10 to 1000, more preferably 100 to 500 mPa · s. The viscosity can be measured, for example, with a B-type viscometer.

The blending amount of hydroxypropyl cellulose (B) in 100% by mass of the composition of the present invention is 0.5 to 5% by mass, preferably 1 to 3% by mass. When the blending amount of hydroxypropyl cellulose (B) is within the above range, the composition is excellent in operability.

<Pigment (C)>
The composition of the present invention contains a pigment (C). Hair can be colored by containing the pigment (C).

Conventionally, in hair mascara compositions, pearl pigments such as mica have been preferably used from the viewpoint of dispersibility. However, since the composition of the present invention is excellent in dispersibility of the pigment (C) by containing the component (A) and the hydroxypropyl cellulose (B) in a specific amount, various kinds of pigments are not limited to pearl pigments. Can be used. Further, since the composition is excellent in dispersibility of the pigment (C), precipitation and precipitation of the pigment (C) are unlikely to occur. Therefore, even after the composition has been allowed to stand for a long period of time, it can be used without stirring or only by simple stirring before use.

The pigment (C) is not particularly limited, and examples thereof include inorganic pigments and organic pigments.
Examples of inorganic pigments include zinc oxide, titanium oxide, red iron oxide, chromium oxide, cobalt oxide, black iron oxide, yellow iron oxide, chromium hydroxide, aluminum hydroxide, dark blue, barium sulfate, hydrous silicate, anhydrous silicic acid, and silicic acid. Examples include aluminum, talc, kaolin, carmine, mica, mica titanium, magnesium carbonate, bentonite, ultramarine, manganese violet, carbon black, aluminum, copper and gold. In the present invention, the pearl pigment used for artificially developing a pearly luster is also included in the inorganic pigment. Examples of the pearl pigment include the above-mentioned mica, titanium oxide, and a pigment in which the surface of thin plate-shaped mica particles is coated with titanium dioxide, that is, mica titanium.

Examples of the organic pigment include red 202, 203, 204, 205, 206, 207, 208, 219, 220, 221, 228, 404, 405, orange 203, 204, 401, and yellow 205. , 401, Blue No. 404, azo pigments, phthalocyanine pigments, slene pigments, quinacridone pigments, dioxazine pigments, and isoindolinone pigments.

The pigment (C) may be used alone or in combination of two or more.
The blending amount of the pigment (C) in 100% by mass of the composition of the present invention is preferably 1 to 2.5% by mass, more preferably 1.5 to 2% by mass.

<Oil (D)>
The composition of the present invention preferably contains an oil agent (D). By containing the oil agent (D), the composition can soften the hair, so that the hair feels good and the hair can be glossed.

Examples of the oil agent (D) include hydrocarbons, ester oils, higher alcohols, vegetable oils, animal oils and waxes.
Examples of the hydrocarbon include isododecane, liquid paraffin, squalene, paraffin, selecin, squalane, petrolatum, and microcrystalline wax.

Examples of the ester oil include di2-ethylhexyl succinate, isopropyl myristate, cetyl octanate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, and dimethyloctanoic acid. Hexyldecyl, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, cholesteryl 12-hydroxystearyl, ethylene glycol di-2-ethylhexylate, dipentaerythritol fatty acid ester, N-alkylglycol monoisostearate, neopentyl dicaprate Glycol, diisostearyl malate, glycerin di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexylate, trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexylate, glycerin tri-2-ethylhexylate , Trimethylol propane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, glycerin trimyristate, glyceride tri-2-heptyl undecanoic acid, castor oil fatty acid methyl ester, oleic acid oil, cetostearyl alcohol, Examples thereof include acetoglyceride, 2-heptyl undesyl palmitate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, ethyl laurate, 2-hexyl decyl myristate, and 2-hexyl decyl palmitate.

Examples of higher alcohols include araquil alcohols, lauryl alcohols, myristyl alcohols, cetyl alcohols, cetostearyl alcohols, stearyl alcohols, behenyl alcohols, oleyl alcohols, and isostearyl alcohols.

Vegetable oils and animal oils include, for example, avocado oil, camellia oil, macadamia nut oil, corn oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, southern ka oil, castor oil, flaxseed oil, safflower oil, cottonseed oil. , Soybean oil, fallen raw oil, tea seed oil, rice bran oil.

Examples of waxes include candelilla wax, carnauba wax, beeswax, whale wax, lanolin, reduced lanolin and derivatives thereof.
As the oil agent (D), hydrocarbons and ester oils are preferable, and specifically, isododecane and isopropyl myristate are preferable.

The oil agent (D) may be used alone or in combination of two or more.
The blending amount of the oil agent (D) in 100% by mass of the composition of the present invention is preferably 1 to 10% by mass, more preferably 3 to 7% by mass.

<Resin (E)>
Since the composition of the present invention contains the component (A) and hydroxypropyl cellulose (B), it has good abrasion resistance without using the resin generally used in the conventional hair mascara composition. It has a fixing force and a covering force such as. When the composition of the present invention contains the resin (E), for example, it has excellent fixing power and covering power even when the blending amounts of the component (A) and the hydroxypropyl cellulose (B) are small. Has excellent abrasion resistance, water resistance, and quick-drying properties.

The resin (E) is not particularly limited, and for example, a resin conventionally used as a set resin can be used.
Examples of the resin (E) include an amphoteric polymer resin compound, a cationic polymer resin compound, an anionic polymer resin compound, and a nonionic polymer resin compound.

As the amphoteric polymer resin compound, for example, dialkylaminoethyl (meth) acrylate, dialkylaminoethyl methacrylate, diacetoneacrylamide and the like are copolymerized with acrylic acid, methacrylic acid, acrylic acid alkyl ester, methacrylic acid alkyl ester and the like. , A compound amphoterized with acetic acid halide or the like, and specific examples thereof include a (methacrylicloyloxyethyl carboxybetaine / alkyl methacrylate) copolymer and a (ethylbetaine methacrylate / acrylic acid) copolymer.

Examples of the cationic polymer resin compound include poly (dimethyldiallylammonium halide) type cationic polymer, copolymer cationic polymer of dimethyldiallylammonium halide and acrylamide, quaternary nitrogen-containing cellulose ether, polyethylene glycol and epichlorohydrin. Examples thereof include a condensate of dipropylenetriamine and beef alkylamine, a condensate of polyethylene glycol, epiclohydrin, dipropylenetriamine and coconut oil alkylamine, and a vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer cationized product.

Examples of the anionic polymer resin compound include acrylic resin alkanolamine, which is a copolymer of (meth) acrylic acid and (meth) acrylic acid alkyl ester, and a copolymer of methyl vinyl ether and maleic acid monobutyl ester. Examples thereof include a copolymer of hydroxypropyl acrylate, butylaminoethyl methacrylate and octylamide acrylate, and a copolymer of vinyl chloride crotonic acid and vinyl neodecanoate. Specific examples thereof include (alkyl acrylate / diacetone). Acrylic) copolymer 2-amino-2-methyl-1-propanol (hereinafter, 2-amino-2-methyl-1-propanol is also referred to as "AMP") and the like can be mentioned.

Examples of the nonionic polymer resin compound include polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, carboxyvinyl polymer, polyvinylpyrrolidone, vinylpyrrolidone, and vinyl acetate copolymer, and vinylpyrrolidone, vinyl acetate, and acrylic amino acrylate. Polymers can be mentioned.

The resin (E) may be used alone or in combination of two or more.
As the resin (E), an amphoteric polymer resin compound and a nonionic polymer resin compound are preferable from the viewpoint of the feel when the composition is applied to the hair.

The blending amount of the resin (E) in 100% by mass of the composition of the present invention is preferably 0 to 6% by mass, more preferably 0 to 4.2% by mass. When the composition of the present invention contains the resin (E), the blending amount of the resin (E) in 100% by mass of the composition is preferably 0.1 to 6% by mass, more preferably 0. .5-4.2% by mass. When the blending amount of the resin (E) is within the above range, the composition is not stiff when applied to hair and has a good feel.

<Other ingredients (F)>
In addition to the above components, the composition of the present invention further comprises a moisturizer, a thickener other than hydroxypropyl cellulose (B), crude drugs, emulsifiers, pH adjusters, and chelating agents, as long as the effects of the present invention are not impaired. , Preservatives, refreshing agents, vitamins, proteins, fragrances, antibacterial agents, antioxidants, anti-inflammatory agents and the like can be contained.

Examples of the moisturizing agent include polyols such as ethylene glycol, propylene glycol, 1,3-butylene glycol, hexylene glycol, glycerin, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol and polyglycerin; amino acids. These moisturizers may be used alone or in combination of two or more.

Examples of thickeners other than hydroxypropyl cellulose (B) include cationic thickeners such as cationized guar gum and cationized cellulose; anionic thickeners such as carboxyvinyl polymer, carboxyethyl cellulose and xanthan gum; and nonionic thickeners. Examples include thickeners. These thickeners may be used alone or in combination of two or more.

Examples of raw medicines include plant extracts, specifically, Daisanchiku extract, Arnica extract, chamomile extract, shikon extract, shinanoki extract, sugina extract, sardine extract, sage extract, touki extract, nobara extract, and biwa leaf. Examples include extracts, malonier extracts, peach leaf extracts, yoquinin extracts and rosemary extracts. These crude drugs may be used alone or in combination of two or more.

Examples of the emulsifier include fatty acid salts obtained from fatty acids such as triethanolamine stearate and alkali, and nonionic, amphoteric, anionic and cationic surfactants. Examples of the surfactant include sorbitan stearate, polysorbate 60, sodium lauryl sulfate, sodium olefin (C14-16) sulfonate, cocamidopropyl betaine, sodium lauroyl glutamate, cetrimonium bromide, stearyltrimonium chloride, and ceteth-20. And PEG-100 hydrogenated castor oil. These emulsifiers may be used alone or in combination of two or more.

Examples of the pH adjuster include acidic substances and basic substances, and specific examples thereof include triethanolamine and aminomethyl propanol. These pH adjusters may be used alone or in combination of two or more.

The chelating agent, preservative, refreshing agent, vitamins, protein, fragrance, antibacterial agent, antioxidant and anti-inflammatory agent can be used without particular limitation, including those known to those skilled in the art.
The composition of the present invention may contain a solvent in addition to the above other components. Examples of the solvent include alcohols such as ethanol.

The blending amount of the solvent in 100% by mass of the composition of the present invention is preferably 45 to 99% by mass, more preferably 75 to 90% by mass.
The composition of the present invention may contain water as a solvent, but it is preferable that the composition contains substantially no water. The blending amount of water in 100% by mass of the composition of the present invention is preferably 8% by mass or less, more preferably 4% by mass or less. When the blending amount of water is within the above range, the composition is excellent in quick-drying property, abrasion resistance and water resistance, and color transfer is less likely to occur after application to hair.

≪Manufacturing method≫
The composition of the present invention can be produced by stirring, mixing, heating, dissolving, dispersing, etc., each of the above-mentioned components by a known method.

The composition of the present invention contains the component (A), hydroxypropyl cellulose (B), and pigment (C). The composition preferably further contains an oil agent (D). Further, the composition may contain a resin (E) or other components (F), if necessary.

The method for producing the composition of the present invention is not particularly limited, but hydroxypropyl cellulose (B) is dispersed in the oil agent (D), and if necessary, a solvent is added and mixed, and then the component (A) and the pigment ( A method of producing the composition by adding C) and, if necessary, the resin (E) and the other component (F) and mixing them is preferable.

≪Applications and dosage forms≫
The composition of the present invention is preferably liquid from the viewpoint of operability.
The method of using the composition of the present invention is not particularly limited. For example, the composition is put into a container with a brush, the composition is impregnated into a brush, and the hair is combed with the brush to obtain the composition into hair. Can be applied to and used.

Since the composition of the present invention has excellent quick-drying properties, it can be applied to hair and then naturally dried, but if necessary, it may be dried using a dryer or the like.
Since the composition of the present invention is excellent in quick-drying property, abrasion resistance and water resistance, it has a feature that color transfer is difficult even if it is sweated or rubbed after being applied to hair. Further, the composition of the present invention has a high covering power that can be uniformly applied to hair, and has a smooth feel without being stiff.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.
[Examples 1 to 21 and Comparative Examples 1 to 6]
In the oil agent (D) of the type and amount shown in Table 1 or Table 2, the amount of hydroxypropyl cellulose (B) shown in Table 1 or Table 2 or the thickener (b) other than the above (B) is dispersed. An appropriate amount of 95% undenatured alcohol was added and mixed. Then, the hair mascara composition was produced by mixing the remaining components with the formulations shown in Table 1 or Table 2, and evaluated by the following method.
The following commercially available products were used as the components shown in Tables 1 and 2.

<Ingredient (A)>
(Crotonic acid / Vinyl isoalkyl (C8-12) esters / VA / Bisvinyl dimethicone) Cross polymer: Silicone copolymer contained in BELSEL P1101 (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) BELSIL P1101 is an ethanol solution of a silicone copolymer. It has an evaporation residue of 46.8% by mass (ethanol content of 53.2% by mass) and a viscosity of 3,000 mPa · s. The evaporation residue was calculated from the mass of the dried product obtained by drying 10 g of BELSIL P1101 in a water bath at 100 ° C. for 2 hours. The viscosity was determined by rotating BEALSIL P1101 at 25 ° C. for 30 seconds at a speed of 30 rotations per minute using a No. 2 rotor of a B-type viscometer (manufactured by BROOK FIELD).

<Hydroxypropyl cellulose (B) or thickener (b) other than (B)>
Hydroxypropyl cellulose: HPC-M (manufactured by Nippon Soda)
Hydroxyethyl cellulose: Hydroxyethyl cellulose SE-600 (manufactured by Daicel)
Hydroxypropyl Methyl Cellulose: Metrose 65SH4000 (manufactured by Shin-Etsu Chemical Co., Ltd.)
<Pigment (C)>
Yellow No. 205: [Examples 1 to 10, 13 to 15, Comparative Examples 1 to 6] Yukaformer Yellow (manufactured by Mitsubishi Chemical Corporation, Yellow No. 205, 10%, (methacryloyloxyethyl carboxybetaine / alkyl methacrylate) copolymer 21%, Yellow 205 contained in (69% ethanol), [Examples 16 to 21] Yellow 205 (manufactured by Ami Kasei Co., Ltd.)
Carbon black: Carbon black pearl pigment contained in Yukaformer SM black (manufactured by Mitsubishi Chemical Co., Ltd., carbon black 10%, (methacryloyloxyethyl carboxybetaine / alkyl methacrylate) copolymer 21%, ethanol 69%): Timiron Supersilk MP-1005 ( A mixture of mica and titanium oxide manufactured by Merck)
<Oil (D)>
Isododecane: ISODDECANE (manufactured by Kaneda)
Isopropyl myristate: Exepearl I. P. M (manufactured by Kao Corporation)
<Resin (E)>
(Methacryloxyethyl Carboxybetaine / Alkyl Methacrylate) Copolymer: [Examples 1 to 10, 13 to 15, Comparative Examples 1 to 6] Included in Yukaformer Yellow (manufactured by Mitsubishi Chemical Corporation) (methacryloyloxyethyl carboxybetaine / methacrylic acid) Alkyl) copolymer, [Example 11] Yukaformer SM Black (manufactured by Mitsubishi Chemical Corporation) (methacryloyloxyethyl carboxybetaine / alkyl methacrylate) copolymer, [Example 12] Yukaformer SM (manufactured by Mitsubishi Chemical Corporation, (methacryloyloxy) (Ethylcarboxybetaine / alkyl methacrylate) copolymer 30%, ethanol 70%)) (methacryloyloxyethyl carboxybetaine / alkyl methacrylate) copolymer (ethylbetaine methacrylate / acrylates) copolymer: RAM Resin-2000 (Osaka Organic Chemistry) (Ethyl methacrylate betaine / acrylates) Copolymer manufactured by Kogyo Co., Ltd. (30%, ethanol 70%) (ethyl betaine methacrylate / acrylates)
(Alkyl acrylate / diacetone acrylamide) copolymer AMP: Plus size L-9480B (manufactured by GOO CHEMICAL CO., LTD., (Alkyl acrylate / diacetone acrylamide) copolymer AMP 40%, ethanol 60%) (alkyl acrylate / diacetone acrylamide) Diacetone Acrylamide) Copolymer AMP
<Other ingredients>
Ethanol: BEALSIL P1101 (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), Yukaformer Yellow, Yukaformer SM Black, Yukaformer SM (manufactured by Mitsubishi Chemical Co., Ltd.), RAM Resin-2000 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Plus size L-9480B (Goo Chemical) Ethanol contained in (manufactured by Kogyo Co., Ltd.) and 95% unmodified alcohol (manufactured by Shinwa Alcohol Corporation)

[Evaluation]
Eucalyptus Japan wigs (YJ / 50WH gray hair coloring wigs) cut to a length of 10 cm were equally divided into 11 blocks, and 1 block was used for each example or comparative example.

The hair mascara composition produced in each Example and Comparative Example in a container with a brush for hair mascara (brush diameter: 0.7 cm, brush length: 3 cm, container diameter: 2.5 cm, container length: 7.5 cm). I put in. The step of impregnating the brush with the hair mascara composition and applying the hair mascara composition impregnated to the brush to the wig was set as one step, and this was repeated 5 times.

Ten specialized panelists (cosmetologists) applied the hair mascara composition to the wig by the above method, and performed sensory evaluation according to the evaluation criteria described in each evaluation item. The step of applying the hair mascara composition to the wig and the sensory evaluation were all carried out under the condition of room temperature (25 ° C.). The average of the evaluation points of the sensory evaluation of 10 persons was calculated, and the evaluation was performed as follows based on the average.
⊚: The average evaluation score of 10 professional panelists (cosmetologists) is 3.5 points or more.
◯: The average evaluation score of 10 professional panelists (cosmetologists) is 2.5 points or more and less than 3.5 points.
Δ: The average evaluation score of 10 professional panelists (cosmetologists) is 1.5 points or more and less than 2.5 points.
X: The average evaluation score of 10 professional panelists (cosmetologists) is less than 1.5 points.

<Evaluation items and evaluation criteria>
(1) Operability When the hair mascara composition was applied to the wig, the ease of application was evaluated.
4 points: Very easy to apply with no dripping 3 points: Easy to apply with almost no dripping 2 points: Easy to dripping, care must be taken when applying, or poor spread and difficult to apply evenly 1 point: Dripping It cannot be applied easily, or it does not spread very well and cannot be applied evenly.

(2) The quick-drying hair mascara composition was applied to the wig, and it was evaluated whether it was dry after 3 minutes.
4 points: completely dry 3 points: almost completely dry 2 points: slightly dry 1 point: not dry

(3) Covering Power After the hair mascara composition was applied to the wig and completely dried by natural drying, the flexibility of the film and the uniformity of the coating were evaluated.
4 points: Uniformly covered with a very smooth film 3 points: Slightly evenly coated with a smooth film 2 points: Unevenly coated or too coated Somewhat inflexible and the finish is a little unnatural 1 point: There is unevenness and the film cannot be formed, or the film is too attached and inflexible, and the finish is unnatural.

(4) Feel The feel of the hair mascara composition after being applied to the wig and completely dried by natural drying was evaluated.
4 points: Very smooth and flexible 3 points: Slightly smooth and flexible 2 points: Feels a little hard 1 point: Feels hardness

(5) After applying the friction-resistant hair mascara composition to the wig and completely drying it by natural drying, the color transfer when rubbed with a filter paper about 3 times was visually evaluated.
4 points: No color transfer at all 3 points: Slight color transfer 2 points: Color transfer 1 point: Significant color transfer

(6) The water-resistant hair mascara composition was applied to the wig and completely dried by natural drying, then sprayed with water and lightly pressed with a filter paper to visually evaluate the color transfer.
4 points: No color transfer at all 3 points: Slight color transfer 2 points: Color transfer 1 point: Significant color transfer

(7) Wash-off The degree of film removal when the hair mascara composition was applied to a wig, completely dried by natural drying, and then washed with water using 1.0 g of Arimino Sherpa D-1 shampoo was evaluated. ..
4 points: No film remains, flexible 3 points: No film remains, but feels firm 2 points: Slight film remains 1 point: Film remains

All of the compositions produced in Examples 1 to 21 gave good evaluations in all the evaluation items (1) to (7). Therefore, the composition of the present invention has good operability, quick-drying property, covering power, abrasion resistance, water resistance and touch when applied to hair. The composition of the present invention is further well washed off.

Since the composition produced in Comparative Example 1 contained a small amount of the component (A), the texture after applying the composition to the hair was poor. Further, since the composition produced in Comparative Example 2 contained a large amount of the component (A), it could not be uniformly coated on the hair and could not be easily washed off.

The compositions produced in Comparative Examples 3 and 4 did not have an appropriate amount of hydroxypropyl cellulose (B), and the compositions produced in Comparative Examples 5 and 6 used the above (B) instead of hydroxypropyl cellulose (B). ), So the operability was poor.

Claims (4)

In 100% by mass of hair mascara composition,
At least one component (A) selected from the silicone copolymer and its saponification product (A) 0.1 to 30% by mass,
Hydroxypropyl cellulose (B) 0.5 to 5% by mass,
The pigment (C),
Contains 1 to 10% by mass of the oil agent (D) .
The silicone copolymer contains (a1) 0.1 to 50 parts by mass of silicone (however, 10% by mass or more of silicone having 2 or more polymerizable groups is contained in 100% by mass of silicone (a1)), (a2) hydrophilicity. monomer 0.5 to 14 parts by weight, and, Ri polymer der of (a3) a hydrophobic monomer from 30 to 99.4 parts by weight mixture including (but the whole mixture to 100 parts by weight),
A hair mascara composition in which the oil agent (D) is at least one selected from isododecane and isopropyl myristate. The hair mascara composition according to claim 1, wherein the silicone having two or more polymerizable groups contained in the silicone (a1) is represented by the formula (2).
(R ¹ ) (R ² ) ₂ SiO (Si (R ² ) ₂ O) _n Si (R ² ) ₂ (R ¹ ) (2)
[In the formula (2), R ¹ there are a plurality of, each independently represent a polymerizable group, the R ² s each independently represent a linear, branched or cyclic, hydrocarbon having 1 to 18 carbon atoms It represents a group or an alkoxy group, and the hydrocarbon group and the alkoxy group may have a substituent, and n represents an integer of 10 to 1,000. ] The hair mascara composition according to claim 1 or 2, wherein the hydrophilic monomer (a2) has a carboxyl group. The hair mascara composition according to any one of claims 1 to 3, wherein the hydrophobic monomer (a3) is a linear or branched vinyl ester of an alkylcarboxylic acid having an alkyl group having 1 to 15 carbon atoms. Stuff.