JP2019085366A - Resin emulsion for eyelash cosmetic agent and eyelash cosmetic agent using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an emulsion for eyelash cosmetics which is excellent in curl retention for a long time under high humidity and washability in water when used for mascara or the like. SOLUTION: The resin emulsion for eyebrows cosmetics containing a polyvinyl alcohol-based resin [I] and a vinyl-based resin (A), and the weight of the polyvinyl alcohol-based resin [I] and the vinyl-based resin (A) in the emulsion. A resin emulsion for eye cream cosmetics having a ratio of 55:45 to 99: 1. [Selection diagram] None

Description

  The present invention relates to a resin emulsion effective as an eyelash cosmetic agent and an eyelash cosmetic agent containing the resin emulsion.

The cosmetic for eyelashes has a cosmetic effect of making the eyes clearer by curling the eyelashes and making the eyelashes thicker and longer.
Conventionally, these eyelash cosmetic agents are known to be of oil type, water-in-oil type, emulsion type of water-in-oil type, and water type, but in the case of emulsion type, compared to oil type, Because it is inferior in water resistance and oil resistance, wax is added to improve adhesion and water resistance. However, the addition of wax reduces the curling effect and causes problems such as no gloss. A technology (patent document 1) using a specific oil-soluble resin, a specific water-soluble film forming agent, and silicic anhydride without blending a wax has been studied.
In addition, an emulsion obtained by emulsion polymerization of triorganosiloxysilicic acid and an ethylenically unsaturated group-containing monomer in the presence of a surfactant or polyvinyl alcohol as an emulsion for imparting water resistance, oil resistance and toughness to various cosmetics. The technique (patent document 2) which uses is examined.

JP, 2006-249023, A JP, 2015-63512, A

  However, when these emulsions are used as eyelash cosmetic agents, it has been revealed that they are excellent in water resistance but inferior in long-term curl retention under high humidity and water washability.

  Then, as a result of earnestly researching in order to solve the said subject, the present inventors use the emulsion whose weight ratio of polyvinyl alcohol-type resin and vinyl-type resin in an emulsion is 55: 45-99: 1 for eyelash cosmetic agent as a result It was found that the curl retention property under high humidity for a long time and the washability with water were excellent.

That is, the present invention includes the following aspects (1) to (5).
(1) A resin emulsion for eyelash cosmetic comprising a polyvinyl alcohol resin [I] and a vinyl resin (A), wherein the weight ratio of the polyvinyl alcohol resin [I] to the vinyl resin (A) in the emulsion Is 55: 45-99: 1, and the resin emulsion for eyelash cosmetic agents characterized by the above-mentioned.
(2) The resin emulsion for eyelash cosmetic composition as described in (1) above, wherein the glass transition temperature of the vinyl resin (A) is 70 ° C. or less.
(3) The resin emulsion for eyelash cosmetic composition as described in (1) or (2) above, wherein the vinyl resin (A) is an acrylic resin.
(4) The vinyl resin (A) obtained by polymerizing the vinyl monomer (a) dispersed and stabilized by the vinyl alcohol resin [I], which is characterized by the above (1) to (3) The resin emulsion for eyelash cosmetic according to any of the above.
(5) An eyelash cosmetic agent comprising the acrylic-containing resin emulsion for eyelash cosmetic according to any one of the above (1) to (4).

  The eyelash cosmetic agent using the resin emulsion for eyelash cosmetic agent of the present invention is excellent in long-term curl retention under high humidity and water washability.

Hereinafter, embodiments of the present invention will be described.
In the present specification, an acrylic resin is a resin obtained by polymerizing a monomer component containing at least one (meth) acrylic monomer, and (meth) acrylic is acrylic or methacrylic (meth) Acrylate means acrylate or methacrylate, and (meth) acrylic acid means acrylic acid or methacrylic acid, respectively.

  The resin emulsion for eyelash cosmetic composition of the present invention is excellent in long-term curl retention under high humidity and water washability when used for eyelash cosmetic composition, and polyvinyl alcohol resin [I] and vinyl It is a resin emulsion for eyelash cosmetic agents containing a resin (A), and the weight ratio of polyvinyl alcohol resin [I] to vinyl resin (A) in the emulsion is 55: 45 to 99: 1. Resin emulsion.

Each component will be described.
<Polyvinyl alcohol-based resin [I]>
The polyvinyl alcohol-based resin (hereinafter sometimes referred to as PVA-based resin) contained in the resin emulsion for eyelash cosmetic composition of the present invention is not particularly limited, but the saponification degree (measured according to JIS K6726) is Usually, it is 85 to 100 mol%, particularly preferably 90 to 99.9 mol%. If the degree of saponification is too low, the emulsion tends to be unstable.
The average degree of polymerization (measured in accordance with JIS K6726) is usually 100 to 4000, preferably 200 to 3,500, and more preferably 250 to 3,000. If the average degree of polymerization is too low, the protective colloid function of the PVA-based resin tends to decrease, and if too high, the viscosity of the emulsion tends to be too high.

  The PVA-based resin is a saponified polymer of a vinyl ester-based monomer such as vinyl acetate, and another vinyl-based monomer may be copolymerized as long as the water solubility is not impaired.

  Examples of vinyl ester monomers other than the above-mentioned vinyl acetate ester include vinyl formate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, and versatic acid. Aliphatic vinyl esters such as vinyl usually having 3 to 20 carbon atoms, preferably 4 to 10 carbon atoms, particularly preferably 4 to 7 carbon atoms; aromatic vinyl esters such as vinyl benzoate; halogen containing such as vinyl trifluoroacetate Aliphatic vinyl esters and the like can be mentioned.

  Examples of the vinyl monomers which may be copolymerized include olefins such as ethylene, propylene, isobutylene, α-octene, α-dodecene, α-octadodecene and the like, acrylic acid, methacrylic acid, crotonic acid, maleic acid, Unsaturated acids such as maleic anhydride and itaconic acid or their salts or mono- or dialkyl esters, nitriles such as acrylonitrile and methacrylonitrile, amides such as acrylamide and methacrylamide, ethylene sulfonic acid, allyl sulfonic acid, methallyl Olefin sulfonic acids such as sulfonic acids or salts thereof, alkyl vinyl ethers, N-acrylamidomethyl ammonium chloride, allyltrimethyl ammonium chloride, cationic groups such as dimethyldiallyl ammonium chloride That compounds, vinyl ketone, N- vinylpyrrolidone, vinyl chloride, vinylidene chloride, polyoxyethylene group, polyoxypropylene group, a vinyl compound having an oxyalkylene group, such as polyoxybutylene group.

  The PVA-based resin that can be used in the emulsion of the present invention is a polymer of a vinyl ester-based monomer, a copolymer with the above-mentioned vinyl-based monomer optionally copolymerized, and further oxyalkylene etherification, cyanoethylation, acetal It may be end-modified with a so-called "post-modified" modified PVA resin, such as esterification, urethanization, esterification, acetoacetylation, stilbazolium quaternary salt pendant type, and further, mercaptan or the like.

  The PVA-based resin used in the emulsion of the present invention is a polyvinyl alcohol having a side chain 1,2-diol unit represented by the following general formula (1) (hereinafter referred to as “side chain 1,2-diol-containing PVA-based resin”) Is preferred. By containing the side chain 1,2-diol-containing PVA-based resin, there is an effect that the polymerization stability of the vinyl-based monomer for dispersoid synthesis is improved.

  In the above general formula (1), R1 to R6 each independently represent a hydrogen atom or an organic group. R1 to R6 are preferably all hydrogen atoms, but may be organic groups as long as the resin properties are not significantly impaired. The organic group is not particularly limited, but is preferably an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and tert-butyl group, If necessary, it may have a substituent such as a halogen group, a hydroxyl group, an ester group, a carboxylic acid group, a sulfonic acid group or the like.

In the above general formula (1), X is a single bond or a bond chain, and is preferably a single bond from the viewpoint of improving the crystallinity and reducing the free volume (intermolecular gap) in the amorphous part. The linking chain is not particularly limited, but other hydrocarbons such as alkylene, alkenylene, alkynylene, phenylene and naphthylene (these hydrocarbons may be substituted with halogens such as fluorine, chlorine and bromine) _{, -O -, - (CH 2} O) m -, - (OCH 2) m -, - (CH 2 O) m CH 2 -, - CO -, - COCO -, - CO (CH 2) m CO- _{, -CO (C 6 H 4)} CO -, - S -, - CS -, - SO -, - SO 2 -, - NR -, - CONR -, - NRCO -, - CSNR -, - NRCS -, - _{NRNR -, - HPO 4 -,} - Si (OR) 2 -, - OSi (OR) 2 -, - OSi (OR) 2 O -, - Ti (OR) 2 -, - OTi (OR) 2 -, - _{OTi (OR) 2 O -,} - Al (OR) -, - OAl (OR) -, - OAl (OR) -, and the like. Each R is independently an arbitrary substituent, preferably a hydrogen atom or an alkyl group, and m is a natural number. Among them, an alkylene group having 6 or less carbon atoms, particularly a methylene group or -CH ₂ OCH ₂ -is preferable in terms of viscosity stability and heat resistance during production.

  In the most preferable structure of the 1,2-diol structural unit represented by the above general formula (1), all of R1 to R6 are hydrogen atoms, and X is a single bond. That is, the structural unit represented by the following structural formula (1a) is most preferable.

  The content of the side chain 1,2-diol structural unit is usually 0.5 to 15 mol%, preferably 1 to 10 mol%, more preferably 1 to 8 mol%. When the content of the side chain 1,2-diol structure is too high, the emulsion polymerization stability tends to be lowered.

  In addition, the content of the 1,2-diol structural unit in the PVA-based resin can be obtained from 1 H-NMR spectrum (solvent: DMSO-d6, internal standard: tetramethylsilane) of PVA-based resin having a degree of saponification of 100%. Can. Specifically, it may be calculated from peak areas derived from a hydroxyl group proton, a methine proton, a methylene proton, a methylene proton of the main chain, a proton of a hydroxyl group linked to the main chain, etc. in a 1,2-diol structural unit.

<Vinyl-based resin (A)>
The vinyl-based resin of the present invention may be a water-insoluble polymer obtained by polymerizing one or two or more of vinyl-based monomers (a) derived from an ethylenically unsaturated bond, preferably acrylic monomers A polymer of at least one monomer selected from the group consisting of styrenic monomers and nitrile monomers, or a copolymer of two or more monomers.
The water-insoluble vinyl-based resin (A) is dispersed in the form of particles in a PVA aqueous solution in which a water-soluble PVA-based resin is dissolved in a dispersion medium composed mainly of water. A polyvinyl alcohol-type resin is not contained in vinyl-type resin (A).

  Examples of the acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate. ) Aliphatic (meth) acrylates such as acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, stearyl (meth) acrylate, and aromatic (meth) acrylates such as phenoxy (meth) acrylate Acrylate, trifluoroethyl (meth) acrylate and the like. Among them, aliphatic (meth) acrylates having 1 to 18, preferably 1 to 10, more preferably 1 to 8 carbon atoms in the alkyl group are preferable in terms of excellent polymerization reactivity.

  Examples of the styrene-based monomer include styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, 2,4-dimethylstyrene, and the like. Examples thereof include styrene derivative monomers such as 6,6-trimethylstyrene, monofluorostyrene, difluorostyrene, monochlorostyrene, dichlorostyrene and methoxystyrene, and aromatic substituted vinyl compounds such as vinyl naphthalene and vinyl anthracene. Preferred is a styrene derivative monomer, and particularly preferred is styrene.

  As a nitrile monomer, an α, β-unsaturated nitrile compound is used. Specifically, acrylonitrile-based monomers such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethyl acrylonitrile and the like; cyano-substituted di-vinyl monomers such as vinylidene cyanide; methyl cyanoacrylate, ethyl cyanoacrylate, butyl cyanoacrylate and the like Unsaturated group-containing cyanoacrylate, tetracyanoquinodimethane, 2,2-diaryl malononitrile and the like. Among these, an acrylonitrile-based monomer is preferable, more preferably (meth) acrylonitrile, and particularly preferably acrylonitrile.

These vinyl monomers can be used alone or in combination of two or more.
Besides acrylic monomers, styrenic monomers, nitrile monomers, vinyl monomers copolymerizable with these monomers can also be used. For example, unsaturated carboxylic acid monomers such as monocarboxylic acid monomers such as acrylic acid, methacrylic acid, crotonic acid and undecylenic acid, dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, and anhydride monomers thereof; (meth) Alkylamides, alkylamides of ethylenically unsaturated carboxylic acids such as N-methylol acrylamide; monoalkyl esters; monoamides; aminos of ethylenically unsaturated carboxylic acids such as aminoethyl acrylamide, dimethylaminomethyl methacrylamide, methyl amino propyl methacrylamide An alkylamide, a crosslinkable monomer, etc. can be used suitably.

  Among the above-mentioned vinyl monomers (a), acrylic monomers are preferable in terms of stability at the time of polymerization.

The resin emulsion for eyelash cosmetic composition of the present invention can be obtained by dispersing the vinyl resin (A) in an aqueous solution of the polyvinyl alcohol resin [I].
In particular, such an emulsion has a vinyl monomer (a) derived from the above-mentioned ethylenic unsaturated bond as a dispersoid, and is emulsion-polymerized using the above-mentioned solvent as a dispersion medium, using a known dispersant, to obtain a vinyl resin (A). When obtained, the vinyl resin (A) is efficiently obtained as an emulsion dispersed in the dispersion medium with good dispersibility.

By adding a solution in which the polyvinyl alcohol resin [I] is dissolved or in which the polyvinyl alcohol resin [I] is dissolved to this emulsion, the vinyl resin (A) is mixed with the polyvinyl alcohol resin [I]. It can be dispersed and stabilized.
At this time, it is also possible to use different types of polyvinyl alcohol resins in addition to the polyvinyl alcohol resin [I] used for preparation of the emulsion. The polyvinyl alcohol-based resin [I] to be added to the prepared emulsion composition is preferably one containing the above-mentioned 1,2-diol structural unit from the viewpoint of improving the stability of the emulsion.

The weight ratio of the polyvinyl alcohol resin [I] to the vinyl resin (A) in the emulsion is preferably 55:45 to 99: 1, and more preferably 58:42 to 90:10. When the ratio of the polyvinyl alcohol resin [I] is lower than the lower limit, the cleaning performance is lowered, and when the ratio is higher than the upper limit, the curl retention performance is lowered.

The glass transition temperature of the vinyl resin (A) in the emulsion is preferably 70 ° C. or less, more preferably 50 to -80 ° C., particularly preferably 30 to -70 ° C., from the viewpoint of easy film formation.
As a method of setting the glass transition temperature to 70 ° C. or less, there are a method of copolymerizing a monomer having a low glass transition temperature and a method of adding a plasticizer.

[Synthesis of emulsion by emulsion polymerization using PVA as emulsifier]
As a method of carrying out the emulsion polymerization, i) by temporarily or continuously blending the dispersed ethylenically unsaturated monomer in the presence of water, a dispersant and a polymerization catalyst, and heating and stirring. Emulsion polymerization method: ii) A dispersion liquid in which an ethylenically unsaturated monomer is mixed and dispersed in a dispersion medium is prepared, and the prepared dispersion liquid is mixed with water, a dispersant and a polymerization catalyst in a system, The method of carrying out emulsion polymerization by mixing | blending temporarily or continuously, heating and stirring is mentioned. The method using the dispersion prepared in this way is particularly called a pre-emulsion method. Such a method is preferable because emulsion polymerization can be performed while maintaining productivity even if the monomer composition to be polymerized is complex.

  The dispersion medium in the reaction solution used for the above-mentioned emulsion polymerization is usually water. If desired, it is also possible to use an organic solvent which can be mixed with the water mentioned above as a solvent together with water. However, from the viewpoint of the dispersibility of the monomers to be subjected to the emulsion polymerization, it is preferably only water.

When using polyvinyl alcohol-based resin [I] as a dispersing agent at the time of emulsion polymerization, the blending amount thereof is somewhat different depending on the kind of polyvinyl alcohol-based resin [I] to be used, the concentration of the emulsion to be synthesized, etc. The amount is usually 0.1 to 80% by weight, preferably 10 to 70% by weight, particularly preferably 20 to 60% by weight, based on the whole system.
When the blending amount of the polyvinyl alcohol resin [I] is too small, the emulsified state of the ethylenically unsaturated monomer becomes unstable, the polymerization reactivity decreases, or the particles in the emulsion obtained by the polymerization The emulsion state stability tends to decrease. On the other hand, when the content of the PVA-based resin is too large, the viscosity of the reaction solution is excessively increased and the uniform dispersibility is reduced, and the polymerization rate can not be increased or the viscosity of the obtained emulsion becomes too high. The yield of the

  As a polymerization catalyst, a polymerization catalyst generally used in the field of emulsion polymerization can be used. For example, potassium persulfate, ammonium persulfate, potassium bromate, sodium acid sulfite, hydrogen peroxide-tartaric acid, hydrogen peroxide-iron salt, hydrogen peroxide-ascorbic acid-iron salt, hydrogen peroxide-long gallite, hydrogen peroxide- There may be mentioned water-soluble redox type polymerization catalysts such as Rongalite-iron salt, etc. These can be used alone or in combination of two or more. Specifically, a catalyst composed of an organic peroxide and a redox system, such as "Kayabutyl B" manufactured by Kayaku Akzo Co., Ltd. and "Kayabutyl A-50C" manufactured by Kayaku Co., Ltd. may be used.

The amount of the polymerization catalyst used is usually 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, particularly preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the monomers used for the polymerization. It is a department. When the amount of the polymerization initiator used is too small, the polymerization rate tends to be slow, and when it is too large, the polymerization stability tends to be reduced.
In addition, there is no restriction | limiting in particular as a compounding method of a polymerization initiator, You may mix | blend to a reaction liquid collectively collectively at the beginning, and you may add continuously with progress of superposition | polymerization.

  In the emulsion polymerization as described above, if necessary, a molecular weight modifier may be included. Specific examples of the molecular weight modifier include, for example, alkyl mercaptan such as n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-stearyl mercaptan; dimethyl xanthogen disulfide, Xantogen compounds such as diisopropyl xanthogen disulfide; Thiuram compounds such as terpinolene, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram monosulfide; 2,6-di-t-butyl-4-methylphenol, styrenated phenol, etc. Phenolic compounds of the formula: allyl compounds such as allyl alcohol; halogenated hydrocarbon compounds such as dichloromethane, dibromomethane, carbon tetrabromide; α-benzyl Vinyl ethers such as xystyrene, α-benzyloxyacrylonitrile, α-benzyloxyacrylamide, etc .; triphenylethane, pentaphenylethane, acrolein, methacrolein, thioglycolic acid, thiomalic acid, 2-ethylhexyl thioglycolate, α-methylstyrene dimer, Carbon tetrachloride etc. are mentioned. In the emulsion polymerization step, these molecular weight modifiers can be used singly or in combination of two or more.

Further, in the above-mentioned polymerization step, surfactants such as nonionic surfactants and anionic surfactants separately from the dispersants contained in advance, to the extent that the dispersion stabilizing effect of the polyvinyl alcohol resin [I] is not impaired. May coexist in the system. The compounding amount of such surfactant is usually 10% by weight or less, preferably 5% by weight or less, based on the whole of the emulsion polymerization reaction system.

  By carrying out the emulsion polymerization as described above, an emulsion in which polymer particles derived from an ethylenically unsaturated monomer are dispersed in a water dispersion medium is obtained.

  The solid content (corresponding to the above particle amount) of the resulting emulsion is usually 10 to 60% by weight, preferably 20 to 58% by weight, particularly preferably 25 to 55% by weight. As the solid content of the emulsion, a value obtained by measuring the residue which has been dried by heating at 105 ° C. for 3 hours with a drier is adopted. The same applies to the solution.

  The viscosity of the resulting emulsion is usually 100 to 20000 mPa · s at 20 ° C., preferably 300 to 10000 mPa · s, and particularly preferably 450 to 8000 mPa · s. The viscosity of the emulsion is a value measured by a B-type viscometer.

The eyelash cosmetic composition of the present invention contains the above emulsion, but as a water-soluble polymer, a small amount of polyethylene glycol, polyvinyl pyrrolidone, polyacrylic acid, water-soluble cellulose, etc. besides polyvinyl alcohol resin [I] You may contain. The content thereof is 10% or less of the solid content in the eyelash cosmetic agent.

  The eyelash cosmetic composition of the present invention may contain an alcohol for the purpose of faster drying of the coating film, and ethanol is particularly preferred. The content of alcohol in the eyelash cosmetic composition is preferably 15% or less, and particularly preferably 10% or less.

  The eyelash cosmetic composition of the present invention may be a component generally used in cosmetics other than the above components, for example, an oily component as a base material or an emollient component, an aqueous component as moisturizing or a powder dispersant, texture control or coloring Powder component, fiber, surfactant for powder dispersion and touch adjustment, UV absorber, moisturizer, anti-fading agent, antioxidant, antifoam agent, cosmetic ingredient, preservative, perfume, wax etc. These can be suitably blended in the range which does not impair the effect of the present invention.

  Examples of the oil component include hydrocarbons, oils and fats, hydrogenated oils, ester oils, fatty acids, higher alcohols, silicone oils, fluorocarbon oils, lanolin derivatives, oily gelling agents and the like. Specifically, liquid paraffin, squalane, vaseline, polybutene, polyisobutylene, hydrocarbons such as light liquid isoparaffin, isododecane, oils and fats such as olive oil, castor oil, mink oil, macadamian oil, jojoba oil, malic acid Diisostearyl, cetyl isooctanate, isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, glyceryl trioctanoate, polyglyceryl diisostearate, diglyceryl triisostearate, glyceryl tribehenate, neopentyl glycol dioctoate, cholesterol fatty acid ester, Esters such as N-lauroyl-L-glutamic acid di (cholesteryl behenyl octyldodecyl), decamethylcyclopentasiloxane, octamethylcyclo Tetrasiloxane, dimethylpolysiloxane, low degree of polymerization dimethylpolysiloxane, high degree of polymerization dimethylpolysiloxane, methylphenylpolysiloxane, polyether modified organopolysiloxane, polyoxyalkylene / alkylmethylpolysiloxane / methylpolysiloxane copolymer, alkoxy Modified polysiloxane, partially crosslinked organopolysiloxane, silicone such as fluorine modified organopolysiloxane, fluorinated oil such as perfluorodecane, perfluorooctane, perfluoropolyether, lanolin, lanolin acetate, lanolin fatty acid isopropyl, lanolin Examples include lanolin derivatives such as alcohols.

  Examples of the aqueous component include alcohols such as isopropyl alcohol, glycols such as propylene glycol, 1,3-butylene glycol, dipropylene glycol and polyethylene glycol, glycerols such as glycerin, diglycerin and polyglycerin, and water. And water soluble ingredients such as sorbitol, maltitol, sucrose, starch sugar, saccharides such as lactitol, guar gum, sodium chondroitin sulfate, sodium hyaluronate, gum arabic, sodium alginate, carrageenan, methylcellulose, hydroxyethylcellulose, carboxymethylcellulose, Water-soluble polymers such as carboxyvinyl polymer and sodium polyacrylate, salts such as sodium chloride, magnesium chloride and sodium lactate, Ebera, witch hazel, hamamelis, cucumber, lemon, lavender, plant extracts such as rose, and the like.

  The powder component is not particularly limited by the plate-like, spindle-like, needle-like shape, particle diameter, particle structure such as porous or nonporous, etc., and inorganic powder, glitter powder, organic Powders, pigment powder, composite powder etc. are mentioned. Specifically, conjo, ultramarine, red iron oxide, yellow iron oxide, black iron oxide, titanium oxide, zinc oxide, aluminum oxide, cerium oxide, magnesium oxide, zirconium oxide, magnesium carbonate, calcium carbonate, chromium oxide, chromium hydroxide, Carbon black, aluminum silicate, magnesium silicate, magnesium aluminum silicate, mica, synthetic mica, synthetic sericite, sericite, talc, kaolin, silicon carbide, barium sulfate, boron nitride and other inorganic powders, bismuth oxychloride Bright powders such as mica titanium, iron oxide coated mica, iron oxide mica titanium, organic pigment treated mica titanium, aluminum powder, organic powders such as magnesium stearate, zinc stearate, N-acyllysine, nylon, Organic tar pigments, organic dyes Pigment powders and other pigment powders, fine particle titanium oxide coated mica titanium, fine particle zinc oxide coated mica titanium, barium sulfate coated mica titanium, titanium oxide containing silicon dioxide, composite powder such as zinc oxide containing silicon dioxide, polyethylene terephthalate · aluminum -Epoxy laminated powder, polyethylene terephthalate-polyolefin laminated film powder, polyethylene terephthalate-polymethyl methacrylate laminated film powder, etc. may be mentioned, and one or more of these may be used. In addition, these powders may be used as one or two or more composites, and may be prepared by a known method using a fluorine compound, silicone oil, metal soap, surfactant, oil, hydrocarbon and the like. It may be surface-treated.

  The fibers are not particularly limited as long as they are generally used in cosmetics, and include synthetic fibers such as nylon and polyester, artificial fibers such as rayon, natural fibers such as cellulose, and semisynthetic fibers such as acetate human silk Be These fibers may be used alone or in combination of two or more, and are surface-treated by a known method using a fluorine compound, silicone oil, powder, oil, gelling agent, emulsion polymer, surfactant and the like. It may be

  As the surfactant, any surfactant which is generally used in cosmetics can be used, and nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants and the like can be used. It can be mentioned. For example, inorganic and organic salts of fatty acids such as stearic acid and lauric acid, glycerin fatty acid esters and alkylene glycol adducts thereof, polyglycerin fatty acid esters and alkylene glycol adducts thereof, sorbitan fatty acid esters and alkylene glycol adducts thereof, polyoxy Ethylene hydrogenated castor oil, polyoxyalkylene alkyl co-modified organopolysiloxane, polyether modified organopolysiloxane, lecithin and the like can be mentioned.

  UV absorbers include, for example, benzophenone type, PABA type, cinnamic acid type, salicylic acid type, 4-tert-butyl-4'-methoxydibenzoylmethane, oxybenzone and the like, and as a humectant, for example, protein, mucopolysaccharide, collagen As elastin, keratin, etc., as an antioxidant, for example, α-tocopherol, ascorbic acid, etc., as a cosmetic component, for example, vitamins, anti-inflammatory agents, herbal medicine, etc., as preservatives, eg, p-hydroxybenzoic acid ester, phenoxyethanol, etc. It can be mentioned.

  The eyelash cosmetic composition of the present invention includes a mascara, mascara overcoat, mascara base and the like, and as a form, a cream, gel, liquid and the like can be mentioned.

  The eyelash cosmetic emulsion according to the present invention is excellent in long-term curl retention under high humidity and water washability.

EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
In the examples, "part" and "%" mean weight basis unless otherwise stated.

<Production of Acrylic Resin Emulsion (1)>
PVA-based resin containing a 1,2-diol structural unit in the side chain in deionized water (355 parts) in an SUS-made reaction can equipped with a cooling pipe and stirring blades (average saponification degree 99 mol%, average polymerization degree 1,200 parts of side chain 1,2-diol structural unit 6 mol% (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 67 parts and anhydrous sodium acetate 0.2 parts were completely dissolved, and the temperature was raised to 80 ° C.
Prepare a mixture of 70 parts of butyl acrylate and 30 parts of methyl methacrylate (i), 22 parts of 1% APS (ammonium persulfate) aqueous solution and 2 parts of 5% sodium bisulfite (iii) in a reaction vessel. First, 10% of (i), 30% of (ii) and all of (iii) were added and allowed to react for 1 hour. Next, the remaining 90% of (i) and 60% of (ii) were added dropwise over 3.5 hours and polymerized at 80 ° C.
After the addition is complete, add 5% of (ii), hold the temperature for 45 minutes, and (ii)
5% of was added and the temperature was maintained for 45 minutes. After cooling, an acrylic resin emulsion (1) (solid content 30%; viscosity 18800 mPa · s (B-type viscometer 10 rpm, 24 ° C.); glass transition temperature (Tg) of acrylic resin = −23 ° C.) was obtained . The acrylic resin emulsion (1) was dispersed and stabilized.

<Production of styrenic resin emulsion>
In a reaction vessel made of SUS provided with a cooling pipe and a stirring blade, 0.4 part of sodium acetate was completely dissolved in deionized water (81 parts), and the temperature was raised to 85 ° C.
In advance, 51 parts of deionized water, 6 parts of unmodified PVA-based resin (manufactured by Japan Synthetic Chemical Industry Co., Ltd .; trade name "GOOSENOL GL05"), 79 parts of styrene, 15 parts of 2-ethylhexyl acrylate, 6 parts of 80% acrylic acid The mixture (i) and 10 parts (ii) of a 5% aqueous solution of APS (ammonium persulfate) were prepared, and 30% of (ii) was first added to the reaction can, and the internal temperature was adjusted to 80 ° C. Next, 50% of (i) and (ii) was dropped over 4 hours, and polymerized at 80 ° C. After completion of the addition, 10% of (ii) was added, the temperature was maintained for 1 hour, and 10% of (ii) was further added, and the temperature was maintained for 1 hour.
After cooling, styrene resin emulsion (2) (solid content 42%; viscosity 5590 mPa · s (B type viscometer 10 rpm, 23 ° C.); glass transition temperature (Tg) of acrylic resin = 59 ° C.) was obtained. The styrenic resin emulsion (2) was dispersed and stabilized.

<Production of PVA-based resin solution>
PVA-based resin containing 1,2-diol structural units in the side chain in deionized water (average saponification degree 99 mol%, average polymerization degree 1200, content 6 mol of 1,2-diol structural units in side chain % / Nippon Synthetic Chemical Industry Co., Ltd. was completely dissolved to a concentration of 20% by weight.

<Production of Acrylic Resin Emulsion (2)>
In a reaction vessel made of SUS equipped with a cooling pipe and a stirring blade, completely dissolve 0.8 parts of sodium lauryl sulfate (Emar O / Kao Co., Ltd.) and 0.2 parts of anhydrous sodium acetate in deionized water (179 parts). And the temperature was raised to 80.degree.
A previously emulsified solution (58 parts of deionized water, 70 parts of butyl acrylate, 30 parts of methyl methacrylate, 1.5 parts of sodium lauryl sulfate (Emar 0 / Kao Co., Ltd.) (i) and 10% aqueous solution of APS (ammonium persulfate) 2.1 parts (ii) were prepared, and 10% of (i) and 25% of (ii) were first added to the reaction can and reacted for 30 minutes.
The remaining 75% of (ii) was then added and 90% of (i) was added dropwise over 3 hours and allowed to polymerize at 80.degree. After completion of the dropping, the temperature was maintained for 2 hours.
After cooling, an acrylic resin emulsion (2) (solid content: 30%; glass transition temperature (Tg) of acrylic resin = -23 ° C) was obtained. The acrylic resin emulsion (2) was dispersed and stabilized.

<Curl retention performance>
The curl retention performance test solution was prepared by diluting the emulsion and solution prepared above with deionized water so that the solid content would be 5% by weight, respectively, and then polyvinyl alcohol resin [I] and vinyl resin (A) The weight ratio of the above was adjusted by adding the PVA-based resin solution to the above-mentioned acrylic resin emulsion (1) to obtain a curl retention performance test solution.
For the curl retention test, a hair bundle (length 5 cm × weight 50 mg; hair bundle) was spread in one direction without gaps, and a portion up to 1 cm from the end was fixed with a tape to make a test hair bundle.
A portion of 3 cm from the end not fixed with the tape is bent with a burer, one drop of the above curl retention performance test solution is applied with a 2 mL dropper, brushed and brushed, and after drying at room temperature using a protractor The angle at which the hair bundle was bent was adjusted to about 20 °.
Thereafter, the sample to which the test solution is applied is placed in a thermostatic humidifier at a temperature of 60 ° C. and a humidity of 90%, and after 24 hours, the bending angle is measured using a protractor and judged by the following evaluation method did.
(Evaluation criteria)
...: The bent angle holds at least 15 ° ...: The bent angle holds at least 10 ° and less than 15 ° × ... The bent angle is less than 10 ° In the above evaluation, “○” is excellent in performance. , “△” is practically acceptable. Moreover, "x" is inferior to performance.

<Cleaning performance>
The washing performance test solution is prepared by diluting the above emulsion and solution with deionized water so that the solid content is 15% by weight, and the weight ratio of polyvinyl alcohol resin [I] to vinyl resin (A) The PVA resin solution was added to the above acrylic resin emulsion (1) and diluted with deionized water to prepare a cleaning performance test solution.
In the cleaning performance test, a resin solution adjusted to a solid content of 15% is applied to a 50 μm thick PET (polyethylene terephthalate) film using a 250 μm applicator, dried at 100 ° C. for 10 minutes, and a thickness of about 37.5 μm (at the time of drying) A coated film of was obtained. The film was rubbed 2 cm with a cotton swab soaked with water (Aswane industrial cotton swab AP-1 manufactured by As One Co., Ltd.), and the number of times of rubbing required to peel off the film was evaluated. The evaluation method is as follows.
(Evaluation criteria)
○: The coating film was peeled off from the film within 15 times of rubbing.
X: The coating did not peel off within 15 times of rubbing.

Example 1
The solid contents of the acrylic resin emulsion (1) and the PVA resin solution prepared above are diluted with deionized water so as to be 5% by weight and 15% by weight respectively, and polyvinyl alcohol resin [I] in the emulsion and The curl retention performance test solution with a solid content of 5% by weight and a solid content of 15% is prepared by mixing an emulsion and a solution of the same solid concentration so that the weight ratio of the vinyl resin (A) is 55:45. % Cleaning performance test solution was prepared, and the above-mentioned curl retention performance and cleaning performance were evaluated. The evaluation results are shown in Table 1.

Example 2
Evaluation was performed in the same manner as in Example 1 except that the weight ratio of the polyvinyl alcohol resin [I] to the vinyl resin (A) in the emulsion was adjusted to be 80:20. The evaluation results are shown in Table 1.

Comparative Example 1
Polyvinyl alcohol-based resin [I, diluted to a solid content of 5% by weight and 15% by weight]
The above-mentioned curl retention performance and cleaning performance were evaluated using an acrylic emulsion (2) not containing The evaluation results are shown in Table 1.

Comparative Example 2
The above-mentioned curl retention performance and cleaning performance were evaluated using a PVA-based resin solution diluted to have a solid content of 5% by weight and 15% by weight. The evaluation results are shown in Table 1.

Comparative Example 3
The solid contents of the styrene resin emulsion (1) and the PVA resin solution prepared above are diluted with deionized water so as to be 5% by weight and 15% by weight respectively, and the polyvinyl alcohol resin [I] in the emulsion and The curl retention performance and the cleaning performance were evaluated by adjusting the weight ratio of the vinyl resin (A) to be 20:80. The evaluation results are shown in Table 1.

The ratio of polyvinyl alcohol resin [I] to vinyl resin (A) is 55: 45 to 99:
It can be seen that Examples 1 and 2 of 1 have good curl retention performance and cleaning performance and are useful as an eyelash cosmetic emulsion. In the case of only the vinyl-based resin (A) of Comparative Example 1 and when the ratio of the polyvinyl alcohol-based resin [I] of Comparative Example 3 is less than 55, the cleaning property is inferior and the polyvinyl alcohol-based resin [I] of Comparative Example 2 It can be understood that the curl retention performance is inferior in the case of only the case.

  The eyelash cosmetic emulsion according to the present invention is excellent in curl retention performance and washing performance, and when used for mascara etc., can maintain both long-term curl retention under high humidity and easy washability with water.

Claims (5)

  A resin emulsion for an eyelash cosmetic comprising a polyvinyl alcohol resin [I] and a vinyl resin (A), wherein the weight ratio of the polyvinyl alcohol resin [I] to the vinyl resin (A) in the emulsion is 55: It is 45-99: 1, The resin emulsion for eyelash cosmetics characterized by the above-mentioned.   The glass transition temperature of a vinyl resin (A) is 70 degrees C or less, The resin emulsion for eyelash cosmetic agents of Claim 1 characterized by the above-mentioned.   The resin emulsion for eyelash cosmetic compositions according to claim 1 or 2, wherein the vinyl resin (A) is an acrylic resin. 4. The eyelash makeup according to any one of claims 1 to 3, comprising a vinyl resin (A) obtained by polymerizing a vinyl monomer (a) dispersed and stabilized by a vinyl alcohol resin [I]. Resin emulsion   An eyelash cosmetic agent comprising the acrylic-containing resin emulsion for eyelash cosmetic agent according to any one of claims 1 to 4.