JP2018184384A - Aqueous resin dispersion for manicure, method for producing the same and manicure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous resin dispersion for a cosmetic having excellent stability with time and three characteristics of makeup durability, water resistance and removability.SOLUTION: There is provided an aqueous resin dispersion for a cosmetic which comprises resin particles and an aqueous medium, wherein the resin is a polymer of a monomer mixture containing a methacrylic acid alkyl ester having an alkyl group having 2 to 4 carbon atoms and acrylic acid and contains more than 10 mass% or 80 mass% or less of the methacrylic acid alkyl ester having an alkyl group having 2 to 4 carbon atoms in 100 mass% of the monomer mixture and the resin has a glass transition temperature of-20 to 100°C.SELECTED DRAWING: None

Description

  The present invention relates to an aqueous resin dispersion for cosmetics.

  In cosmetics such as hair cosmetics, makeup cosmetics, beauty nails, and skin care cosmetics, water-soluble polymer compounds have been mainly used as film forming agents in consideration of environmental aspects and hygiene. However, since water-soluble polymers are inferior in moisture resistance and water resistance, aqueous resin dispersions are widely used in recent years as aqueous film forming agents.

  The water resistance and water resistance of the aqueous resin dispersion are good compared to the water-soluble polymer, but tend to be slightly inferior compared to the solvent-based resin. In addition, since the aqueous resin dispersion is a dispersion of resin fine particles, stability over time is required when it is made into a cosmetic. Patent Document 1 discloses a cosmetic containing an aqueous resin dispersion containing 10 to 20% by mass of a carboxyl group-containing monomer such as acrylic acid. Patent Document 2 discloses a cosmetic containing an aqueous resin dispersion using a silane coupling agent.

JP 2005-002207 A JP 2002-327019 A

  However, the aqueous resin dispersion of Patent Document 1 has a problem of poor water resistance. In addition, the aqueous resin dispersions in the patent literature have a problem that the stability over time when used as a cosmetic is poor.

  An object of the present invention is to provide an aqueous resin dispersion for cosmetics, a method for producing the same, and cosmetics, which are excellent in stability over time, have three characteristics of long-lasting makeup, water resistance and removability.

The aqueous resin dispersion for cosmetics of the present invention comprises resin particles and an aqueous medium,
The resin is a polymer of a monomer mixture containing a methacrylic acid alkyl ester having 2 to 4 carbon alkyl groups and acrylic acid,
Including 100% by mass of the methacrylic acid alkyl ester having an alkyl group having 2 to 4 carbon atoms in 100% by mass of the monomer mixture,
The glass transition temperature of the resin is -20 to 100 ° C.

  INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an aqueous resin dispersion for cosmetics, a method for producing the same, and cosmetics, which are excellent in stability over time, have a combination of cosmetic properties, water resistance and removability.

The aqueous resin dispersion for cosmetics of the present invention comprises resin particles and an aqueous medium,
The resin is a polymer of a monomer mixture containing a methacrylic acid alkyl ester having 2 to 4 carbon alkyl groups and acrylic acid,
Including 100% by mass of the methacrylic acid alkyl ester having an alkyl group having 2 to 4 carbon atoms in 100% by mass of the monomer mixture,
The glass transition temperature of the resin is -20 to 100 ° C, preferably -10 to 90 ° C, and more preferably 0 to 80 ° C. The average particle diameter of the resin particles is preferably 30 nm to 500 nm, more preferably 40 to 400 nm, and even more preferably 50 to 300 nm. In addition, a monomer is an ethylenically unsaturated group containing monomer.

  The aqueous resin dispersion for cosmetics of the present invention uses a specific amount of methacrylic acid alkyl ester having 2 to 4 carbon atoms and acrylic acid in combination, and the resin has a glass transition temperature of 0 to 100 ° C. It can have the three characteristics of makeup retention, water resistance and removability. Thereby, the cosmetic using the aqueous resin dispersion for cosmetics can be easily removed after use, although it is difficult to be removed by sweat or sebum.

  The cosmetic of the present invention is characterized in that it contains the cosmetic aqueous resin dispersion. The cosmetic of the present invention is preferably, for example, a hair treatment agent, a hair styling agent, an aqueous beauty nail agent, an eyeliner, mascara, skin cream, sunscreen agent, or the like. Needless to say, the cosmetic can be applied to cosmetics other than those described above. The cosmetic of the present invention is not a face wash.

<Methacrylic acid alkyl ester having an alkyl group having 2 to 4 carbon atoms>
The methacrylic acid alkyl ester having a C2-4 alkyl group used in the present invention is a C2-4 alkyl ester of methacrylic acid.
Examples of the methacrylic acid alkyl ester having an alkyl group having 2 to 4 carbon atoms include ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, secondary butyl methacrylate, and tertiary butyl methacrylate. Among these, methacrylic acid alkyl esters having an alkyl group having 4 carbon atoms are preferred in terms of cosmetic durability.
The methacrylic acid alkyl ester having an alkyl group having 2 to 4 carbon atoms can be used alone or in combination of two or more.

  The methacrylic acid alkyl ester having an alkyl group having 2 to 4 carbon atoms is preferably contained in an amount of more than 10% by mass and not more than 80% by mass in 100% by mass of the monomer mixture, and more preferably 20 to 75% by mass. When a suitable amount of an alkyl methacrylate having 2 to 4 carbon atoms is used, the cosmetic durability is further improved.

  Examples of the carboxyl group-containing monomer used in the present invention include acrylic acid and methacrylic acid, and acrylic acid is preferable in terms of further improving the polymerization stability. It is preferable that a carboxyl group-containing monomer contains 0.1-10 mass% in a monomer mixture, 0.3-8 mass% is more preferable, 0.5-6 mass% is further more preferable.

<Polymerizable silane compound>
The polymerizable silane compound is a silane compound having an ethylenically unsaturated double bond. Polymerizable silane compounds include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acrylic. Roxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldi Examples include ethoxysilane, parastyryltrimethoxysilane, and parastyryltriethoxysilane. Among these, a polymerizable silane compound having an ethoxy group is preferable in terms of removability.
The polymerizable silane compound can be used alone or in combination of two or more.

  The polymerizable silane compound is preferably contained in an amount of 0.1 to 10% by mass, more preferably 0.1 to 5% by mass in 100% by mass of the monomer mixture. When an appropriate amount of the polymerizable silane compound is used, makeup is maintained and the storage stability of the resin particles is further improved.

<Other monomers>
Other monomers are monomers other than C2-C4 methacrylic acid alkyl esters, acrylic acid, and polymerizable silane compounds. Other monomers include, for example, methacrylic acid alkyl esters, acrylic acid alkyl esters, (meth) acrylic acid alkyl esters having an aliphatic ring or an aromatic ring, hydroxyl group-containing monomers, glycidyl groups. Preferred are monomers containing monomers, polyoxyalkylene group-containing monomers, crosslinkable monomers, and other vinyl group-containing monomers. The polymerizable surfactant is not included in the monomer.

  Examples of the methacrylic acid alkyl ester having 1 or 5 carbon atoms include methyl methacrylate, pentyl methacrylate, neopentyl methacrylate, hexyl methacrylate, 3-pentyl methacrylate, hexyl methacrylate, 2-ethylbutyl methacrylate, heptyl methacrylate, 2-heptyl methacrylate, Octyl methacrylate, 2-octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, tetradecyl methacrylate, pentadecyl methacrylate, hexadecyl methacrylate, heptadecyl methacrylate, octadecyl methacrylate, nona Decyl methacrylate , Icosyl methacrylate, behenyl methacrylate, and the like.

  Acrylic acid alkyl ester is, for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, secondary butyl acrylate, tertiary butyl acrylate, pentyl acrylate, neopentyl acrylate, hexyl acrylate, 3-pentyl acrylate, Hexyl acrylate, 2-ethylbutyl acrylate, heptyl acrylate, 2-heptyl acrylate, octyl acrylate, 2-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, tridecyl acrylate, tetradecyl acrylate , Pentadecyl acrylate DOO, hexadecyl acrylate, heptadecyl acrylate, octadecyl acrylate, nonadecyl acrylate, icosyl acrylate, behenyl acrylate, and the like.

  Examples of the (meth) acrylic acid alkyl ester having an aliphatic ring or an aromatic ring include cyclohexyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, and the like.

  Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, and allyl alcohol. .

Examples of the glycidyl group-containing monomer include glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether.
Polyoxyalkylene group-containing monomers include, for example, diethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polyethylene glycol / polypropylene glycol mono (meth) acrylate, methoxydiethylene glycol mono (meth) acrylate, methoxypolyethylene glycol mono (Meth) acrylate, phenoxydiethylene glycol mono (meth) acrylate, phenoxypolyethylene glycol mono (meth) acrylate, and the like.

The crosslinkable monomer is a monomer having a vinyl group or a (meth) acryloyl group in addition to the ethylenically unsaturated group. Examples of the crosslinkable monomer include allyl (meth) acrylate, vinyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and polyethylene glycol di (meth). ) Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate , Neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate DOO, pentaerythritol tetra (meth) acrylate, divinylbenzene, divinyl adipate, diallyl isophthalate, diallyl phthalate, and diallyl maleate, and the like.
Examples of other vinyl group-containing monomers include styrene, α-methylstyrene, and vinyl acetate.
Other monomers can be used alone or in combination of two or more.

The synthesis of the aqueous resin dispersion for cosmetics includes emulsion polymerization, solution polymerization, bulk polymerization and the like, and emulsion polymerization is preferred.
In the method for producing an aqueous resin dispersion for cosmetics of the present invention, a monomer mixture containing a methacrylic acid alkyl ester having 2 to 4 carbon atoms and an acrylic acid is emulsion-polymerized to have a glass transition temperature of -20 to 20. It is preferable that the resin particle of 100 degreeC is included. It is preferable that the methacrylic acid alkyl ester having an alkyl group having 2 to 4 carbon atoms is contained more than 10% by mass and 100% by mass or less in 100% by mass of the monomer mixture. The monomer mixture does not contain a polymerizable surfactant.

  The emulsion polymerization is preferably performed in the presence of at least one of a surfactant and a protective colloid. The surfactant is preferably an anion, a cation or a nonion as an ionic species, and more preferably an anion or a nonion. The surfactant is preferably a polymerizable surfactant having an ethylenically unsaturated double bond in terms of water resistance.

<Polymerizing surfactant>
The polymerizable surfactant is an anionic or nonionic surfactant having one or more unsaturated double bonds capable of radical polymerization in the molecule, and is other than the above-described polymerizable silane compound.
In the polymerizable anionic surfactant, the main skeleton is preferably a sulfosuccinic acid ester, an alkyl ether, an alkylphenyl ether, an alkylphenyl ester, a (meth) acrylate sulfate, or a phosphate.
In the polymerizable nonionic surfactant, the main skeleton is preferably an alkyl ether, an alkylphenyl ether, or an alkylphenyl ester.

<Non-polymerizable surfactant>
Non-polymerizable anionic surfactants include, for example, higher fatty acid salts such as sodium oleate, alkylaryl sulfonates such as dodecylbenzene sulfonic acid, alkyl sulfate esters such as sodium lauryl sulfate, polyoxyethylene lauryl ether sodium sulfate Polyoxyethylene alkyl ether sulfates such as sodium monooctylsulfosuccinate, sodium dioctylsulfosuccinate, sodium polyoxyethylene laurylsulfosuccinate and derivatives thereof, polyoxyethylene distyrenated phenyl ether sulfate Examples include salts.
Examples of the non-polymerizable nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether, polyoxyethylenes such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether. Sorbitan higher fatty acid esters such as alkyl phenyl ether, sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, poly Polyoxyethylene higher fatty acid esters such as oxyethylene monolaurate and polyoxyethylene monostearate, Phosphate monoglycerides, glycerin higher fatty acid esters such as stearic acid monoglyceride, polyoxyethylene polyoxypropylene block copolymers, polyoxyethylene distyrenated phenyl ether and the like.

  The surfactant preferably contains 1 to 10 parts by mass with respect to 100 parts by mass of the monomer mixture. When an appropriate amount of the surfactant is used, the mechanical stability of the resin particles is further improved, and when an appropriate amount of the polymerizable surfactant is used, the mechanical stability is further improved.

In the emulsion polymerization, it is preferable to use a radical polymerization initiator (hereinafter referred to as a polymerization initiator). As the polymerization initiator, a known oil-soluble polymerization initiator or water-soluble polymerization initiator can be used.
Examples of the oil-soluble initiator include benzoyl peroxide, tertiary butyloxybenzoate, tertiary butyl hydroperoxide, tertiary butyl peroxy-2-ethylhexanoate, tertiary butyl peroxy-3,5,5, Organic peroxides such as trimethylhexanoate, ditertiary butyl peroxide, cumene hydroperoxide, and p-menthane hydroperoxide, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2 Azobis compounds such as 1,4-dimethylvaleronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), and 1,1′-azobis-cyclohexane-1-carbonitrile.
Examples of the water-soluble polymerization initiator include ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, and 2,2′-azobis (2-methylpropionamidine) dihydrochloride.

In the synthesis, a reducing agent can be used in combination with the polymerization initiator. Thereby, the polymerization reaction can be promoted. Such reducing agents include reducing organic compounds such as metal salts such as ascorbic acid, erythorbic acid, tartaric acid, citric acid, glucose, formaldehyde sulfoxylate, sodium sulfite, sodium bisulfite, sodium metabisulfite (SMBS) And reducing inorganic compounds such as sodium hyposulfite, ferrous chloride, Rongalite and the like.
In the present invention, it is preferable to use a water-soluble polymerization initiator for emulsion polymerization. It is preferable that a polymerization initiator uses 0.03-5 mass parts with respect to 100 mass parts of monomer mixtures. The reducing agent is preferably used in an amount of 0.01 to 2.5 parts by mass with respect to 100 parts by mass of the monomer mixture.

The aqueous resin dispersion for cosmetics can use a buffer, a chain transfer agent, a basic compound, etc. as needed at the time of emulsion polymerization. Examples of the buffer include sodium acetate, sodium citrate, sodium bicarbonate and the like. Examples of the chain transfer agent include octyl mercaptan, tertiary decyl mercaptan, lauryl mercaptan, stearyl mercaptan, 2-ethylhexyl mercaptoacetate, octyl mercaptoacetate, 2-ethylhexyl mercaptopropionate, and octyl mercaptopropionate.
Basic compounds are used for neutralization, for example, alkylamines such as trimethylamine, triethylamine, and butylamine; alcohol amines such as 2-dimethylaminoethanol, diethylaminoethanol, diethanolamine, triethanolamine, and aminomethylpropanol; morpholine, ammonia, and the like Is mentioned.

  Examples of the emulsion polymerization method include a batch reaction in which a monomer, a surfactant, and water are all charged and reacted in a reaction tank, and a drop reaction in which a monomer is gradually dropped into the reaction tank to react. Among these, the dropping reaction is preferable in terms of easy control of heat generation in the polymerization reaction. In order to further improve the polymerization stability, the dropping reaction is preferably carried out after the monomer, water, and the surfactant are mixed and stirred to form an emulsified monomer pre-emulsion.

<Resin particles>
The average particle diameter of the resin particles is preferably 30 to 500 nm, and more preferably 50 to 400 nm. By setting the average particle diameter to 30 to 500 nm, water resistance and stability over time are further improved.

<Silane compound>
The silane compound is a compound other than the polymerizable silane compound. Silane compounds include, for example, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, hexyltrimethoxysilane, Hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, 1,6-bis (trimethoxysilyl) hexane, 1,6-bis (triethoxysilyl) hexane, tri Fluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, hexamethyldisilazane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3 4-epoxycyclohexyl) ethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldi Ethoxysilane, 3 Trimethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3- Mercaptomethyldimethoxysilane, 3-mercaptomethyldiethoxysilane, bis (trimethoxysilylpropyl) tetrasulfide, bis (triethoxysilylpropyl) tetrasulfide, 3-ureidopropyltrialkoxysilane, 3-isocyanatopropylate Examples include limethoxysilane, 3-isocyanatopropyltriethoxysilane, tris- (trimethoxysilylpropyl) isocyanurate, and tris- (triethoxysilylpropyl) isocyanurate. Among these, a silane compound having an ethoxy group is preferable in terms of removability.

The cosmetics of the present invention essentially require an aqueous resin dispersion for cosmetics, and depending on the use of the cosmetics, for example, thickeners, film-forming aids, plasticizers, humectants, ultraviolet absorbers, preservatives Further, a known material such as a coloring material can be included.

  Examples of the thickener include alkali swelling type thickener, associative polyurethane, carboxyvinyl polymer, thickening polysaccharide, and clay mineral.

  Examples of film forming aids and plasticizers include cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, carbitols such as carbitol, dimethyl carbitol, diethyl carbitol, butyl carbitol, dibutyl carbitol; ethylene carbonate, diethylene Carbonates such as carbonate and propylene carbonate; acetates such as cellosolve acetate, butyl cellosolve acetate, butyl carbitol acetate, and sucrose acetate; ethanol, propanol, butanol, pentanol, hexanol, benzyl alcohol, 2-phenylethanol alcohol, ethylene glycol, propylene glycol Diols such as butylene glycol and hexylene glycol; phthalic acid diester, adipic acid Esters, diesters of succinic acid, sebacic acid diester, an ester such as Abiechikuen ester; benzoic acid esters such as sucrose benzoate, diethylbenzene and the like.

  The humectant is, for example, sorbitol, xylitol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, glycerin, diglycerin, polyethylene glycol, hyaluronic acid, chondroitin sulfate, pyrrolidone carboxylate, and DL-pyrrolidone carboxylic acid. Examples include salts.

  Examples of the ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, sodium 2-hydroxy-4-methoxybenzophenone-5-sulfonate, dihydromethoxybenzophenone, dihydroxy Benzophenone derivatives such as sodium methoxybenzophenone-sodium sulfonate, 2,4-dihydroxybenzophenone, tetrahydroxybenzophenone; paraaminobenzoic acid, ethyl paraaminobenzoate, glyceryl paraaminobenzoate, amyl paradimethylaminobenzoate, and paradimethylaminobenzoic acid Benzoic acid derivatives such as octyl; ethyl paramethoxycinnamate, isopropyl paramethoxycinnamate, octyl paramethoxycinnamate, 2-methoxyparacinnamic acid 2- Methoxycinnamic acid derivatives such as toxiethyl, sodium paramethoxycinnamate, potassium paramethoxycinnamate, and glycerin mono-2-ethylhexanoate; octyl salicylate, phenyl salicylate, homomenthyl salicylate, dipropylene salicylate Salicylic acid derivatives such as glycol, ethylene glycol salicylate, myristyl salicylate, methyl salicylate; urocanic acid, ethyl urocanate, urocanic acid ethyl ester, 4-tert-butyl-4′-methoxybenzoylmethane, 2- (2′-hydroxy-5 '-Methylphenyl) benzotriazole, 2-phenyl-5-methylbenzoxazole, methyl anthranilate, dimethoxybenzylidene dioxoimidazolidinepropionate 2-ethyl Hexyl, and the like.

  Examples of the preservative include paraoxybenzoic acid alkyl ester, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol, and dehydroacetic acid, and salts thereof.

  EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, parts means parts by mass and% means mass%.

Example 1 Synthesis of Aqueous Resin Dispersion for Cosmetics As a methacrylic acid alkyl ester having 2 to 4 carbon atoms, 20 parts of ethyl methacrylate, 40 parts of butyl methacrylate, 3 parts of acrylic acid, and KBE-503 1 as a polymerizable silane compound A monomer pre-emulsion was prepared by mixing 36 parts of butyl acrylate as a monomer, 1.8 parts of PD-104 as a polymerizable surfactant, and 55 parts of water, and charged in a dropping tank.
Separately, a four-necked flask equipped with a reflux condenser, a stirrer, a thermometer, a nitrogen inlet tube, and a raw material inlet was used as a reaction vessel, and 90 parts of water was charged into the reaction vessel. Subsequently, nitrogen was introduced and the liquid temperature was heated to 70 ° C. while stirring. Then, 0.2 part of PD-104 is added to the reaction vessel, the monomer pre-emulsion is continuously dropped from the dropping tank over 3 hours, and the liquid temperature is reduced by using 0.3 part of ammonium persulfate. Emulsion polymerization was performed while maintaining the temperature at 80 ° C. After completion of the dropwise addition, the emulsion polymerization was continued for another 2 hours. Then, it cooled to 50 degreeC and obtained the aqueous solution dispersion for cosmetics by filtering the obtained solution with the filter cloth made from a 180 mesh polyester. There was no aggregate remaining on the filter cloth, and the polymerization stability was good. The obtained aqueous resin dispersion had a nonvolatile content of 40% and an acid value of 23 mgKOH / g.

The glass transition temperature (Tg) of the resin constituting the aqueous resin dispersion was measured using DSC (Differential Scanning Calorimeter TA Instruments). Specifically, 2 mg of the above emulsion was weighed on an aluminum pan, the aluminum pan from which the dispersion medium was evaporated was set on a DSC measurement holder, and the endothermic peak obtained by measuring under a temperature rising condition of 5 ° C./min was obtained. Tg. Moreover, the average particle diameter of the resin particles constituting the aqueous resin dispersion is a D50 average particle diameter using a dynamic light scattering measurement method. For the measurement, a diluted solution was prepared by diluting the aqueous resin dispersion 500 times (volume ratio) with water, and about 5 mL of the diluted solution was measured with Nanotrac (Nikkiso Co., Ltd.).

<Water resistance>
The water resistance of the aqueous resin dispersion was evaluated by the method shown below. The aqueous resin dispersion was applied on a glass plate using an applicator so that the thickness after drying was 40 μm, and dried at 80 ° C. for 1 hour to prepare a resin film. The obtained resin film was put into 40 degreeC warm water, and the state of the film after 1 hour was confirmed visually. The evaluation criteria are shown below.
A: No change is observed in the film (very good B: the film is slightly whitened (good)
Δ: Whitening of film (somewhat poor)
X: The film peeled off from the glass plate (defective)

<Machine stability>
The mechanical stability of the aqueous resin dispersion was evaluated by the method shown below. Using a Maron mechanical stability tester AB-802 manufactured by Tester Sangyo Co., Ltd., measurement was performed under the following conditions.
Resin content: 20%
Amount used: 50 g
Number of revolutions: 1000 rpm (± 20 rpm)
Time: Over 20 minutes: 30 kgf
The aqueous resin dispersion after the measurement was filtered through a 100 mesh wire mesh, the dry mass (Wg) of the aggregate on the wire mesh was measured, and the amount (%) of the generated aggregate was calculated according to the following formula and evaluated as follows. .
Generated aggregate amount (%) = W (g) / [50 (g) × resin content of emulsion (20%)] × 100
The evaluation criteria are shown below.
A: Generated aggregate amount <0.1% (very good)
◯: 0.1% ≦ generated aggregate amount <0.3% (good)
Δ: 0.3% ≦ the amount of generated aggregates <1% (slightly poor)
×: 1% ≦ Aggregate generated (bad)

<Stability over time>
The temporal stability of the aqueous resin dispersion was evaluated by the following method. The viscosity was measured immediately after production of the obtained aqueous resin dispersion, then placed in a sealed container, and after one month at 60 ° C., the viscosity was measured again. For the viscosity measurement, a B-type viscometer was used, and measurement was performed under the conditions of 25 ° C. and 30 rpm.
Viscosity change rate (%) = | initial viscosity−viscosity after aging | × 100
The evaluation criteria are shown below.
A: Viscosity change rate <10% (very good)
◯: 10% ≦ viscosity change rate <20% (good)
Δ: 20% ≦ viscosity change rate <50% (slightly poor)
×: 50% ≦ viscosity change rate (defect)

<Examples 2 to 10 and Comparative Examples 1 to 6> Synthesis of Aqueous Resin Dispersion for Cosmetics Examples 2 to 10 and Comparative Example were the same as Example 1 except that the composition shown in Table 1 was changed. The aqueous resin dispersions for cosmetics of Examples 1 to 6 were obtained. The numerical values in the table indicate “part” if the unit is not described, and the blank indicates that it is not used.

Abbreviations in the table are as follows.
<Methyl methacrylate alkyl ester having 2 to 4 carbon atoms and acrylic acid>
EMA: ethyl methacrylate BMA: butyl methacrylate iBMA: isobutyl methacrylate tBMA: tertiary butyl methacrylate AA: acrylic acid

<Other monomers>
MMA: Methyl methacrylate LMA: Lauryl methacrylate (dodecyl methacrylate)
EA: ethyl acrylate BA: butyl acrylate 2EHA: 2-ethylhexyl acrylate 4HBA: 4-hydroxybutyl methacrylate MAA: methacrylic acid EGDMA: ethylene glycol dimethacrylate

<Polymerizable silane compound>
KBE-503: 3-methacryloxypropyltriethoxysilane

<Polymerizing surfactant>
PD-104: ammonium polyoxyalkylene alkenyl ether sulfate (Latemul PD-104, manufactured by Kao Corporation)

<Non-polymerizable surfactant>
EO: Sodium lauryl sulfate (Emar O, manufactured by Kao Corporation)

<Silane compounds other than polymerizable silane compounds>
HTS-E: Hexyltriethoxysilane

  From the results of Table 1, the resin is a polymer of a monomer mixture containing a methacrylic acid alkyl ester having an alkyl group having 2 to 4 carbon atoms and acrylic acid, and an aqueous resin dispersion having a glass transition temperature of -20 to 100 ° C. The body was excellent in water resistance, mechanical stability and stability over time.

<Example 11> Blending of mascara 5 parts of stearic acid and 3 parts of liquid paraffin were blended and dissolved at 80 ° C to obtain an oil phase. Next, 5 parts of propylene glycol, 2 parts of Bengel FW, 0.5 part of sodium lauryl sulfate and 64.5 parts of water were blended, dissolved at 80 ° C., and BLACK PEARLS 4350.
10 parts were dispersed to obtain an aqueous phase. The aqueous phase was added to the oil phase and emulsified using a homomixer, and then 10 parts of the dispersion obtained in Example 1 was gradually added and stirred with the homomixer. Then, it cooled to normal temperature and obtained the mascara. The mascara performance was evaluated by a use test with 15 subjects. As evaluation items, water resistance, makeup durability, and removability were evaluated in four stages. The evaluation criteria are shown below.
A: 13 or more subjects answered that they were good (very good)
A: 10 to 12 subjects answered good (good)
Δ: 5-9 subjects answered good (somewhat poor)
×: 0 to 4 subjects answered good (bad)

<Examples 12-15 and Comparative Examples 7-9> Formulation of Mascara The mascara of Examples 12-15 and Comparative Examples 7-9 were prepared in the same manner as in Example 11 except that the formulation shown in Table 2 was changed. I got each. The numerical values in the table indicate “part” if the unit is not described, and the blank indicates that it is not used.

Abbreviations in the table are as follows.
Wenger FW: Natural bentonite (manufactured by Hojun Co.)
BLACK PEARLS 4350: Carbon black (manufactured by Cabot)

  As can be seen from Table 2, the resin is a polymer of a monomer mixture containing a methacrylic acid alkyl ester having 2 to 4 carbon atoms and acrylic acid, and the glass transition temperature of the resin is -20 to 100 ° C. The mascara of Examples 11 to 15 in which the aqueous resin dispersions of certain Examples 1, 3, 5, 7, and 9 are blended, the resin does not contain a methacrylic acid alkyl ester having an alkyl group having 2 to 4 carbon atoms. Comparative Example 7 in which the aqueous resin dispersion of Comparative Example 1 as a polymer was blended, Comparative Example 8 in which the aqueous resin dispersion of Comparative Example 5 in which the glass transition temperature of the resin was −20 ° C. or lower was blended, and aqueous resin dispersion Compared with the mascara of the comparative example 9 which has not mix | blended the body, water resistance, makeup lasting, and removability were excellent.

<Example 16> Blending of nail polish A solution prepared by mixing 10 parts of ethylene glycol monoethyl ether, 3 parts of acetyltributyl citrate and 7 parts of water was gradually blended into 80 parts of the dispersion obtained in Example 2, Stir with a disper until uniform to obtain a beautiful nail material. The performance evaluation of the nail polish was performed by a use test by 15 subjects. As evaluation items, water resistance, makeup durability, and removability were evaluated in four stages. The evaluation criteria are the same as for mascara.

<Examples 17 to 20 and Comparative Examples 10 and 11> Blending of nail polishes Examples 17 to 20 and Comparative Examples 10 and 11 were the same as Example 16 except that the blending composition shown in Table 3 was changed. Each of the beautiful nail materials was obtained. The numerical values in the table indicate “part” if the unit is not described, and the blank indicates that it is not used.

  As can be seen from Table 3, the resin is a polymer of a monomer mixture containing a methacrylic acid alkyl ester having 2 to 4 carbon atoms and acrylic acid, and the resin has a glass transition temperature of -20 to 100 ° C. The nail polish of Examples 16-20 which mix | blended the aqueous resin dispersion of a certain Example 2, 4, 6, 8, 10 has 10 mass of methacrylic acid alkylester in which resin has a C2-C4 alkyl group. Comparative Example 10 blended with the aqueous resin dispersion of Comparative Example 2, which is a monomer polymer containing only less than or equal to 10%, and comparative blended with the aqueous resin dispersion of Comparative Example 6 having a glass transition temperature of 100 ° C. or higher. Compared to the beauty nail preparation of Example 11, the water resistance, makeup lasting and removability were excellent.

<Example 21> Blending of eyeliner 1 part of Rhedol TW-S120V, 0.5 part of Echo Gum, 10 parts of BLACK PEARLS 4350 and 72.5 parts of water were blended and dispersed uniformly using a colloid mill. To this dispersion, 5 parts of glycerin and 1 part of acetyltributyl citrate were blended, and further 10 parts of the dispersion obtained in Example 1 were gradually blended and stirred until uniform to obtain an eyeliner. . The performance evaluation of the eyeliner was performed by a use test by 15 subjects. As evaluation items, water resistance, makeup durability, and removability were evaluated in four stages. The evaluation criteria are the same as for the eyeliner.

<Examples 22 to 25 and Comparative Example 12> Blending of Eyeliner The eyeliners of Examples 22 to 25 and Comparative Example 12 were the same as in Example 21 except that the blending composition shown in Table 4 was changed. Obtained. The numerical values in the table indicate “part” if the unit is not described, and the blank indicates that it is not used.

Abbreviations in the table are as follows.
Rheodor TW-S120V: Polyoxyethylene sorbitan monostearate (manufactured by Kao Corporation)
Echo gum: Xanthan gum (made by DSP Gokyo Food & Chemical)
BLACK PEARLS 4350: Carbon black (manufactured by Cabot)

  As can be seen from Table 4, the resin is a polymer of a monomer mixture containing a methacrylic acid alkyl ester having 2 to 4 carbon atoms and acrylic acid, and the resin has a glass transition temperature of -20 to 100 ° C. The eyeliner of Examples 21 to 25 in which the aqueous resin dispersions of certain Examples 1, 3, 5, 7, and 9 were blended was 80% by mass of methacrylic acid alkyl ester having an alkyl group having 2 to 4 carbon atoms. Compared with the eyeliner of Comparative Example 12 in which the aqueous resin dispersion of Comparative Example 3 which is a monomer polymer containing an amount exceeding 35% was added, the water resistance and makeup lasting were excellent.

<Example 26> Blending of hair styling agent 15 parts of the dispersion obtained in Example 2 were gradually blended into a solution obtained by mixing 5 parts of dipropylene glycol, 1 part of ethanol, 1 part of BELSIL DM3102E and 78 parts of water. The hair styling agent was obtained by stirring with a disper until uniform. The performance evaluation of the hair styling agent was performed by a use test by 15 subjects. As evaluation items, water resistance, makeup durability, and removability were evaluated in four stages. The evaluation criteria are the same as for the eyeliner.

<Examples 27 to 30 and Comparative Example 13> Blending of hair styling agents The hair styling agents of Examples 27 to 30 and Comparative Example 13 were the same as in Example 26 except that the blending composition shown in Table 4 was changed. Respectively. The numerical values in the table indicate “part” if the unit is not described, and the blank indicates that it is not used.

Abbreviations in the table are as follows.
BELSIL DM 3102E: Polydimethylsiloxane (manufactured by Asahi Kasei Wacker Silicone)

  As can be seen from Table 5, the resin is a polymer of a monomer mixture containing a methacrylic acid alkyl ester having 2 to 4 carbon atoms and acrylic acid, and the resin has a glass transition temperature of -20 to 100 ° C. The hair styling agents of Examples 26 to 30 in which the aqueous resin dispersions of Examples 2, 4, 6, 8, and 10 were blended were comparative examples 4 in which the resin was a polymer of a monomer mixture containing no acrylic acid. Compared with the hair styling agent of Comparative Example 13 in which the aqueous resin dispersion was blended, the water resistance, setting power and removability were excellent.

The present invention relates to a beauty nail fees aqueous resin dispersion.

The present invention is stable with time, lasting cosmetic, and an object thereof is to provide a beauty nail fee aqueous resin dispersion and a production method thereof, and beauty nail charges that combines three characteristics that water resistance and removability.

Beauty nail fee aqueous resin dispersion of the present invention comprises a resin particle and an aqueous medium,
The resin is a polymer of a monomer mixture containing a methacrylic acid alkyl ester having 2 to 4 carbon alkyl groups and acrylic acid,
20% by mass to 80% by mass of methacrylic acid alkyl ester having 2 to 4 carbon atoms is contained in 100% by mass of the monomer mixture, and 0.1% by mass or more and less than 10% by mass of acrylic acid. ,
The glass transition temperature of the resin is -20 to 100 ° C.

Stable with time by the present invention, makeup, can provide beauty nail fee aqueous resin dispersion and a production method thereof, and beauty nail charges that combines three characteristics that water resistance and removability.

Beauty nail fee aqueous resin dispersion of the present invention comprises a resin particle and an aqueous medium,
The resin is a polymer of a monomer mixture containing a methacrylic acid alkyl ester having 2 to 4 carbon alkyl groups and acrylic acid,
The methacrylic acid alkyl ester having an alkyl group having 2 to 4 carbon atoms in 100% by mass of the monomer mixture contains 20% by mass to 80% by mass,
The glass transition temperature of the resin is -20 to 100 ° C, preferably -10 to 90 ° C, and more preferably 0 to 80 ° C. The average particle diameter of the resin particles is preferably 30 nm to 500 nm, more preferably 40 to 400 nm, and even more preferably 50 to 300 nm. In addition, a monomer is an ethylenically unsaturated group containing monomer.

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”. In this specification, Examples 1, 3, 5, 7, 9, and 11 to 15, and 21 to 30 are reference examples.

Claims (9)

Including resin particles and an aqueous medium,
The resin is a polymer of a monomer mixture containing a methacrylic acid alkyl ester having 2 to 4 carbon alkyl groups and acrylic acid,
Including 100% by mass of the methacrylic acid alkyl ester having an alkyl group having 2 to 4 carbon atoms in 100% by mass of the monomer mixture,
The aqueous resin dispersion for cosmetics whose glass transition temperature of the said resin is -20-100 degreeC.   The aqueous resin dispersion for cosmetics according to claim 1, wherein the alkyl ester of methacrylic acid having an alkyl group having 2 to 4 carbon atoms includes an alkyl ester of methacrylic acid having an alkyl group having 4 carbon atoms.   The aqueous resin dispersion for cosmetics according to claim 1 or 2, comprising 0.1 to 10% by mass of acrylic acid in 100% by mass of the monomer mixture.   The aqueous resin dispersion for cosmetics according to any one of claims 1 to 3, wherein the mixture further contains a polymerizable silane compound as a monomer.   The aqueous resin dispersion for cosmetics according to any one of claims 1 to 4, wherein the mixture further contains a polymerizable surfactant (excluding a polymerizable silane compound) as a monomer.   The aqueous resin dispersion for cosmetics according to claim 5, wherein the mixture contains 1 to 10 parts by mass of a polymerizable surfactant with respect to 100 parts by mass of a monomer other than the polymerizable surfactant.   Furthermore, the aqueous resin dispersion for cosmetics of any one of Claims 1-6 containing a silane compound.   Cosmetics containing the aqueous resin dispersion for cosmetics of any one of Claims 1-7. For cosmetics in which a monomer mixture containing a methacrylic acid alkyl ester having 2 to 4 carbon atoms and acrylic acid is emulsion-polymerized in the presence of an aqueous medium, and the resin has a glass transition temperature of -20 to 100 ° C. A method for producing an aqueous resin dispersion comprising:
The manufacturing method of the aqueous resin dispersion for cosmetics which contains more than 10 mass% and 80 mass% or less of the alkyl methacrylate which has the said C2-C4 alkyl group in 100 mass% of said mixtures.