JP5191781B2 - Resin particles - Google Patents

Description

  The present invention relates to cross-linked (meth) acrylic ester resin particles, a process for producing the same, and a cosmetic containing the resin particles.

  As cosmetics containing cosmetic powder, body cosmetics such as body powders, makeup cosmetics such as foundations, lotions such as body lotions, and the like are commercially available. In cosmetics containing these cosmetic powders, polymethyl methacrylate particles, cross-linked polystyrene particles, polyethylene are provided for the purpose of imparting functions such as improved elongation on skin, improved touch, and hiding effect. Resin particles such as particles are blended.

  However, although polymethyl methacrylate particles are excellent in imparting excellent elongation to cosmetics, they are insufficient in terms of imparting a soft feel and a smooth feel.

Patent Document 1 discloses resin particles obtained by adhering organic powder to the surface of crosslinked (meth) acrylate resin particles having a compressive strength of 0.05 to 0.6 kgf / mm ² . However, although such particles have good elongation and feel, they are not yet satisfactory, and particles having both excellent elongation, smoothness, soft feeling and the like have been demanded.

Patent Document 2 discloses a crosslinked (meth) acrylic copolymer obtained by copolymerizing a monomer component containing a monomer having a carboxyl group, and having a surface coated with a surfactant having a sulfonic acid group or a sulfonic acid group. Acid ester resin particles are disclosed. Although the resin particles had good smoothness and smoothness, they were not satisfactory in dispersibility in a hydrophobic medium.
JP 2000-302624 A JP 2006-8980 A

  The object of the present invention is to provide resin particles that impart not only elongation and smoothness, but also a smooth feel to the cosmetics, and that have a smoothness and a smooth feeling by the particles alone, particularly resin particles that have good dispersibility in a hydrophobic medium, And a method for producing the resin particles, and a cosmetic containing the resin particles.

  In the present invention, at least one monomer selected from an acrylic ester and a methacrylic ester (hereinafter referred to as (meth) acrylic ester) and a monomer component containing a monomer having a carboxyl group are copolymerized. Cross-linked (meth) acrylate resin particles, wherein at least a part of the surface is coated with a surfactant represented by the general formula (1) (hereinafter referred to as surfactant (1)), and further the surface Provided are resin particles in which at least a part thereof is coated with a surfactant having a sulfonic acid group or a sulfonic acid group (hereinafter referred to as sulfonic acid (salt) group), a method for producing the same, and a cosmetic containing the resin particles To do.

[Wherein, R ¹ is a monovalent hydrocarbon group having 8 to 23 carbon atoms, R ² and R ³ are each independently —OM ¹ (M ¹ is a hydrogen atom or a cation) or —O (AO) _n —R. ¹ is a group represented by ¹ , A is an alkylene group having 2 to 4 carbon atoms, n is a number of 0 to 40 indicating the average number of moles added of the oxyalkylene group, and n A may be the same or different. . ]

  The crosslinked (meth) acrylic acid ester resin particles of the present invention have good dispersibility in a hydrophobic medium and have smoothness and smoothness when used alone, and are included in cosmetics. When used, a cosmetic that exhibits a smooth and smooth use feeling can be provided.

[Resin particles]
The resin particles of the present invention are obtained by copolymerizing at least one monomer selected from (meth) acrylic acid esters and a monomer component containing a monomer having a carboxyl group, and at least a part of the surface. Are cross-linked (meth) acrylic ester resin particles coated with a surfactant (1).

The (meth) acrylic acid ester used in the present invention is preferably an alkyl (meth) acrylate having an alkyl group having 1 to 18 carbon atoms. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate , Stearyl (meth) acrylate and the like. Among these, alkyl (meth) acrylates having 4 to 18 carbon atoms in the alkyl group such as butyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate are particularly preferable. You may use these in combination of multiple types. 30-98 mass% is preferable and, as for the ratio of the (meth) acrylic acid ester in all the monomer components, 50-85 mass% is more preferable.
In the present specification, “(meth) acryl” is a concept including both acrylic and methacrylic.

  Examples of the monomer having a carboxyl group used in the present invention include (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, and itaconic acid. You may use these in combination of multiple types. The proportion of the monomer having a carboxyl group in all the monomer components is 0.1 to 30 mass from the viewpoint of suppressing the coalescence of particles and obtaining a good powder feel (smoothness, smooth feeling). % Is preferable, and 1 to 10% by mass is more preferable.

  Some of the carboxyl groups contained in the resin particles of the present invention may be neutralized. The base for neutralization is preferably an inorganic base such as sodium hydroxide, potassium hydroxide or ammonia, but organic bases such as amines and basic amino acids can also be used. The degree of neutralization is preferably 0 to 30%, particularly preferably 0 to 20%.

  Here, the degree of neutralization means the ratio of the number of moles of the added base to the number of moles of the carboxyl group of the monomer having a carboxyl group, expressed as a percentage.

  The monomer component of the present invention preferably contains a crosslinkable monomer having two or more vinyl groups as a crosslinking agent.

  Such crosslinkable monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, decaethylene glycol di (meth) acrylate, pentadecaethylene glycol di ( (Meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, (meth) Allyl acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, diethylene glycol di (meth) acrylate phthalate, caprolactone-modified dipentaerythritol hexa (meth) Acrylate, caprolactone-modified hydroxypivalate ester neopentyl glycol di (meth) acrylate, polyester (meth) acrylate, urethane (meth) acrylate and other (meth) acrylate crosslinkable monomers, divinylbenzene, divinylnaphthalene and these And aromatic divinyl monomers such as derivatives thereof. These may be used alone or in combination of two or more. Among these crosslinkable monomers, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4- (Poly) alkylene glycol di (meth) acrylate such as butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified hydroxypivalate ester neo Since pentyl glycol di (meth) acrylate and polyester (meth) acrylate have low skin irritation, they are particularly suitable for applications such as cosmetics. The proportion of these crosslinkable monomers is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass, based on the total amount of monomer components, from the viewpoint of obtaining good smoothness and smooth feeling.

  In the present invention, in addition to the (meth) acrylic acid ester, the monomer having a carboxyl group, and the crosslinkable monomer, other monomers that can be copolymerized therewith within the range not inhibiting the effects of the present invention. Can be copolymerized. Examples of the copolymerizable monomer include styrene, (meth) acrylonitrile, (meth) acrylamide, vinyl acetate, vinyl pyrrolidone, and one-terminal (meth) acryloyl-modified polysiloxane.

  As for the resin particle of this invention, at least one part of the surface is coat | covered with surfactant (1). Thereby, the resin particle which has favorable dispersibility with respect to a hydrophobic medium, and has a smoother and smooth feeling can be obtained. Here, the coating means that it is present on at least a part of the resin particle surface.

In the surfactant (1) used in the present invention, R ¹ is a monovalent hydrocarbon group having 8 to 23 carbon atoms, R ² and R ³ are each independently -OM ¹ (M ¹ is a hydrogen atom or a cation). or -O (AO) _n -R ¹ group represented by, a is an alkylene group having 2 to 4 carbon atoms, n represents shows the number of 0 to 40 showing an average addition mol number of the oxyalkylene group, R ¹ Is preferably an alkyl group having 8 to 23 carbon atoms or an alkylaryl group, more preferably an alkyl group having 8 to 23 carbon atoms or a monoalkyl (2 to 17 carbon atoms) phenyl group, and an alkyl group having 8 to 23 carbon atoms. Is more preferable. As A, a C2-C3 alkylene group is preferable and an ethylene group is more preferable. Moreover, you may have both an ethylene group and a propylene group. n is preferably 1 to 34, more preferably 2 to 12, and still more preferably 2 to 6. Examples of the cation represented by M ¹ include cations such as alkali metal, ammonium, alkyl or alkenylamine having 1 to 22 carbon atoms, alkanolamine having 1 to 22 carbon atoms, and basic amino acid, lithium, sodium, Alkali metal ions such as potassium are preferred, and sodium ions are particularly preferred.

The surfactant (1) may be any of phosphoric acid monoester, phosphoric acid diester, phosphoric acid triester, or a mixture thereof, but in the case of phosphoric acid diester or phosphoric acid triester, it is bonded to a phosphorus atom. The two or three groups represented by —O (AO) _n —R ¹ are preferably the same group.

Examples of the surfactant (1) include polyoxyethylene nonylphenyl ether phosphate, polyoxyethylene octylphenyl ether phosphate, polyoxyethylene tridecyl ether phosphate, polyoxyethylene cetyl ether phosphate, polyoxyethylene lauryl ether. Phosphoric acid, polyoxyethylene dinonyl phenyl ether phosphoric acid, polyoxyethylene-2-ethylhexyl ether phosphoric acid, polyoxyethylene distyrenated phenyl ether phosphoric acid, polyoxyethylene octadecyl ether phosphoric acid, polyoxyethylene octadodecyl ether phosphorous acid, polyoxyethylene dodecyl phenyl ether phosphate, dicetyl, dilauryl phosphate, 2-hexyl decyl arginine neutralized product, polyoxyethylene-flop Etc. pyrene octyl ether phosphate.
Some of these are sold as a mixture of phosphoric acid, phosphoric acid monoester, phosphoric acid diester, and phosphoric acid triester, but the weight mixing ratio of phosphoric acid / monoester / diester / triester is arbitrary. Can be used. Some of these may be neutralized.

  Surfactant (1) may be added before copolymerization of the monomer component, or may be added after copolymerization of the monomer component. Moreover, you may add to the resin particle obtained by copolymerizing a monomer component and drying further.

  The proportion of the surfactant (1) in the resin particles of the present invention is 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin particles from the viewpoint of obtaining good dispersibility in a hydrophobic medium and a feeling of use. Is preferable, 1-30 mass parts is more preferable, and 2-20 mass parts is especially preferable.

  It is preferable that at least a part of the surface of the resin particles of the present invention is coated with a surfactant having a sulfonic acid (salt) group, from the viewpoint of obtaining smoother and smoother resin particles.

  Examples of the surfactant having a sulfonic acid (salt) group include those described in paragraph Nos. 0032 to 0036 of JP-A No. 2003-146826. Among them, an alkyl or alkenyl ether sulfonic acid or a salt thereof, which has an alkyl group or alkenyl group having 5 to 30 carbon atoms and may be added with an average of 0.5 to 25 mol of alkylene oxide in one molecule, and carbon Acylated taurine having an alkyl group or alkenyl group of 5 to 30 or a salt thereof is preferable, and a compound represented by the following general formula (2) is particularly preferable.

R ⁴ CONR ⁵ CH ₂ CH ₂ SO ₃ M ² (2)
[Wherein, R ⁴ represents an optionally substituted alkyl group or alkenyl group having 5 to 30 carbon atoms, R ⁵ represents a hydrogen atom or a methyl group, and M ² represents a hydrogen atom or a cation. ]
In the general formula (2), R ⁴ is preferably an alkyl group or alkenyl group having 6 to 24 carbon atoms. Specific examples include hexyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl, eicosenyl and the like. Examples of the substituent for the alkyl group or alkenyl group include a hydroxyl group, a carboxyl group, an ester group, an ether group, and an amide group.

Examples of the cation represented by M ² include the same cations as the cation represented by M ¹ described above. Alkali metal ions such as lithium, sodium and potassium are preferred, and sodium ions are particularly preferred.

  The ratio of the surfactant having a sulfonic acid (salt) group in the resin particles of the present invention is preferably 0.01 to 50 parts by mass, more preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the resin particles. Preferably, 0.1-5 mass parts is especially preferable.

  The method for producing the resin particles of the present invention is not particularly limited. For example, the resin particles obtained by copolymerizing a (meth) acrylic acid ester and a monomer component containing a monomer having a carboxyl group are bonded to the interface. A method comprising a step of contacting an activator (1) (hereinafter referred to as method 1), a surfactant (1) as a dispersant, a (meth) acrylic acid ester and a monomer comprising a monomer having a carboxyl group And a method of copolymerizing body components (hereinafter referred to as method 2).

  The polymerization can be carried out by a method such as aqueous suspension polymerization, emulsion polymerization, seed polymerization, or dispersion polymerization. From the viewpoint that resin particles can be easily obtained, aqueous suspension polymerization is preferred.

  The aqueous suspension polymerization is performed by mixing the phase containing the monomer and the aqueous phase and then raising the temperature while stirring. In this case, in the above method (1), it is preferable to perform copolymerization using a surfactant having a sulfonic acid (salt) group as a dispersant, and in method (2), the surfactant (1) is used as a dispersant. Copolymerize. In the method (1), the surfactant (1) is added to the dispersion of resin particles after polymerization, and the surfactant (1) is brought into contact with the resin particles. Although the temperature of the dispersion liquid at the time of making it contact is not specifically limited, 0-100 degreeC is preferable and 10-90 degreeC is more preferable.

  Thereafter, by removing the solvent, the surfactant (1) or the surfactant having the surfactant (1) and the sulfonic acid (salt) group can be coated on the surface of the resin particles.

  Further, the contact with the surfactant (1) can be performed in the aqueous dispersion as described above, or in contact with the dried powder after drying. Drying may be performed by freeze-drying or by heating. Although the temperature at the time of drying is not specifically limited, 0-300 degreeC is preferable and 20-200 degreeC is more preferable. Although the temperature at the time of adding surfactant (1) to the powder obtained by drying is not specifically limited, 0-100 degreeC is preferable and 10-90 degreeC is more preferable.

Examples of the polymerization initiator used for the polymerization include benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate, cumene hydroperoxide, t-butyl hydroperoxide and the like. And oil-soluble azo compounds such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile). The addition amount of the polymerization initiator is preferably 0.1 to 10% by mass with respect to the total amount of the monomer mixture.
The polymerization temperature and the polymerization time are not particularly limited, but the polymerization temperature is preferably 40 to 100 ° C. and the polymerization time is preferably 1 to 15 hours.

  The average particle size of the resin particles of the present invention is preferably 1 μm or more, more preferably 1.5 μm or more, from the viewpoint of reducing squeaky feeling. On the other hand, 10 μm or less is preferable, 8 μm or less is more preferable, and 6 μm or less is more preferable from the viewpoint of suppressing the roughness and further improving the skin fixing property.

  The average particle size was measured by using a laser diffraction type particle size distribution measuring device (for example, LA-920 manufactured by Horiba, Ltd.), and the water suspension of particles was weighted at a relative refractive index of 1.1 at room temperature (20 ° C.) It can be determined by measuring the average particle size.

  The average particle diameter of the resin particles can be appropriately determined by controlling the mixing conditions and stirring conditions of the monomer and water, and the composition and amount of the dispersant. Control of mixing conditions and stirring conditions is, for example, using a homogenizer, an emulsifying disperser using a high shear applied to the gap between the rotating blades and the vessel wall or the rotating blades, or using an ultrasonic disperser, It can be carried out by pressurizing an aqueous monomer solution through a ceramic microporous membrane and pressing it into a dispersion medium.

  The shape of the resin particles of the present invention is preferably a spherical body because the feel on the skin is good.

[Cosmetics]
In the cosmetic of the present invention, the content of the crosslinked (meth) acrylic ester resin particles of the present invention can be appropriately selected according to the purpose of the cosmetic and is not particularly limited. .1 to 50% by mass is preferable, and 1 to 30% by mass is more preferable.

  The form of the cosmetic of the present invention is not particularly limited, and any of emulsified cosmetics, aqueous cosmetics, sheet cosmetics, spray cosmetics, stick cosmetics, gel cosmetics and the like may be used. Further, the type of the cosmetic of the present invention is not particularly limited, for example, pack, foundation, lotion, cold cream, hand cream, softening cosmetic, nutritional cosmetic, astringent cosmetic, whitening cosmetic, wrinkle improving cosmetic, aging Skin cosmetics such as prevention cosmetics, antiperspirants, deodorants, oil absorbing agents; hair cosmetics such as hair styling agents and hair nourishing agents.

  Since the resin particles of the present invention are uniformly dispersed in a hydrophobic medium, the cosmetic of the present invention is preferably a cosmetic containing a hydrophobic medium. The hydrophobic medium is not particularly limited, and examples thereof include silicone oils such as dimethyl silicone, decamethylcyclopentasiloxane, and methylphenyl silicone; hydrocarbons such as squalane and liquid paraffin; glycerin, 1,3-butylene glycol, 1, Polyhydric alcohols such as 4-butylene glycol; branched fatty acids; branched alcohols such as isopropyl alcohol and 2-ethylbutyl alcohol; fatty acid esters such as myristyl myristate, isopropyl myristate, isopropyl palmitate, and neopentyl glycol dicaprate Examples: Diglycerides such as glyceryl myristate isostere; triglycerides such as triglyceride isostearate and coconut oil fatty acid triglyceride. In the case of spray cosmetics, for example, Freon gas such as Freon 134a and Freon 113, hydrocarbon gas such as propane, isobutane and isopentane, liquefied gas such as dimethyl ether, carbon dioxide gas, nitrogen gas and the like can be mentioned.

  In the cosmetic of the present invention, other components generally used as cosmetic ingredients can be appropriately blended according to the form, type, etc. of the cosmetic as long as the effects of the present invention are not impaired.

  Examples of such cosmetic ingredients include extender pigments such as mica, talc, sericite, kaolin, nylon powder, polymethylsilsesquioxane, and barium sulfate; inorganic pigments such as titanium oxide, zinc white, and iron oxide; these powders Hydrophobized powder such as silicone treatment; hydrocarbons such as solid paraffin, microcrystalline wax, petrolatum, ceresin, ozokerite, montan wax; higher grades such as cetyl alcohol, stearyl alcohol, palmityl alcohol, hexyl decyl alcohol Alcohols; feel-improving agents such as cationized cellulose and carboxybetaine type polymers; whitening agents, analgesic / anti-inflammatory agents, antipruritics, bactericidal / disinfecting agents, astringents, emollients, hormones, and other medicinal ingredients; water; surfactants W / O or O / W type emulsifier; Octylmethyl Cyclic silicone such as tetrasiloxane and dodecamethylcyclohexasiloxane, chain silicone such as dimethylpolysiloxane and methylphenylpolysiloxane, amino-modified silicone, polyether-modified silicone, methylphenylpolysiloxane, fatty acid-modified silicone, alcohol-modified silicone, alkoxy Silicone compounds such as modified silicone, epoxy-modified silicone, fluorine-modified silicone, alkyl-modified silicone, polyether / alkyl-modified silicone, and glyceryl ether-modified silicone; Viscosity agent: Other, emulsification stabilizer, chelating agent, UV protection agent, pH adjuster, preservative, pigments, fragrance, etc. It is.

Example 1
In a beaker, 164 g of lauryl methacrylate (LMA), 30 g of ethylene glycol dimethacrylate (EGDMA), 6 g of methacrylic acid (MAA), and 6 g of lauroyl peroxide were mixed and stirred to dissolve. To this, 300 g of ion-exchanged water in which 1.0 g of sodium N-stearoyl-N-methyltaurine (SMT) was dissolved was added and dispersed with a homomixer until the particle size became 2.2 μm.

  The dispersion was poured into a four-necked flask and purged with nitrogen for 30 minutes while stirring. The temperature inside the flask was heated to 70 ° C. with an oil bath, and after heating for 30 minutes after reaching 70 ° C., the temperature inside the flask was heated to 80 ° C. Heating was performed for hours. Neutralization was performed by dropping 3.5 g of 1N NaOH into the dispersion at 80 ° C., and SPE-104NB [manufactured by Kao Corporation, polyoxyethylene (average added mole number of oxyethylene group 4 (hereinafter referred to as 4EO) )) 30 g of sodium lauryl ether phosphate (monoester: diester = 40: 60 (mass ratio))] was added, and the mixture was further heated for 2.5 hours. Then, it cooled to room temperature and obtained the resin particle dispersion. The resin particle dispersion was freeze-dried to obtain resin particles.

Example 2
In a beaker, 144 g of LMA, 50 g of EGDMA, 6 g of MAA, and 6 g of lauroyl peroxide were charged and mixed to dissolve. To this, 300 g of ion-exchanged water in which 0.8 g of SMT was dissolved was added and dispersed with a homomixer until the particle size became 2.0 μm.

  The dispersion was poured into a four-necked flask and purged with nitrogen for 30 minutes while stirring. The temperature inside the flask was heated to 70 ° C. with an oil bath, and after heating for 30 minutes after reaching 70 ° C., the temperature inside the flask was heated to 80 ° C. Heating was performed for hours. To this 80 ° C. dispersion, Hostafat KW340D [manufactured by Clariant Japan, polyoxyethylene (4EO) cetyl ether phosphoric acid (phosphoric acid: monoester: diester: triester = 15: 10: 50: 25 (mass ratio)) )] 20 g was added and further heated for 2.5 hours. Then, it cooled to room temperature and obtained the resin particle dispersion. The resin particle dispersion was freeze-dried to obtain resin particles.

Example 3
Instead of hosta fat KW340D, MEP08-PEL [manufactured by Kao Corporation, polyoxyethylene (4EO) polyoxypropylene (30PO) octyl ether phosphate (phosphoric acid: monoester: diester = 1: 79: 20 (mass ratio) ))] Resin particles were obtained in the same manner as in Example 2 except that 300 g of water in which 20 g and 0.96 g of 1N NaOH were dissolved was used.

Example 4
Example 2 except that the amount of SMT is 0.6 g, and 20 g of DAP-60H (manufactured by Kao Corporation, dicetyl phosphate) and 300 g of water in which 9.1 g of 1N NaOH is dissolved are used instead of Hosta Fat KW340D. Similarly, resin particles were obtained.

Example 5
Example 4 except that 20 g of MAP-16G-ARG (manufactured by Kao Corporation, neutralized 2-hexyldecylarginine phosphate) was used instead of 300 g of water in which 20 g of DAP-60H and 9.1 g of 1N NaOH were dissolved. In the same manner, resin particles were obtained.

Reference example 1
In a beaker, 164 g of LMA, 30 g of EGDMA, 6 g of MAA, and 6 g of lauroyl peroxide were charged, mixed and stirred to dissolve. To this, 300 g of ion-exchanged water in which 1.0 g of SPE-104NB was dissolved was added and dispersed with a homomixer until the particle size became 2.2 μm.

  The dispersion was poured into a four-necked flask and purged with nitrogen for 30 minutes while stirring. Heat the temperature inside the flask to 70 ° C with an oil bath, and after heating for 30 minutes after reaching 70 ° C, heat the temperature inside the flask to 80 ° C and heat for 4 hours after reaching 80 ° C. Went. Then, it cooled to room temperature and obtained the resin particle dispersion. The resin particle dispersion was freeze-dried to obtain resin particles.

Comparative Example 1
A dispersion having a particle size of 2.2 μm was obtained in the same manner as in Example 1. This dispersion was poured into a four-necked flask and purged with nitrogen for 30 minutes while stirring. Heat the temperature inside the flask to 70 ° C with an oil bath, and after heating for 30 minutes after reaching 70 ° C, heat the temperature inside the flask to 80 ° C and heat for 4 hours after reaching 80 ° C. Went. Thereafter, the mixture was cooled to room temperature, and 3.5 g of 1N NaOH was added dropwise to the dispersion of polymerized particles to neutralize it to obtain a resin particle dispersion. The resin particle dispersion was freeze-dried to obtain resin particles.

Comparative Example 2
Resin particles were obtained in the same manner as in Example 1 except that 30 g of Rheodor Super TW-L120 (manufactured by Kao Corporation, polyoxyethylene (20EO) coconut oil fatty acid sorbitan) was used instead of SPE-104NB.

Comparative Example 3
Resin particles were obtained in the same manner as in Example 1 except that 30 g of Rheodor Super TW-S120 (manufactured by Kao Corporation, polyoxyethylene (20EO) sorbitan monostearate) was used instead of SPE-104NB.

  The compositions of the resin particles of Examples 1 to 7 and Comparative Examples 1 to 3 are summarized in Table 1. Moreover, the average particle diameter of these resin particles was measured by the following method, and the dispersibility in a hydrophobic medium and the feel on the skin were evaluated by the following methods. These results are shown in Table 1.

<Method for measuring average particle diameter of resin particles>
Using a Horiba, Ltd. laser diffraction scattering particle size distribution analyzer (model number: LA920), the relative refractive index is 1.10 (the refractive index of the resin particles is 1.46, the refractive index of water is 1.33). And the median diameter when the particle diameter was measured was defined as the average particle diameter.

<Method for evaluating dispersibility in hydrophobic media>
3 g of each resin particle, 0.05 g of polyoxyethylene / methylpolysiloxane copolymer (KF-6015 manufactured by Shin-Etsu Chemical Co., Ltd.) and 1.5 g of isopropyl palmitate are uniformly mixed, and the resulting mixture is used as an aerosol pressure-resistant glass container. And then filled with 95.45 g of LPG to obtain a spray. The dispersion state of the particles in the spray was observed, and the dispersibility was evaluated in four stages according to the following criteria. Further, in order to evaluate dispersibility in more detail, a 10-step evaluation was performed according to the following criteria.
-Four-stage evaluation criteria 4-Particles are uniformly dispersed after 2 days of mixing 3-Particle aggregates can be confirmed after 2 days of mixing. In addition, when the ultrasonic treatment is performed for 15 minutes immediately after mixing, the particles are uniformly dispersed 2... Particle agglomerates can be confirmed after 2 days of mixing. In addition, particle agglomerates can be confirmed even if the ultrasonic treatment is performed for 15 minutes immediately after mixing, but further, particle agglomerates can be confirmed after 1 day of mixing, which is dispersed after 14 days. In addition, particle agglomerates can be confirmed even after ultrasonic treatment for 15 minutes immediately after mixing, and agglomerates can be confirmed after 14 days.

・ 10-level evaluation criteria
10: Particles are uniformly dispersed immediately after mixing 9 ... Particles are uniformly dispersed after 1 day of mixing 8 ... Particles are uniformly dispersed after 2 days of mixing 7 ... Aggregation of particles after 2 days of mixing Things can be confirmed. In addition, when the ultrasonic treatment is performed for 15 minutes immediately after mixing, the particles are uniformly dispersed 6... Aggregation of particles can be confirmed after 2 days of mixing. In addition, particle agglomerates can be confirmed even if the ultrasonic treatment is performed for 15 minutes immediately after mixing, but the particles are further dispersed after 1 day 5... In addition, particle agglomerates can be confirmed even if the sonication is performed for 15 minutes immediately after mixing, but further dispersed after 2 days 4... In addition, particle agglomerates can be confirmed even if the sonication is performed for 15 minutes immediately after mixing, but further dispersed after 5 days 3... In addition, particle agglomerates can be confirmed even if the sonication is performed for 15 minutes immediately after mixing, but further dispersed after 7 days 2... Particle agglomerates can be confirmed after 2 days of mixing. In addition, particle agglomeration can be confirmed even if sonication is performed for 15 minutes immediately after mixing, but the particles are further dispersed after 14 days.
1 ... Aggregates of particles can be confirmed after 2 days of mixing. In addition, particle agglomerates can be confirmed even after ultrasonic treatment for 15 minutes immediately after mixing, and agglomerates can be confirmed after 14 days.

<Skin feel evaluation method>
3 g of each resin particle, 0.05 g of polyoxyethylene / methylpolysiloxane copolymer (KF-6015 manufactured by Shin-Etsu Chemical Co., Ltd.) and 1.5 g of isopropyl palmitate are uniformly mixed, and the resulting mixture is used as an aerosol pressure-resistant glass container. And then filled with 95.45 g of LPG to obtain a spray. An appropriate amount of spray was uniformly applied to the upper arm, and the smoothness and smoothness were subjected to sensory evaluation, and scored according to the following criteria.

・ Smoothness Evaluation Criteria 5 ... very smooth 4 ... smooth 3 ... slightly smooth 2 ... slightly rough 1 ... gritty 0 ... very gritty ・ Smoothness Evaluation Criterion 5 ... very smooth 4 ... smooth 3 ... smooth 2 ... Somewhat wet 1 ... Wet 0 ... Very wet

Note) Abbreviations in the table have the following meanings.
LMA: lauryl methacrylate EGDMA: ethylene glycol dimethacrylate MAA: methacrylic acid SMT: N-stearoyl-N-methyltaurine sodium surfactant (1-1): SPE-104NB (manufactured by Kao Corporation)
Surfactant (1-2): Hosta Fat KW340D (manufactured by Clariant Japan)
Surfactant (1-3): MEP08-PEL (manufactured by Kao Corporation)
Surfactant (1-4): DAP-60H (manufactured by Kao Corporation)
Surfactant (1-5): MAP-16G-ARG (manufactured by Kao Corporation)
Surfactant (1-6): TEP-2 (manufactured by Kao Corporation)
Surfactant (1'-1): Rheodor Super TW-L120 (manufactured by Kao Corporation)
Surfactant (1′-2): Rheodor Super TW-S120 (manufactured by Kao Corporation)

Example 8: Spray cosmetics 3 g of the resin particles obtained in Example 1, 0.05 g of a polyoxyethylene / methylpolysiloxane copolymer (KF-6015 manufactured by Shin-Etsu Chemical Co., Ltd.), and 1.5 g of isopropyl palmitate are uniformly added. After the mixture was packed in a pressure-resistant glass container for aerosol, LPG 95.45 g was filled to obtain a spray cosmetic. An appropriate amount of spray-like cosmetic was uniformly applied to the upper arm of five professional panelists, and sensory evaluation was performed. As a result, all five persons obtained a smooth and smooth feel.

Claims (3)

Resin particles obtained by copolymerizing at least one monomer selected from acrylic acid ester and methacrylic acid ester, a monomer component containing a monomer having a carboxyl group , and a crosslinkable monomer comprising contacting a surfactant represented by general formula (1), cross-linked (meth) preparation of acrylate resin particles.

[Wherein, R ¹ is a monovalent hydrocarbon group having 8 to 23 carbon atoms, R ² and R ³ are each independently —OM ¹ (M ¹ is a hydrogen atom or a cation) or —O (AO) _n — The group represented by R ¹ , A is an alkylene group having 2 to 4 carbon atoms, n is a number of 0 to 40 indicating the average number of moles added of the oxyalkylene group, and n A's may be the same or different. good. ]   The manufacturing method of Claim 1 whose ratio of surfactant (1) in bridge | crosslinking (meth) acrylic acid ester-type resin particle is 2-50 mass parts with respect to 100 mass parts of resin particles. The process according to claim 1 or 2 , wherein copolymerization is performed using a surfactant having a sulfonic acid group or a sulfonic acid group as a dispersant.