KR20100015442A - Acrylic hollow particles, process for production of the particles, and cosmetics containing the particles - Google Patents

Abstract

The invention aims at providing acrylic hollow particles which can be produced at a far lower cost than that of nylon particles and which exhibit softness, moistness, and spreadability which are equivalent or near to those of nylon particles; a process for the production of the particles; and cosmetics containing the particles. Acrylic hollow particles made from both a copolymer of a non-crosslinking (meth)acrylate ester monomer (A-1) which can give a homopolymer having a glass transition temperature of 50°C or below and a monomer (A-2) having two or more unsaturated double bonds and a (meth)acrylic polymer (B), characterized in that the copolymer comprises 45 to 90wt% of the monomer (A-1) and 10 to 55wt% of the monomer (A-2) and that the openings of the particles are formed in prescribed sizes; a process for the production of the acrylic hollow particles; and cosmetics containing the particles.

Description

ACRYLIC HOLLOW PARTICLES, PROCESS FOR PRODUCTION OF THE PARTICLES, AND COSMETICS CONTAINING THE PARTICLES}

The present invention relates to an acrylic hollow particle, a method for producing acrylic hollow particle, and a cosmetic containing the particle. More specifically, the present invention relates to acrylic hollow particles having a hole of a predetermined size and capable of obtaining a texture close to nylon particles, a method for producing acrylic hollow particles, and a cosmetic containing the particles.

Cosmetic particles, such as foundation, are nylon particles, acrylic particles, for the purpose of imparting functions such as softness, moistness, spreadability, and spreading on the skin. Particles, such as a urethane particle and polyethylene particle, are mix | blended. Among these particles, nylon particles are most excellent in terms of softness, moistness, and spreadability. However, since the nylon particles for cosmetics are produced by treating cyclic lactam with a specific solution precipitation method in the presence of an alkali polymerization catalyst (see Patent Document 1, for example), the production cost is much higher than that of acrylic particles. high. Therefore, the cosmetics which can mix | blend a nylon particle are limited to the high quality goods of high price.

On the other hand, acrylic particles are used in general cosmetics because they have excellent applicability and are cheaper than nylon particles. However, there is a drawback that the softness and moisture are considerably inferior to the nylon particles, but various improvements have recently been proposed. Patent Literature 2 discloses an application property of a porous resin fine particle composed of a predetermined crosslinked (meth) acrylic acid ester-based resin by blending a fine particle having a predetermined compressive strength and a recovery rate with an external agent. It is described that the feel is excellent. However, according to the experiment conducted by the present inventors, it was confirmed that the porous resin fine particles described in Patent Document 2 cannot obtain the softness and moisture of the nylon particle level.

In addition, Patent Document 3 describes hollow fine particles composed of a mixture of a polymer of a polyfunctional monomer and a polymer of a monofunctional monomer, and a simple manufacturing method thereof. However, the hollow fine particles described in Patent Literature 3 are used for assisting in dispersing fine powder in a medium, and have not been described as excellent in softness, moistness, and spreadability as hollow particles for cosmetics. not.

Patent Document 1: Japanese Patent Application Publication No. 47-25157

Patent Document 2: Japanese Unexamined Patent Publication No. 2002-265529

Patent Document 3: Japanese Patent Application Laid-Open No. 2005-232426

(Challenge to be solved)

In view of the above circumstances, the present inventors have made a thorough examination in order to provide acrylic hollow particles that solve the above-mentioned various drawbacks, and have therefore completed the present invention. That is, an object of the present invention, acrylic hollow particles which can be produced much cheaper than nylon particles, and have a softness, moistness and spreadability equivalent to or close to those of nylon particles, a method for producing the particles, and a cosmetic containing the particles. To provide.

(Solution solution)

1st invention is a copolymer of the non-crosslinkable (meth) acrylic acid ester monomer (A-1) whose glass transition temperature of a homopolymer is 50 degrees C or less, and the monomer (A-2) provided with two or more unsaturated double bonds, and As an acrylic hollow particle which consists of a (meth) acrylic-type polymer (B),

45-90 weight% of non-crosslinkable (meth) acrylic acid ester monomers (A-1) whose glass transition temperature of the said homopolymer is 50 degrees C or less, and the monomers (A-2) which have two or more said unsaturated double bonds are 10- Copolymerized in a proportion of 55% by weight,

The acrylic hollow particles have a hollow core and an outer shell,

The outer diameter α of the shell of the acrylic hollow particles is 3 to 10 μm,

The ratio {(α) / (β)} of the outer diameter α of the shell to the diameter β of the core is 1.1 to 3.5,

The shell is formed with two or more holes through the core,

The maximum hole diameter (gamma) is 0.3-2.5 micrometers among the said 2 or more holes,

The ratio {(β) / (γ)} of the diameter β of the core and the maximum hole diameter γ is 1.1 to 25.0, wherein the acrylic hollow particles are present.

Further, the second invention is a non-crosslinkable (meth) acrylic acid ester monomer (A-1) having a glass transition temperature of 50 ° C. or less, a monomer (A-2) having two or more unsaturated double bonds, and a polymerization initiator (C ) And an aqueous medium (D) are mixed and stirred to prepare an aqueous dispersion,

Subsequently, the obtained aqueous dispersion was mixed and stirred with a seed particle dispersion obtained by dispersing a separately prepared (meth) acrylic polymer (B) in an aqueous medium, and the glass transition temperature of the homopolymer contained in the aqueous dispersion was 50 ° C. or less. The (meth) acrylic-type polymer (B) is made to absorb the monomer (A-2) which has a (meth) acrylic acid ester monomer (A-1) and two or more unsaturated double bonds,

Subsequently, the aqueous dispersion containing the obtained (meth) acrylic polymer was heated, and the non-crosslinkable (meth) acrylic acid ester monomer (A-1) having a glass transition temperature of 50% or less of the homopolymer and two unsaturated double bonds were obtained. As a manufacturing method of the acrylic hollow particle obtained by copolymerizing the monomer (A-2) provided above,

45-90 weight% of non-crosslinkable (meth) acrylic acid ester monomers (A-1) whose glass transition temperature of the said homopolymer is 50 degrees C or less, and the monomers (A-2) which have two or more said unsaturated double bonds are 10- Copolymerized in a proportion of 55% by weight,

The obtained acrylic hollow particle is provided with a hollow core and an outer shell,

The outer diameter (alpha) of the shell of the obtained acrylic hollow particle is 3-10 micrometers,

The ratio {(α) / (β)} of the outer diameter α of the shell to the diameter β of the core is 1.1 to 3.5,

The shell is formed with two or more holes through the core,

The maximum hole diameter (gamma) is 0.3-2.5 micrometers among the said 2 or more holes,

A ratio {(β) / (γ)} of the diameter β of the core and the maximum hole diameter γ is 1.1 to 25.0, wherein the acrylic hollow particles are produced.

(Effects of the Invention)

This invention can obtain especially the following outstanding effect, and its industrial use value is very large.

1. The acrylic hollow particles according to the present invention can be blended into various cosmetics as well as high-quality cosmetics because the production cost is much lower than that of the nylon particles.

2. Acrylic hollow particles according to the present invention is a copolymer of a non-crosslinkable (meth) acrylic acid ester monomer having a glass transition temperature of 50 ° C. or less with a monomer having two or more unsaturated double bonds in a specific ratio, as a main component. In addition, since a hole having a predetermined size is provided, a soft feeling and a moisture equivalent to that of the nylon particles are provided, and a pleasant touch is provided.

3. Since the method for producing acrylic particles according to the present invention does not use a hydrophobic organic solvent, the obtained acrylic hollow particles are hard to cause swelling and fusion of particles even after a long time, and thus long-term stability. This is excellent.

4. Cosmetics containing the acrylic hollow particles according to the present invention have a good feeling because they are excellent in softness, moistness and spreadability.

1 is a SEM image of the acrylic hollow particles prepared in Example 1. FIG.

FIG. 2 is a SEM image of a cross section of the acrylic hollow particles prepared in Example 1. FIG.

The acrylic hollow particle which concerns on this invention is a non-crosslinkable (meth) acrylic acid ester monomer whose glass transition temperature (henceforth Tg) of a homopolymer is 50 degrees C or less. A copolymer of a monomer (A-2) having two or more unsaturated double bonds and a (meth) acrylic ester monomer (A-1) and an (meth) acrylic polymer (B) It is prepared as a main component. In the present invention, (meth) acrylic acid means both acrylic acid and methacrylic acid, and (meth) acrylate means both acrylate and methacrylate. .

<Raw material used for preparation of acrylic hollow particle>

Homopolymer Tg Is below 50 ℃ Non-crosslinking  ( Meta Acrylic Acid Ester Monomer (A-1)

As for the (A-1) component used for this invention, it is essential that Tg of a homopolymer is 50 degrees C or less. When the Tg of the homopolymer exceeds 50 ° C, the obtained acrylic hollow particles are not preferable because they are inferior in softness and moisture.

As an example of the non-crosslinkable (meth) acrylic acid ester monomer whose Tg is 50 degrees C or less, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acryl Acrylic esters such as late; Methacrylic acid ester, such as butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, and 2-ethylhexyl methacrylate, is mentioned. Among these, butyl acrylate is preferable. The non-crosslinkable (meth) acrylic acid ester monomer whose Tg is 50 degrees C or less can be used individually or in combination of 2 or more types.

Moreover, as long as the performance of the acryl hollow particle obtained does not fall, the non-crosslinkable (meth) acrylic acid ester monomer whose Tg of a homopolymer is 50 degrees C or less can be used together, and the copolymerizable monomer can be used together. Examples of the copolymerizable monomers include non-crosslinkable (meth) acrylic acid ester monomers, monovinyl aromatic monomers, vinyl ester monomers, vinyl ether monomers, monoolefin monomers, halogenated olefin monomers having a Tg of homopolymer of more than 50 ° C. Diolefin, acrylic acid, methacrylic acid, etc. are mentioned. The monomer used together can be used individually or in combination of 2 or more types.

As an example of the non-crosslinkable (meth) acrylic acid ester monomer whose Tg of a homopolymer exceeds 50 degreeC, methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, etc. are mentioned. Examples of the monovinyl aromatic monomers include styrene, α-methylstyrene, vinyltoluene, α-chlorostyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, sodium styrene sulfonate, and the like. Examples of the vinyl ester monomers include vinyl formate, vinyl acetate, vinyl propionate and the like. Examples of the vinyl ether monomers include vinyl methyl ether, vinyl ethyl ether, vinyl-n-butyl ether, vinyl phenyl ether and vinyl cyclohexyl ether.

Examples of the monoolefin monomers include ethylene, propylene, butene-1, pentene-1,4-methylpentene-1 and the like. Examples of the halogenated olefin monomers include vinyl chloride and vinylidene chloride. Examples of the diolefins include butadiene, isoprene and chloroprene.

In addition, when using the non-crosslinkable (meth) acrylic acid ester monomer whose Tg of a homopolymer is 50 degrees C or less, and a copolymerizable monomer, Tg of the copolymer obtained should be 50 degrees C or less. In addition, although Tg of a copolymer can be measured by a well-known method, you may calculate from the formula of Fox shown next.

1 / Tg = Σ (Wn / Tgn) / 100

In this formula, Wn represents the weight% of monomer (n), and Tgn represents the Tg of the homopolymer consisting of monomer (n).

With two or more unsaturated double bonds Monomer (A-2)

As (A-2) component used for this invention, it is equipped with 2 or more (especially 2-4) polymerizable C = C double bonds, such as a polyfunctional (meth) acrylic-ester monomer and an aromatic divinyl monomer. Monomers are preferred.

Examples of the polyfunctional (meth) acrylic acid ester monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and decaethylene glycol di (meth) acrylate. Pentadecaethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate , Glycerin di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, diethylene glycol di (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylic Elate, caprolactone modified hydroxy pivaric acid ester neopentyl glycol diacrylate, polyester acrylate, urethane acrylate, etc. are mentioned. The. Examples of the aromatic divinyl monomers include divinylbenzene, divinylbiphenyl, divinylnaphthalene, diarylphthalate and derivatives thereof. The monomer which has two or more of said unsaturated double bonds can be used individually or in combination of 2 or more types.

The component (A-1) and the component (A-2) are copolymerized at a ratio of 45 to 90% by weight of the component (A-1) and 10 to 55% by weight of the component (A-2). If the component (A-2) is less than 10% by weight, particles of the desired shape cannot be obtained. If the component (A-2) is more than 55% by weight, the elasticity of the obtained particles is lowered, softness and moisture are obtained. It is not desirable because it falls. More preferable copolymerization ratio is the ratio of 50-80 weight% of (A-1) component, and 20-50 weight% of (A-2) component.

( Meta Acrylic Polymer (B)

(B) component used for this invention is comprised by the (meth) acrylic-acid alkylester (co) polymer.

As an example of the (meth) acrylic-acid alkylester which can be used as (B) component, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl ( Meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-propyl (meth) acrylate, chloro 2-hydroxyethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, methoxyethyl (meth) acrylate, glycidyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dish Clopentenyl (meth) acrylate, isobornyl (meth) acrylate, etc. are mentioned. These (meth) acrylic-acid alkylester can be used individually or in combination of 2 or more types.

As the component (B), a (meth) acrylic acid alkyl ester and another copolymerizable monomer may be copolymerized, and examples of the other copolymerizable monomers include a styrene monomer, a vinyl monomer, and an unsaturated carboxylic acid monomer.

Examples of styrene monomers copolymerizable with (meth) acrylic acid alkyl esters include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene and heptyl styrene. And alkyl styrenes such as octyl styrene; Halogenated styrenes such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, iodine styrene and chloromethyl styrene; And nitrostyrene, acetyl styrene, methoxy styrene, and the like.

Examples of the vinyl monomers include vinylpyridine, vinylpyrrolidone, vinylcarbazole, vinyl acetate and acrylonitrile; Conjugated diene monomers such as butadiene, isoprene and chloroprene; Vinyl halides such as vinyl chloride and vinyl bromide; Vinylidene halides such as vinylidene chloride, and the like. Moreover, as an unsaturated carboxylic acid monomer, (meth) acrylic acid, (alpha)-ethyl (meth) acrylic acid, crotonic acid, (alpha)-methyl crotonic acid, (alpha)-ethyl crotonic acid, isocrotonic acid, tigrinic acid, and Addition polymerizable unsaturated aliphatic monocarboxylic acids such as angelic acid; Maleic acid, fumaric acid, itaconic acid, itraconic acid, citraconic acid, mesaconic acid, glutaconic acid and hydromuconic acid The addition polymerizable unsaturated aliphatic dicarboxylic acid, etc. are mentioned.

The component (B) is a crosslinked structure obtained by copolymerizing a monomer having two or more unsaturated double bonds in addition to the (meth) acrylic acid alkyl ester and other monomers copolymerizable with the (meth) acrylic acid alkyl ester as necessary. (Iii) may be formed. As a monomer provided with two or more unsaturated double bonds, the monomer described by the said (A-2) component can be used.

As (B) component, when using the copolymer which consists of a (meth) acrylic-acid alkyl ester and the monomer which has two or more unsaturated double bonds copolymerizable with the other monomer copolymerizable with (meth) acrylic-acid alkylester, (meth) acrylic acid It is preferable to copolymerize in the ratio of 0.005-0.05 weight part of monomers which have 0-20 weight part of other monomers copolymerizable with (meth) acrylic-acid alkyl ester, and the monomer which has two or more unsaturated double bonds with respect to 100 weight part of alkyl esters.

In the present invention, the component (B) is a soap-free emulsion polymerization or emulsion polymerization of the above-mentioned (meth) acrylic acid alkyl ester and other monomers copolymerizable with the (meth) acrylic acid alkyl ester, if necessary. It is preferable to prepare seed particles by a polymerization method of an aqueous system such as weight polymerization, suspension polymerization, and seed polymerization. More preferable among these polymerization methods is preparation by soap-free emulsion polymerization which can obtain the particle | grains of narrow particle size distribution.

When preparing a suspension containing seed particles by soap free emulsion polymerization, a polymerization initiator is usually used. The polymerization initiator to be used may be a polymerization initiator soluble in an aqueous medium used for polymerization, and preferable are potassium persulfate and ammonium persulfate. As for the usage-amount of a polymerization initiator, the range of 0.1-10 weight part is preferable with respect to 100 weight part of said monomers used at the time of soap free emulsion polymerization. In addition, any of the aqueous medium (D) mentioned later can be used as an aqueous medium.

In preparing a suspension containing seed particles by emulsion polymerization, an emulsifier and a polymerization initiator are usually used. As an example of the emulsifier used, polyethylene glycol alkyl ethers, such as alkyl benzene sulfonate, such as sodium dodecylbenzene sulfonate, and polyethylene glycol nonyl phenyl ether, etc. are mentioned. It is preferable to use an emulsifier in 0.01-5 weight part with respect to 100 weight part of monomers.

Moreover, as a polymerization initiator used, what is necessary is just a polymerization initiator soluble in the aqueous medium used at the time of superposition | polymerization, Preferably, potassium persulfate and ammonium persulfate are preferable. As for the usage-amount of a polymerization initiator, the range of 0.1-10 weight part is preferable with respect to 100 weight part of said monomers used at the time of soap free emulsion polymerization. In addition, any of the aqueous medium (D) mentioned later can be used as an aqueous medium.

The seed particles prepared by the above method have a spherical spherical shape having an average particle diameter of 0.05 to 2.0 μm, preferably 0.2 to 0.6 μm, and a relative standard deviation (hereinafter abbreviated as CV value) of the particle diameter of 10% or less. It is preferable that they are monodisperse particle | grains of (眞 球狀). In the present invention, seed particles having a small particle diameter prepared as described above may be used as they are, but seed particle polymerization for absorbing a monomer into a seed particle having a small particle diameter and polymerizing the absorbed monomer is performed at least once. , Seed particles having a large particle diameter may be prepared and used.

Seed polymerization for preparing seed particles having a large particle diameter may be performed by mixing an aqueous medium with the seed particles having a small particle diameter, a monomer and a polymerization initiator, and an emulsifier and a dispersion stabilizer as necessary. As a monomer used for seed particle superposition | polymerization, the said (meth) acrylic-acid alkylester which comprises seed particle | grains with small particle diameter, and the other monomer copolymerizable with (meth) acrylic-acid alkylester as needed can be used. The monomer to be used may be the same as or different from the monomer constituting the seed particles having a small particle diameter. Examples of the polymerization initiator used include persulfates such as potassium persulfate and ammonium persulfate, peroxides such as benzoyl peroxide and lauryl peroxide, and azo compounds such as azobisisobutyronitrile. A polymerization initiator may be used individually or in combination of 2 or more types, It is preferable to use in the range of 0.1-10 weight part with respect to 100 weight part of (meth) acrylic-acid alkylesters. In addition, any of an emulsifier (E) and a dispersion stabilizer (F) mentioned later can be used for an emulsifier and a dispersion stabilizer.

In preparation of seed particle | grains, said seed polymerization may be repeated in order to obtain seed particle | grains of a desired particle diameter, and it is 1 to 10 times normally, Preferably it is 1 to 5 times. The seed particles having the desired particle diameter may be seed polymerized by absorbing a monomer using a seed particle having a small particle diameter prepared in one step of polymerization such as soap free emulsion polymerization, and polymerizing the absorbed monomer. Polymerization), and if necessary, the same seed polymerization can be repeated again. As for the average particle diameter of the seed particle finally obtained, the range of 0.7-5.0 micrometers is preferable. In addition, the weight of the seed particles finally obtained is preferably in the range of 2 to 80 times, preferably 5 to 40 times, particularly 10 to 30 times, the seed particles having a small particle diameter prepared in one-step polymerization.

The (B) component prepared by the above-mentioned polymerization method has a gel fraction of 10 to 85% and a weight average molecular weight (hereinafter abbreviated as Mw) of the sol portion of 100,000 to 1,000,000. It is preferable. When the gel fraction of (B) component exceeds 85%, since the acrylic particle finally obtained does not become a predetermined shape, especially hollow shape, it is unpreferable. Moreover, since the acrylic particle finally obtained may become a predetermined shape as Mw of a sol powder exists in the range of 100,000-1,000,000, it is preferable. Moreover, in order for the finally obtained acrylic particle to form a predetermined | prescribed shape, it is preferable that the sol in (B) component has few polymers whose molecular weight is 20000 or less. The gel fraction or Mw can be adjusted by the kind, combination and ratio of the monomers to be used, the kind and blending amount of the polymerization initiator, the kind and blending amount of the emulsifier, the method and conditions of the polymerization and the like. For example, the gel fraction of (B) component can be adjusted with the kind, compounding quantity, etc. of the monomer which has two or more unsaturated double bonds. Moreover, Mw of sol powder can be adjusted with the kind and compounding quantity of a chain transfer agent, the kind and compounding quantity of a polymerization initiator, the conditions of superposition | polymerization, etc.

In addition, in this invention, the gel fraction of (B) component weighs about 0.1 g of samples, and after immersing this in about 50 ml of ethyl acetate for 1 week at room temperature, it is a solvent-insoluble content. The residue was removed, dried at 130 ° C. for about 1 hour, ethyl acetate was evaporated and then weighed, and calculated from the following formula.

Gel fraction (% by weight) = (weight of non-volatile components after immersion and drying) / weight of sample x 100

In the present invention, Mw of the sol powder in the component (B) is approximately 0.1 g of a sample, and after immersing it in about 50 ml of ethyl acetate for 1 week at room temperature, the insoluble content and the sol powder are dissolved acetic acid. The mixture was separated with an ethyl solution, and the ethyl acetate solution in which the sol was dissolved was dried under reduced pressure at 30 ° C. to remove ethyl acetate, followed by a differential refractometer (manufactured by Tosoh Corporation, Model: HLC-8120, Column: HXL- It is the molecular weight of standard polystyrene conversion measured by gel permeation chromatography method (GPC method) using H, G7000HXL, GMHXL-L, G2500HXL).

Polymerization initiator (C)

In this invention, (C) component has a role which starts copolymerization of (A-1) component and (A-2) component in the manufacturing method mentioned later. In the present invention, a known polymerization initiator can be used, but it is preferable to use a peroxide or an azo compound. Examples of the peroxide include potassium persulfate, ammonium persulfate, benzoyl peroxide, lauroyl peroxide, dialkyl perester, and the like.

Examples of azo compounds include 2,2'-azobis (2-methylpropionitrile), 2,2'-azobis (2-methylbutyronitrile) and 2,2'-azobis (2,4- Dimethylvaleronitrile), 2,2'-azobis (2-cyclopropylpropionitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), dimethyl-2,2'-azobis ( 2-methylpropionate) etc. are mentioned. These polymerization initiators can be used individually or in combination of 2 or more types. As for the usage-amount of (C) component in this invention, the range of 0.1-10 weight part is preferable with respect to a total of 100 weight part of (A-1) component and (A-2) component.

Aqueous medium (D)

In the present invention, the component (D) may be a mixture in which a hydrophilic organic solvent is added to water in addition to water. As water, purified water (ion exchange water, distilled water, etc.), groundwater, tap water, etc. are mentioned. As an example of a hydrophilic organic solvent, Lower alcohol, such as methanol, ethanol, isopropanol; Polyhydric alcohols such as ethylene glycol, propylene glycol, butanediol, diethylene glycol and triethylene glycol; Cellosolves such as methyl cellosolve and ethyl cellosolve; Ketones such as acetone; Ethers such as tetrahydrofuran (THF); Ester, such as methyl formate, etc. are mentioned. These hydrophilic organic solvents can be used individually or in combination of 2 or more types. As for the addition amount of a hydrophilic organic solvent, the range of 0.1-10 weight part is preferable with respect to 100 weight part of water.

In the present invention, the aqueous medium (D) may contain an emulsifier (E), a dispersion stabilizer (F) and a polymerization inhibitor (G) as necessary.

Emulsifier (E)

As an example of an emulsifier (E) component in this invention, Alkyl sulfonates, such as sodium dodecyl sulfonate; Alkyl benzene sulfonates such as sodium dodecyl benzene sulfonate; Alpha sulfone fatty acid ester salts such as 2-sulfotetradecanoic acid 1-methyl ester sodium; Polyethylene glycol alkyl ethers such as polyethylene glycol nonylphenyl ether; Salts of polyoxyethylene alkyl ethers, polyoxyethylene polycyclic phenyl ethers, allyl ethers and their sulfate esters; These etc. are mentioned, Among these, sodium dodecyl sulfonate and sodium dodecylbenzene sulfonate are preferable. These emulsifiers can be used individually or in combination of 2 or more types. As for the usage-amount of (E) component in this invention, the range of 0.1-10 weight part is preferable with respect to a total of 100 weight part of (A-1) component and (A-2) component.

Dispersion Stabilizer (F)

Examples of the dispersion stabilizer (F) component in the present invention include polyvinyl alcohol partially saponified (saponified); Fully vinylated polyvinyl alcohol; Polyacrylic acid, its copolymers, and their neutralized products; Polymethacrylic acid, copolymers thereof and neutralizations thereof; Celluloses such as carboxymethyl cellulose and hydroxypropyl methyl cellulose; Polyvinylpyrrolidone, etc. are mentioned. These dispersion stabilizers can be used individually or in combination of 2 or more types. As for the usage-amount of (F) component in this invention, the range of 0.1-5 weight part is preferable with respect to a total of 100 weight part of (A-1) component and (A-2) component.

Polymerization inhibitor (G)

Examples of the polymerization inhibitor (G) component in the present invention include sodium nitrite, hydroquinon, dibutylhydroxytoluene and the like. These polymerization inhibitors can be used individually or in combination of 2 or more types. It is preferable to make the usage-amount of (G) component in this invention contain in 0.01 to 0.5 weight% in (D) component.

<Method for Preparing Acrylic Hollow Particles>

The manufacturing method of the acrylic hollow particle which concerns on this invention is demonstrated.

In the present invention, first, the above-mentioned (A-1) component, (A-2) component, (C) component and (D) component, and (E) component, (F) component, and (G) component are mixed as needed. And stirring to prepare an aqueous dispersion. It is preferable to add (D) component in 80-500 weight part with respect to a total of 100 weight part of (A-1) component and (A-2) component. The method of mixing and stirring the component (A-1), the component (A-2), the component (C) and the component (D) to obtain an aqueous dispersion liquid is a known method using mechanical shear force. According to the present invention, for example, a homomixer, a homogenizer, an emulsion disperser, or an ultrasonic disperser may be used. The temperature at the time of mixing and stirring should just be below the temperature of the grade which (C) component does not decompose by the heat from the surroundings, and 0-30 degreeC is preferable. Moreover, in the manufacturing method of the acrylic hollow particle which concerns on this invention, since a hydrophobic organic solvent is not used, an organic solvent does not remain in the acrylic hollow particle finally obtained, and a particle is hard to fall off. In addition, as a hydrophobic organic solvent, it means non-polymeric organic solvents, such as toluene, ethyl acetate, hexane, 1-chlorododecane, adipic acid, and dioctyl.

Subsequently, the seed particle by the said (B) component prepared separately is thrown into the aqueous dispersion obtained above, The said (A-1) component, (A-2) component, (C) is added to the seed particle by the said (B) component. Absorb the ingredients. It is preferable to introduce | blend the injection amount of the seed particle by (B) component in the range of 1.25-50 weight part with respect to a total of 100 weight part of (A-1) component and (A-2) component.

Subsequently, the aqueous dispersion liquid containing (A) component and (A) component which absorbed (A) component was heated, and the acrylic hollow particle was copolymerized by copolymerizing (A-1) component and (A-2) component. Can be prepared. It is preferable to set the heating temperature at this time in the range of 50-90 degreeC. The obtained acrylic hollow particle can be isolate | separated in aqueous dispersion liquid suitably by well-known methods, such as filtration and dehydration, and can wash and produce it as needed.

<Shape of Acquired Acrylic Hollow Particles>

In the present invention, the obtained acrylic hollow particles have a hollow core and an outer shell, and two or more holes communicating with the core are formed in the shell. The acrylic hollow particles according to the present invention give a softer texture than the solid particles, and absorb oil, absorbency and sustained release of volatile components than hollow particles having only one hole communicating with the core. It is useful as an acrylic hollow particle for cosmetics because of its excellent 徐 放 性. In addition, the dimension of the acrylic hollow particle which concerns on this invention satisfy | fills the following requirements.

Shell outer diameter (α)

In this invention, it is essential that the average particle diameter of acrylic hollow particle obtained, ie, the outer diameter (alpha) of a shell, is 3-10 micrometers. If the outer diameter (alpha) of a shell is less than 3 micrometers, the target hollow shape cannot be obtained, and the obtained acrylic hollow particle | grains will be inferior to application | coating property, and will give a sticky feeling, and it is unpreferable. Moreover, when the outer diameter (alpha) of a shell exceeds 10 micrometers, the acrylic hollow particle obtained is unpreferable because moisture is inferior. The range with preferable outer diameter (alpha) of a shell is 3.5-8.0 micrometers.

Diameter of core (β)

In this invention, it is preferable that the diameter (beta) of the core of the acryl-type hollow particle obtained is 0.5-8.5 micrometers. If the diameter β of the core is less than 0.5 µm, it is difficult to obtain a soft feeling in the particles, which is not preferable. Moreover, when the diameter (beta) of a core exceeds 8.5 micrometers, it is unpreferable because particle | grains fall back and a feeling of use falls. As diameter (beta) of a core, the range with a more preferable range is 1.0-8.0 micrometers.

In the present invention, the ratio {(α) / (β)} between the outer diameter α of the shell and the diameter β of the core is essentially in the range of 1.1 to 3.5. If {(α) / (β)} is less than 1.1, it is not preferable because the particles recede and the feeling of use decreases. Moreover, when {((alpha)) / ((beta)) exceeds 3.5, it is difficult to obtain a soft feeling to particle | grains, and it is unpreferable. The preferred range in {(α) / (β)} is 1.1 to 3.5.

Hole diameter (γ) of the hole through the core

In this invention, it is essential that the largest hole diameter (gamma) is 0.3-2.5 micrometers among two or more holes formed in the obtained acrylic hollow particle and communicate with a core. If the maximum hole diameter (gamma) is in the range of 0.3-2.5 micrometers, it is preferable because it is excellent as oil absorption, water absorption, and sustained release property of a volatile component, and it is useful as acrylic hollow particle for cosmetics. The range with preferable maximum hole diameter (gamma) is 0.4-1.6 micrometers.

In the present invention, the ratio {(β) / (γ)} of the diameter β of the core and the maximum hole diameter γ is required to be in the range of 1.1 to 25.0. When {((beta)) / ((gamma))} exists in the range of 1.1-25.0, since it is excellent in oil absorption, water absorption, and sustained release property of a volatile component, it is preferable as it is an acrylic particle for cosmetics. The preferred range in {(β) / (γ)} is 1.15 to 24.0.

In this invention, the dimension {((alpha)), ((beta), (gamma)) of an acrylic hollow particle is measured by the following method.

(I) The obtained acrylic hollow particle is added to an unreacted epoxy resin, and it embeds.

(II) Next, it is left to stand in the environment of 23 degreeC and 65% RH, and an epoxy resin is hardened.

(III) Subsequently, the cured epoxy resin is frozen.

(IV) The frozen epoxy resin is cut into diamond knife or glass knife to prepare a sample for measurement.

(VI) Next, using a scanning electron microscope (hereinafter abbreviated as SEM), the outer diameter α of the shell of the prepared sample for measurement, the diameter β of the core, and the maximum hole diameter γ passing through the core were determined. It measured and computed the average value of each 10 measured.

The acrylic hollow particle which concerns on this invention is used for cosmetics, a composite particle, an ink additive, a lubricating oil additive, a sintered compact, a laminated adhesive, etc., and is especially suitably used as a compounding component for cosmetics. As cosmetics, Hair cosmetics, such as a barber, a hair dye, a scalp, a hair coloring, a hair coloring, and a hair rinse; Skin cosmetics such as a lotion, a cosmetic liquid, a cream, an emulsion, a face wash, a facial rinse, a pack, and a cosmetic oil; Makeup cosmetics such as foundation, makeup base, powder, lipstick, body powder, eye shadow, eyebrow pencil, teak color, nail enamel, light-treating liquid, etc .; And perfumes, eau de cologne, bath oils, baby oils, baby powders, baby lotions and the like. In addition, the acrylic hollow particle can mix | blend active ingredients, such as a chemical agent, before mix | blending with cosmetics.

(Example)

Although this invention is demonstrated further more concretely based on an Example, this invention is not limited by the following Example, unless the summary is exceeded.

Preparation Example 1 Preparation of Seed Particles

(Polymerization of the first step: soap free emulsion polymerization)

Into a 1 liter four-necked flask equipped with a thermometer and a nitrogen inlet tube, 100 parts by weight of methyl methacrylate (hereinafter abbreviated as MMA) and 300 parts by weight of ion-exchanged water were added, stirred, and stirred under a nitrogen stream. It heated up at 80 degreeC.

Subsequently, 0.5 weight part of potassium persulfate was added to the heated liquid mixture, it was made to react for 6 hours, maintaining at 80 degreeC, and the dispersion liquid (a) of the (meth) acrylic-type polymer particle was obtained. The (meth) acrylic polymer particles in the dispersion (a) were observed by SEM (manufactured by Hitachi High-Technologies Co., Ltd., model: S-4800, the same as below). As a result, the (meth) acrylic polymer particles had an average particle diameter. This 0.4 micrometer and CV value were 2.0-%, spherical monodisperse particles. Moreover, solid content in the dispersion (a) was 24 weight%.

(Polymerization of the second stage: seed polymerization)

In the same apparatus, 100 parts by weight of MMA, 0.02 parts by weight of ethylene glycol dimethacrylate (hereinafter abbreviated as EGDMA), 1.0 part by weight of benzoyl peroxide, 113.2 parts by weight of ion-exchanged water, 0.5 part by weight of sodium dodecylbenzenesulfonate, and 0.1 weight part of sodium nitrate was thrown in, and it mixed and stirred, and obtained the liquid mixture.

Subsequently, 64.2 parts by weight of the dispersion (A) and partially saponified polyvinyl alcohol (product name: PV-420) were dissolved in ion-exchanged water at 5% in this mixed solution. 40 parts by weight of an aqueous solution (hereinafter abbreviated as PVA 5% aqueous solution) was added, and the mixture was slowly stirred, followed by stirring at 75 ° C. for 2 hours to obtain a dispersion (b) of (meth) acrylic polymer particles. SEM observation of the (meth) acrylic polymer particles in the dispersion (b) revealed that the (meth) acrylic polymer particles were spherical monodisperse particles having an average particle diameter of 0.75 µm and a CV value of 2.5%. Moreover, solid content in the dispersion (b) was 30.5 weight%.

(3rd step polymerization: seed polymerization)

In the same apparatus, 5.4 parts by weight of butyl acrylate (hereinafter abbreviated as BA), 94.6 parts by weight of MMA, 0.022 part by weight of EGDMA, 1.1 parts by weight of benzoyl peroxide, 144.3 parts by weight of ion-exchanged water, sodium dodecylbenzenesulfonate 0.55 Part by weight and 0.11 part by weight of sodium nitrite were added and stirred to obtain a mixed liquid.

Subsequently, 27.3 parts by weight of the dispersion (B) obtained by the polymerization in the second step and 43.3 parts by weight of a PVA 5% aqueous solution were added to the mixed solution, and stirred slowly at 75 ° C. for 2 hours, thereby dispersing (meth) acrylic polymer particles ( C)

SEM observation of the (meth) acrylic polymer particles in the dispersion liquid (C) revealed that the (meth) acrylic polymer particles were spherical monodisperse particles having an average particle diameter of 1.7 μm and a CV value of 2.5%. Moreover, solid content in this dispersion (c) was 30.1 weight%, the gel fraction of the obtained (meth) acrylic-type polymer was 65%, and Mw of the sol powder was 400,000.

In addition, the gel fraction of (B) component weighs about 0.1 g of samples, and after immersing this in about 50 ml of ethyl acetate for 1 week at room temperature, removes an insoluble solvent, it is dried at 130 degreeC for about 1 hour, and ethyl acetate is made into After evaporation, it was weighed and calculated from the following equation.

Gel fraction (% by weight) = (weight after immersion and drying) / weight of sample x 100

The Mw of the sol powder in the seed particles is approximately 0.1 g of a sample, which is immersed in about 50 ml of ethyl acetate for 1 week at room temperature, and then separated into an insoluble matter and an ethyl acetate solution in which the sol powder is dissolved, and the sol powder is dissolved. The ethyl acetate solution was dried under reduced pressure at 30 ° C. to remove ethyl acetate, and the GPC method was performed using a differential refractometer (manufactured by Tosoh Co., Ltd., HLC-8120, column: HXL-H, G7000HXL, GMHXL-L, G2500HXL). It is the molecular weight of standard polystyrene conversion measured by.

Preparation Example 2 Preparation of Seed Particles

In the same apparatus, 100 parts by weight of MMA, 0.025 parts by weight of EGDMA, 1.0 part by weight of benzoyl peroxide, 145.5 parts by weight of ion-exchanged water, 0.63 parts by weight of sodium dodecylbenzenesulfonate and 0.13 parts by weight of sodium nitrate were mixed and stirred, and the mixed solution was mixed. Got it. Subsequently, 82.0 weight part of said dispersion liquid (a) and 50 weight part of PVA 5% aqueous solution were added to this liquid mixture, and it stirred slowly, and stirred at 75 degreeC for 2 hours, and obtained the dispersion liquid of (meth) acrylic-type polymer particle (d). . SEM observation of the (meth) acrylic polymer particles in the dispersion (d) revealed that the (meth) acrylic polymer particles were spherical monodisperse particles having an average particle diameter of 1.28 µm and a CV value of 2.7%. Moreover, solid content in dispersion (d) was 30.2 weight%, the gel fraction of the obtained (meth) acrylic-type polymer was 60%, and Mw of sol was 350,000.

Preparation Example 3 Preparation of Seed Particles

In the same apparatus, 100 parts by weight of MMA, 0.025 parts by weight of EGDMA, 1.0 part by weight of benzoyl peroxide, 145.5 parts by weight of ion-exchanged water, 0.63 parts by weight of sodium dodecylbenzenesulfonate and 0.13 parts by weight of sodium nitrate were mixed and stirred, and the mixed solution was mixed. Got it. Subsequently, 82.0 weight part of said dispersion liquid (C) and 50 weight part of PVA 5% aqueous solution were added to this liquid mixture, and it stirred gradually, and stirred at 75 degreeC for 2 hours, and obtained the dispersion liquid of (meth) acrylic-type polymer particle. SEM observation of the (meth) acrylic polymer particles in the dispersion liquid (e) revealed that the (meth) acrylic polymer particles were spherical monodisperse particles having an average particle diameter of 2.9 µm and a CV value of 3.2%. Moreover, solid content in a dispersion liquid (e) was 30.2 weight%, the gel fraction of the obtained (meth) acrylic-type polymer particle was 60%, and Mw of the sol powder was 380,000.

Preparation Example 4 Preparation of Seed Particles

In the same apparatus, 100 parts by weight of MMA, 1.0 part by weight of normal dodecyl mercaptan, 2.0 parts by weight of benzoyl peroxide, 144.5 parts by weight of ion-exchanged water, 0.5 part by weight of sodium dodecylbenzenesulfonate and 0.1 part by weight of sodium nitrite were charged. The mixture was stirred under air flow to obtain a mixed solution. Subsequently, 25.2 weight part of said dispersion liquids (B) and 40 weight part of PVA 5% aqueous solution were added to this liquid mixture, and it stirred slowly, and stirred at 75 degreeC for 2 hours, and obtained the dispersion liquid (bar) of (meth) acrylic-type polymer particle. SEM observation of the (meth) acrylic polymer particles in the dispersion (bar) revealed that the (meth) acrylic polymer particles were spherical monodisperse particles having an average particle diameter of 1.7 μm and a CV value of 2.8%. Moreover, solid content in a dispersion liquid (bar) was 30.2 weight%, the gel fraction of the obtained (meth) acrylic-type polymer particle was 0%, and Mw of the sol powder was 50,000.

Example 1

As a non-crosslinkable (meth) acrylic acid ester monomer (A-1) whose homopolymer Tg is 50 degrees C or less,

110 parts by weight of BA,

As monomer (A-2) which has two or more unsaturated double bonds, 80 weight part of EGDMA,

As polymerization initiator (C), 2.0 weight part of benzoyl peroxides,

As the aqueous medium (D), 263 parts by weight of ion-exchanged water,

1.0 weight part of sodium dodecylbenzenesulfonate as an emulsifier (E)

And

0.2 weight part of sodium nitrites as a polymerization inhibitor (G)

The mixture was stirred at 10,000 rpm for 3 minutes by a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd., Model: TK Homo Mixer MARK II, below).

Subsequently, 33.2 parts by weight of the dispersion liquid (C) prepared in Preparation Example 1 was added to the mixture, and the mixture was slowly stirred at 50 ° C for 30 minutes. Thereafter, 120 parts by weight of a 5% aqueous solution of PVA was added as the dispersion stabilizer (F), the reaction was carried out at 75 ° C for 1.5 hours, and then at 90 ° C for 1 hour. Subsequently, the obtained aqueous dispersion was filtered under reduced pressure with a filter paper using a Buchner funnel, and the cake was dried with a hot air dryer set at 105 ° C to obtain acrylic hollow particles. The obtained acrylic hollow particles were subjected to dimensional measurement and characteristic evaluation by the following method, and the results are shown in Tables 1 and 2.

<Examples 2 to 3, Comparative Examples 1 to 2>

Acrylic hollow particles were obtained in the same manner as in Example 1 except that (A-1) and (A-2) were used as the ratios shown in Table 1. The obtained acrylic hollow particles were subjected to dimensional measurement and characteristic evaluation by the following method, and the results are shown in Tables 1 and 2.

Example 4

Acrylic hollow particles were prepared in the same manner as in Example 1 except that 33.2 parts by weight of the dispersion (D) was added instead of 33.2 parts by weight of the dispersion (C). The obtained acrylic hollow particles were subjected to dimensional measurement and characteristic evaluation by the following method, and the results are shown in Tables 1 and 2.

Example 5

Acrylic particles were prepared in the same manner as in Example 1, except that 33.2 parts by weight of the dispersion (e) was added instead of 33.2 parts by weight of the dispersion (c). The obtained acrylic particles were measured in size and evaluated by the following method, and the results are shown in Tables 1 and 2.

Example 6

Acrylic hollow particles were obtained in the same manner as in Example 1 except that 110 parts by weight of n-butyl methacrylate was added as (A-1). The obtained acrylic hollow particles were subjected to dimensional measurement and characteristic evaluation by the following method, and the results are shown in Tables 1 and 2.

Comparative Example 3

Acrylic particles were prepared in the same manner as in Example 1 except that 33.2 parts by weight of the dispersion (bar) was added instead of 33.2 parts by weight of the dispersion (C). The obtained acrylic particles were measured in size and evaluated by the following method, and the results are shown in Tables 1 and 2.

Comparative Example 4

As a non-crosslinkable (meth) acrylic acid ester monomer (A-1) whose homopolymer Tg is 50 degrees C or less,

100 parts by weight of BA,

As a monomer (A-2) which has two or more unsaturated double bonds, 50 weight part of 1, 6- hexanediol dimethacrylates,

As a hydrophobic organic solvent, 150 parts by weight of n-hexane,

As polymerization initiator (C), 1.0 weight part of benzoyl peroxides,

As the aqueous medium (D), 744 parts by weight of ion-exchanged water,

As emulsifier (E), 0.12 weight part of sodium lauryl sulfate,

480 parts by weight of a PVA 5% aqueous solution as a dispersion stabilizer (F)

And

0.1 weight part of sodium nitrites as a polymerization inhibitor (G)

The mixture was stirred at 6,500 rpm for 3 minutes by a homomixer to obtain a dispersion.

Subsequently, the dispersion was placed in a polymerization reactor equipped with a stirrer and a thermometer, followed by suspension polymerization for 6 hours while maintaining at 60 ° C. This suspension was filtered, and the obtained reaction product was washed, dried and pulverized to obtain spherical porous resin fine particles having an average particle diameter of 5.5 µm. Subsequently, the obtained aqueous dispersion was filtered under reduced pressure with a filter paper using a Buchner funnel, and the cake was dried with a hot air dryer set at 105 ° C to obtain acrylic porous particles. The obtained acrylic porous particles were subjected to dimensional measurement and characteristic evaluation by the following method, and the results are shown in Tables 1 and 2.

Comparative Example 5

Commercially available nylon particles were measured and characterized in the following manner, and the results are shown in Table 2.

[Measurement]

Acrylic hollow particles and nylon particles prepared by the above-mentioned method are mixed with an epoxy resin (a mixture kneaded with a Speci Fix Resin from Spectrus and Speci Fix-20Curing Agent at a ratio of 7: 1 (by weight)) 23 It left to stand for 24 hours in the environment of 65 degreeC and RH. After the cured plate-like epoxy resin was allowed to stand for 1 hour under the condition of -30 ° C, sections were made with a glass knife inside an ultramicrotome (Leica, model name: EMUC6). The sample for a measurement was produced. Subsequently, using an SEM, the outer diameter (α) of the shell of the prepared sample, the diameter (β) of the core, and the maximum pore diameter (γ) through the core in the hollow particles were further measured, and the average value of each of the ten particles measured was measured. Was calculated (unit [μm]).

[Characteristic evaluation]

Acrylic hollow particles and nylon particles were characterized by the method described below.

(1) Compression rate (unit [%]): The micro-compression tester measures the displacement of the acrylic hollow particles and the nylon particles when a load of 1 gf is applied to the acrylic hollow particles and the nylon particles prepared by the above method. Measurement was carried out using (manufactured by Shimadzu Seisakusho, Model: MCT-W200, hereinafter identical). This measurement was made about ten particles obtained arbitrarily, the average value was computed, and the compression rate was computed by the following formula.

Compression ratio = average value of displacement / outer diameter of shell (α) x 100

(2) Low displacement displacement (unit [μm]): The displacement amount of the acrylic hollow particle and the nylon particle when a load of 0.2 gf was applied to 10 randomly collected acrylic hollow particles and nylon particles prepared by the above method, It measured using the micro compression tester, and computed the average value.

(3) Sensory test (soft feeling, moisture, application ability): In the acrylic particles and nylon particles produced by the above method, the softness, moisture and application properties are very good by a sensory test by ten panelists. : 5 points, Good: 4 points, Moderate: 3 points, Slightly bad: 2 points, Very bad: One point was scored, and 10 points were summed and evaluated by the following criteria.

(Reference) A: 40 or more points, B: 31 to 39 points, C: less than 30 points

Table 1

[Table 2]

Table 1 and Table 2 clearly show the following facts.

1. The acrylic hollow particles satisfying all of the requirements of claim 1 are excellent in balance in all of softness, moisture, and spreadability, and thus have no inferiority to nylon particles (see Examples 1 to 6).

2. On the other hand, the acrylic hollow particles with many (A-1) components are inferior in performance to the acrylic hollow particles of Examples 1 to 6 because of poor applicability (see Comparative Example 1).

3. Acrylic hollow particles having less component (A-1) are inferior in performance to the acrylic hollow particles of Examples 1 to 6 because of poor softness and moisture (see Comparative Example 2).

4. The acrylic solid particles whose core is not hollow or the acrylic porous particles having no pores communicating with the core cannot obtain the soft feeling and spreadability of the acrylic hollow particles of Examples 1 to 6, and are particularly inferior in moisture (comparatively). Example 3, Comparative Example 4).

[Preparation of Cosmetics]

Example 7

5 parts by weight of the acrylic hollow particles obtained in Example 1, 5 parts by weight of zinc laurate, 6 parts by weight of pigment grade titanium oxide, 35 parts by weight of sericite, 35.6 parts by weight of talc, and bengala 0.7 Parts by weight, 2.1 parts by weight of iron sulfate, and 0.6 parts by weight of black iron oxide were mixed in an Oster blender (Osaka Chemical Co., Ltd., ST-1) at 15700 rpm for 3 minutes, and then mixed in advance. A mixed solution consisting of 5 parts by weight of ethylhexanoin and 5 parts by weight of dimethicone was added thereto, and mixed under conditions of 10300 rpm and 3 minutes to obtain a cosmetic.

Comparative Example 6

Instead of the acrylic hollow particles obtained in Example 1, using the acrylic hollow particles obtained in Comparative Example 3, a cosmetic was obtained in the same manner as in Example 7.

Comparative Example 7

The cosmetics were obtained by the same method as Example 7 using the acrylic hollow particles obtained in Comparative Example 4 instead of the acrylic hollow particles obtained in Example 1.

Reference Example 1

Instead of the acrylic hollow particles obtained in Example 1, commercially available nylon particles of Comparative Example 5 were used to obtain a cosmetic by the same method as in Example 7.

The above-described sensory test was carried out on the cosmetics obtained in Example 7, Comparative Example 6, Comparative Example 7, and Reference Example 1, and the results are shown in Table 3.

Table 3

The following facts can be clearly seen from Table 3.

1. The cosmetics using the acrylic hollow particles satisfying all the requirements of claim 1 are inferior to the cosmetics using the nylon particles in any of softness, moisture, and spreadability (see Example 7 and Reference Example 1).

2. On the other hand, the cosmetics using acrylic solid particles whose core is not hollow or acrylic porous particles without pores communicating with the core are inferior in softness and moisture to the cosmetics of Example 7 (see Comparative Example 6 and Comparative Example 7). .

Since the acrylic hollow particle which concerns on this invention is excellent also in any of a soft feeling, moisture, and applicability | paintability, it can be used suitably as a particle component mix | blended with cosmetics, such as a foundation and a face powder, as a substitute of nylon particle.

Claims (10)

The nonpolymerizable (meth) acrylic ester monomer (A-1) having a glass transition temperature of 50 ° C. or less of homopolymer and an unsaturated double bond As an acrylic hollow particle which consists of a copolymer of the monomer (A-2) with which more than one is provided, and a (meth) acrylic-type polymer (B), 45-90 weight% of non-crosslinkable (meth) acrylic acid ester monomers (A-1) whose glass transition temperature of the said homopolymer is 50 degrees C or less, and the monomers (A-2) which have two or more said unsaturated double bonds are 10- Copolymerized in a proportion of 55% by weight, The acrylic hollow particles have a hollow core and an outer shell, The outer diameter α of the shell of the acrylic hollow particles is 3 to 10 μm, The ratio {(α) / (β)} of the outer diameter α of the shell to the diameter β of the core is 1.1 to 3.5, The shell is formed with two or more holes through the core, The maximum hole diameter (gamma) is 0.3-2.5 micrometers among the said 2 or more holes, The ratio {(β) / (γ)} of the diameter β of the core and the maximum hole diameter γ is 1.1 to 25.0, wherein the acrylic hollow particle is used. The method of claim 1, 0.005-the monomer in which a (meth) acrylic-type polymer (B) is equipped with 100 weight part of (meth) acrylic-acid alkylesters, 0-20 weight part of other monomers copolymerizable with the (meth) acrylic-acid alkylester, and two or more unsaturated double bonds. Acrylic hollow particles, characterized in that the (co) polymer polymerized 0.05 parts by weight. The method according to claim 1 or 2, The gel fraction of the (meth) acrylic polymer (B) is 10 to 85%, and the weight average molecular weight of the sol is 100,000 to 1,000,000, wherein the acrylic hollow particles are used. The method according to any one of claims 1 to 3, (Meth) acrylic polymer (B) may be used in any one or more of the following methods: soap-free emulsion polymerization, emulsion polymerization, suspension polymerization, and seed polymerization. An acrylic hollow particle characterized in that the seed particles are prepared by the above, wherein the average particle diameter of the seed particles is 0.7 to 5.0 µm. Cosmetics which contain the acrylic hollow particle of any one of Claims 1-4. Non-crosslinkable (meth) acrylic acid ester monomer (A-1) having a glass transition temperature of homopolymer of 50 ° C. or less, monomer having two or more unsaturated double bonds (A-2), polymerization initiator (C) , And an aqueous medium (D) are mixed and stirred to prepare an aqueous dispersion. Subsequently, the obtained aqueous dispersion was mixed and stirred with a dispersion prepared by dispersing a separately prepared (meth) acrylic polymer (B) in an aqueous medium, and the non-crosslinkable (meth) having a glass transition temperature of the homopolymer contained in the aqueous dispersion was 50 ° C. or less. A monomer (A-2) having an acrylic ester monomer (A-1) and two or more unsaturated double bonds is absorbed into the (meth) acrylic polymer (B), Subsequently, the aqueous dispersion containing the obtained (meth) acrylic polymer was heated, and the non-crosslinkable (meth) acrylic acid ester monomer (A-1) having a glass transition temperature of 50% or less of the homopolymer and two unsaturated double bonds were obtained. As a manufacturing method of the acrylic hollow particle obtained by copolymerizing the monomer (A-2) provided above, 45-90 weight% of non-crosslinkable (meth) acrylic acid ester monomers (A-1) whose glass transition temperature of the said homopolymer is 50 degrees C or less, and the monomers (A-2) which have two or more said unsaturated double bonds are 10- Copolymerized in a proportion of 55% by weight, The obtained acrylic hollow particle is provided with a hollow core and an outer shell, The outer diameter (alpha) of the shell of the obtained acrylic hollow particle is 3-10 micrometers, The ratio {(α) / (β)} of the outer diameter α of the shell to the diameter β of the core is 1.1 to 3.5, The shell is formed with two or more holes through the core, The maximum hole diameter (gamma) is 0.3-2.5 micrometers among the said 2 or more holes, A ratio {(β) / (γ)} of the diameter β of the core and the maximum hole diameter γ is 1.1 to 25.0. The method of claim 6, 0.005-the monomer in which a (meth) acrylic-type polymer (B) is equipped with 100 weight part of (meth) acrylic-acid alkylesters, 0-20 weight part of other monomers copolymerizable with the (meth) acrylic-acid alkylester, and two or more unsaturated double bonds. It is a (co) polymer which superposed | polymerized 0.05 weight part, The manufacturing method of the acrylic hollow particle characterized by the above-mentioned. The method according to claim 6 or 7, The gel fraction of the (meth) acrylic polymer (B) is 10 to 85%, and the weight average molecular weight of the sol is 100,000 to 1,000,000. The method according to any one of claims 6 to 8, The (meth) acrylic polymer (B) is a seed particle prepared by at least one polymerization method among soap free emulsion polymerization, emulsion polymerization, suspension polymerization, and seed polymerization, wherein the average particle diameter of the seed particles is 0.7 to 5.0 µm. Acrylic hollow particle manufacturing method characterized in that. Cosmetics which contain the acrylic hollow particle obtained by the manufacturing method in any one of Claims 6-9.

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