JP2011068774A - Hollow particle, manufacturing method and application of the same - Google Patents

Abstract

An object of the present invention is to provide a simple method for producing hollow particles.
(Meth) acrylic acid having a branched alkyl group having 4 to 18 carbon atoms in 100 parts by weight of a (meth) acrylic acid ester monomer mixture containing 5 to 50% by weight of a crosslinkable vinyl monomer. A step of obtaining a mixed solution by dissolving 2 to 10 parts by weight of a (meth) acrylic ester resin containing 50 to 100% by weight of an ester-derived component and 0.01 to 10 parts by weight of a polymerization initiator; The above-mentioned problem is solved by a method for producing hollow particles, comprising a step of suspension polymerization of a monomer mixture in the mixed solution in an aqueous medium to obtain hollow particles.
[Selection] Figure 1

Description

  The present invention relates to hollow particles, a method for producing the same, and uses thereof. More specifically, the present invention relates to a hollow particle useful as a raw material for a resin composition, a coating composition, a display device composition, cosmetics, etc., a production method thereof, and an application thereof.

  Resin particles produced by suspension polymerization are used as light diffusing agents contained in paints, cosmetics, etc., and light diffusing agents contained in light diffusing plates for liquid crystal backlights. That is, resin particles have the role of imparting whiteness by refracting and reflecting light in paints, cosmetics, etc., and in light diffusing plates, light incident from the side by cold cathode tubes etc. Has a role of scattering light so that the light is emitted with uniform brightness. As such resin particles, for example, acrylic resin particles or styrene resin particles are used. Resin particles (hollow particles) having pores inside are also known. Such resin particles have enhanced light reflectivity and light scattering properties.

  As a method for producing hollow particles, a method described in JP-A-5-125127 (Patent Document 1) is known. In this method, it is said that hollow particles can be obtained by allowing a monomer mixture comprising a hydrophilic monomer and a crosslinkable monomer to coexist with a different resin, and then subjecting the monomer mixture to suspension polymerization. Yes. The different types of resins used in this method have a special property that they are soluble in the monomer mixture but are not compatible with the resin produced by the polymerization of the monomer mixture. It is said that hollow particles can be obtained by using a resin having such special properties.

Specifically, an example is described in which an acrylic monomer having excellent transparency is used as the monomer mixture, and a styrene resin is used as a different resin having special properties.
In addition, techniques described in Japanese Unexamined Patent Application Publication No. 2009-67946 (Cited Document 2) and Japanese Unexamined Patent Application Publication No. 2009-79086 (Cited Document 3) are also known.

Japanese Patent Laid-Open No. 5-125127 JP 2009-67946 A JP 2009-79086 A

However, in the technique described in JP-A-5-125127, since a considerable amount of styrene resin is present in the hollow particles, it is difficult to obtain hollow particles having excellent hydrophilicity.
In addition, in the techniques described in JP-A-2009-67946 and JP-A-2009-79086, styrene-based resin is used as a raw material, so that weather resistance, yellowing resistance, and the like are not sufficient.

Thus, according to the present invention, 100 parts by weight of a (meth) acrylic acid ester monomer mixture containing 5 to 50% by weight of a crosslinkable vinyl monomer has a branched alkyl group having 4 to 18 carbon atoms (meta 2) 10 to 10 parts by weight of a (meth) acrylic acid ester resin containing 50 to 100% by weight of a component derived from an acrylate ester and 0.01 to 10 parts by weight of a polymerization initiator are dissolved to prepare a mixed solution. Obtaining a step;
And a step of suspension polymerization of the monomer mixture in the mixed solution in an aqueous medium to obtain hollow particles, and a method for producing hollow particles is provided.
Moreover, according to this invention, the hollow particle obtained by the said manufacturing method is provided.
Furthermore, according to this invention, the resin composition, coating composition, display apparatus composition, or cosmetics containing the said hollow particle are provided.

According to the present invention, hollow particles having excellent light reflectivity and light scattering properties can be produced.
The (meth) acrylic acid ester monomer mixture contains 1 to 30% by weight of (meth) acrylic acid ester having an alkylene oxide group of the structure of Formula 1, thereby having more excellent light reflectivity and light scattering properties. Hollow particles can be produced.
In formula 1, by using a (meth) acrylic acid ester having an alkylene oxide group in which m is 0 to 30 and n is 0 to 30, it has more excellent light reflectivity and light scattering properties and is hydrophilic. The hollow particle which has can be manufactured.
When the mixed solution contains a specific amount of pigment, a desired color can be imparted to the hollow particles.

The hollow particles obtained by the above method are incorporated into a resin composition, a coating composition, a display device composition, or a cosmetic, so that the excellent properties of the hollow particles can be obtained in the resin composition, the coating composition, and the display. It can be applied to a device composition or a cosmetic.
Further, the hollow particles have 100 parts by weight of a resin derived from a (meth) acrylic acid ester monomer mixture containing 5 to 50% by weight of a crosslinkable vinyl monomer and a branched alkyl group having 4 to 18 carbon atoms. By including 2 to 10 parts by weight of a (meth) acrylic ester resin containing 50 to 100% by weight of a component derived from (meth) acrylic acid ester, the hollow particles have excellent light reflectivity and light scattering properties. , Can impart hydrophilicity.

2 is a scanning electron micrograph of hollow particles of Example 1. FIG.

The present invention will be described below. In the production method of the present invention, a (meth) acrylic acid ester monomer mixture (hereinafter also referred to as a monomer mixture) is dissolved in a (meth) acrylic acid ester resin and a polymerization initiator. A step of obtaining (dissolution step);
Hollow particles are obtained through at least two steps of suspension polymerization of the monomer mixture in the mixed solution in an aqueous medium (suspension polymerization step).
(Meth) acryl means acryl or methacryl.

(Hollow particle shape)
The hollow particles obtained by the production method of the present invention are substantially spherical particles and have one or more independent pores inside the particles. Such hollow particles refract the light incident on the particles in a complicated manner due to the internal holes. Therefore, the hollow particles have higher light reflectivity and light diffusibility than solid particles without pores.
The shape of the holes is not particularly limited and is usually spherical.
The average particle diameter of the hollow particles is, for example, 1 to 20 μm. Moreover, this average particle diameter can be suitably set according to the use. Specifically, it is in the range of 1 to 10 μm for the resin composition application as the raw material of the light diffusion plate, 5 to 20 μm for the coating composition application, 1 to 10 μm for the display composition application, and 5 to 10 μm for the cosmetic application. It is preferable that

(Dissolution process)
(1) (Meth) acrylic acid ester monomer mixture The (meth) acrylic acid ester monomer mixture is a mixture containing a (meth) acrylic acid ester monomer and a crosslinkable vinyl monomer.
(A) (meth) acrylic acid ester monomer As (meth) acrylic acid ester monomer, (meth) acrylic acid methyl, (meth) acrylic acid ethyl, (meth) acrylic acid n-propyl, (meth) Isopropyl acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, 2- (meth) acrylic acid 2- And ethyl hexyl. These monomers may be used alone or in combination of two or more.
Of these (meth) acrylic acid ester monomers, methyl (meth) acrylate and ethyl (meth) acrylate are preferred from the viewpoint of improving heat resistance.

(B) Crosslinkable vinyl-type monomer A crosslinkable vinyl-type monomer is contained in the monomer mixture in the ratio of 5 to 50 weight%. When it is less than 5% by weight, phase separation between the resin derived from the monomer mixture and the (meth) acrylic acid ester resin becomes insufficient, and hollow particles may not be obtained. Moreover, when it exceeds 50 weight%, a hollow particle may not be obtained by a phase separation progressing excessively. A more desirable ratio is 10 to 40% by weight.

  Examples of the crosslinkable vinyl monomer include trimethylolpropane triacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, decaethylene glycol dimethacrylate, and pentadecaethylene dimethacrylate. Examples include glycol, pentamethaethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, allyl methacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, diethylene glycol dimethacrylate phthalate, and the like. These monomers may be used alone or in combination of two or more.

(C) (Meth) acrylic acid ester having alkylene oxide group The monomer mixture has an alkylene oxide group in order to stably form a hollow shape by reducing the collapse and deformation of the particles (meta ) It is preferable that an acrylic ester is contained. Examples of such esters include the following formula 1

(Meth) acrylic acid ester having an alkylene oxide group shown in FIG.
In the formula, R ₁ and R ₄ are H or CH ₃ .
R ₂ and R ₃ are different and are alkylene groups having 2 to 5 carbon atoms selected from C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ and C ₅ H ₁₀ . The alkylene group may have a branched chain.
m is 0 to 50, and n is 0 to 50 (provided that m and n are not 0 at the same time). In Formula 1, when m is larger than 50 and when n is larger than 50, polymerization stability may be lowered and coalescence particles may be generated. A preferable range of m and n is 0 to 30, and a more preferable range of m and n is 0 to 15.
These (meth) acrylic acid esters having an alkylene oxide group may be used singly or as a mixture of two or more.

A commercially available product can be used as the (meth) acrylic acid ester having an alkylene oxide group. Examples of commercially available products include the Bremer series manufactured by NOF Corporation. Furthermore, in the Blemmer series, Blemmer 50PEP-300 (R ₁ is CH ₃ , R ₂ is C ₂ H ₅ , R ₃ is C ₃ H ₆ , m and n average m = 3.5 and n = 2.5, R ₄ is H), Blemmer 70PEP-350 (R ₁ is CH ₃ , R ₂ is C ₂ H ₅ , R ₃ is C ₃ H ₆ , m and n are averages A mixture of m = 3.5 and n = 2.5, R ₄ is H), Blemmer PP-1000 (R ₁ is CH ₃ , R ₃ is C ₃ H ₆ , m is 0, n Is a mixture of 4 to 6 on average, R ₄ is H), Blemmer PME-400 (R ₁ is CH ₃ , R ₂ is C ₂ H ₅ , m is a mixture of 9 on average, n is 0 and R ₄ are CH ₃ ).

  The amount of (meth) acrylic acid ester having an alkylene oxide group is preferably 0 to 30% by weight, more preferably 1 to 30% by weight, still more preferably 5 to 30% by weight, based on the total amount of the monomer mixture. Particularly preferred is 10 to 20% by weight. If the amount used exceeds 30% by weight, the polymerization stability may decrease and the number of coalesced particles may increase.

(D) Other monomers The monomer mixture may contain other monomers copolymerizable with the (meth) acrylic acid ester monomer as long as the effects of the present invention are not hindered. Good. The other monomer may be a crosslinkable monomer or a non-crosslinkable monomer. Among these, non-crosslinkable monomers include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, vinyl chloride, vinyl acetate, acrylonitrile, (meth) acrylamide, N-vinyl. Examples include pyrrolidone and the like. These monomers may be used alone or in combination of two or more.

(2) (Meth) acrylic acid ester resin (Meth) acrylic acid ester resin is a resin containing a component derived from a (meth) acrylic acid ester having a branched alkyl group having 4 to 18 carbon atoms.
(A) (meth) acrylic acid ester having a branched alkyl group having 4 to 18 carbon atoms Examples of the branched alkyl group having 4 to 18 carbon atoms include an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, and an isohexyl group. , Isoheptyl group, isooctyl group, isononyl group, isodecyl group, isostearyl group and the like. The branched alkyl group preferably has 4 to 18 carbon atoms.

More specific examples of the (meth) acrylic acid ester having a branched alkyl group having 4 to 18 carbon atoms include isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ( (Meth) acrylic acid isostearyl etc. are mentioned. These esters may be used alone or in combination of two or more.
The amount of the (meth) acrylic acid ester having a branched alkyl group having 4 to 18 carbon atoms is preferably 50 to 100% by weight, more preferably 60 to 100% by weight, based on the total amount of the (meth) acrylic ester resin. Preferably, it is 70 to 100% by weight. When the amount used is less than 50% by weight, phase separation may be insufficient and desired hollow particles may not be obtained.

(B) Other monomer The (meth) acrylic acid ester resin may be a copolymer of a (meth) acrylic acid ester having a branched alkyl group having 4 to 12 carbon atoms and another monomer. Good. Other monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth) Examples include dodecyl acrylate and stearyl (meth) acrylate. These monomers may be used alone or in combination of two or more.

(C) Weight average molecular weight It is preferable that the (meth) acrylic acid ester resin has a weight average molecular weight of 50,000 to 400,000. When the weight average molecular weight is less than 50000, phase separation from the monomer mixture becomes insufficient, and particles having desired pores may not be obtained. When it is larger than 400,000, dissolution in the monomer mixture becomes difficult, and the productivity of the hollow particles may be insufficient. A more preferred weight average molecular weight is 70000-300000.

(D) Manufacturing method of (meth) acrylic acid ester resin The manufacturing method of (meth) acrylic acid ester resin is not specifically limited, Well-known methods, such as suspension polymerization, solution polymerization, and block polymerization, are mentioned. Among these, in order to shorten the dissolution time in the monomer mixture, suspension polymerization is preferred in which it is easy to obtain a particulate (meth) acrylate resin having an appropriate size.

(E) Use amount of (meth) acrylic acid ester resin The (meth) acrylic acid ester resin is used in an amount of 2 to 10 parts by weight based on 100 parts by weight of the monomer mixture. If the amount used is less than 2 parts by weight, hollow particles may not be obtained. If it exceeds 10 parts by weight, dissolution in the monomer mixture may be difficult. A more preferable usage amount is 3 to 8 parts by weight.

(3) Polymerization initiator Examples of the polymerization initiator include oil-soluble peroxide-based initiators and azo-based initiators that are usually used for suspension polymerization. For example, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate, cumene hydroperoxide, cyclohexanone peroxide, t-butyl hydroxide, Peroxide-based initiators such as diisopropylbenzene hydroperoxide; 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2 , 3-dimethylbutyronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,3,3-trimethylbutyronitrile), 2,2′-azobis ( 2-isopropylbutyronitrile), 1,1 ′ -Azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2- (carbamoylazo) isobutyronitrile, 4,4'-azobis (4 -Cyanovaleric acid) and azo compounds such as dimethyl-2,2'-azobisisobutyrate. Among these, 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile) are preferable.

  A polymerization initiator is used in 0.01-10 weight part with respect to 100 weight part of monomer mixtures. When the amount used is less than 0.01 parts by weight, the polymerization time may be long. On the other hand, when the amount used exceeds 10 parts by weight, an effect commensurate with the amount used cannot be expected. A preferred amount of use is 0.1 to 3 parts by weight.

(4) Pigment A pigment may be added to the monomer mixture. Examples of the pigment include inorganic pigments such as titanium oxide, barium sulfate, calcium carbonate, and carbon black, and colored organic pigments such as red, blue, and yellow. Among these pigments, titanium oxide, barium sulfate, and calcium carbonate have a high refractive index, so that the light diffusibility and concealment of the hollow particles can be further improved.
Dispersibility in the monomer mixture may be improved by subjecting the surface of the pigment to a hydrophobic treatment using a coupling agent such as a silane coupling agent, a titanate coupling agent, or an aluminum coupling agent.
The pigment is preferably contained in the mixed solution at a ratio of 50 to 120 parts by weight with respect to 100 parts by weight of the monomer mixture.

(5) Dissolution condition The (meth) acrylate resin and the polymerization initiator are dissolved in the monomer mixture. It is visually confirmed that there is no suspended solids after stirring the mixed solution obtained by adding (meth) acrylate resin and polymerization initiator into the monomer mixture. Judge by. The stirring condition is not particularly limited as long as it dissolves.

(Suspension polymerization process)
In the suspension polymerization process, the monomer mixture in the droplets of the mixed solution is polymerized in an aqueous medium to obtain hollow particles.

(1) Aqueous medium Examples of the aqueous medium include water and a mixed medium of water and a water-soluble solvent (for example, lower alcohol). The usage-amount of an aqueous medium is 100-1000 weight part normally with respect to 100 weight part of mixed solutions. The aqueous medium is preferably composed of water.

The aqueous medium preferably contains a dispersion stabilizer.
Examples of the dispersion stabilizer include phosphates such as calcium phosphate, magnesium phosphate, aluminum phosphate and zinc phosphate, pyrophosphates such as calcium pyrophosphate, magnesium pyrophosphate, aluminum pyrophosphate and zinc pyrophosphate, calcium carbonate, Examples thereof include poorly water-soluble inorganic compounds such as magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate and colloidal silica, and water-soluble polymers such as polyvinyl alcohol. Among these, tricalcium phosphate, magnesium pyrophosphate, calcium pyrophosphate, and colloidal silica are particularly preferable from the viewpoint that target hollow particles can be stably obtained. The addition amount of the dispersion stabilizer is usually 0.5 to 30 parts by weight with respect to 100 parts by weight of the monomer mixture.

The aqueous medium may contain a surfactant.
As the surfactant, any of anionic, cationic, nonionic and zwitterionic active agents can be used.
Examples of anionic surfactants include fatty acid oils such as sodium oleate and castor oil, alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, and alkylnaphthalene sulfone. Acid salts, alkane sulfonates, dialkyl sulfosuccinates such as sodium dioctyl sulfosuccinate, alkenyl succinates (dipotassium salts), alkyl phosphate esters, naphthalene sulfonate formalin condensates, polyoxyethylene alkyl phenyl ether sulfates Examples thereof include salts, polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate, and polyoxyethylene alkyl sulfate salts.

Examples of the cationic surfactant include alkylamine salts such as laurylamine acetate and stearylamine acetate, and quaternary ammonium salts such as lauryltrimethylammonium chloride.
Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxysorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, oxyethylene- An oxypropylene block polymer etc. are mentioned.

Examples of zwitterionic surfactants include lauryl dimethylamine oxide and phosphate ester or phosphite ester surfactants.
You may use the said surfactant individually or in combination of 2 or more types. Of the above surfactants, anionic surfactants are preferred from the viewpoint of dispersion stability during polymerization.
The usage-amount of surfactant is 0.001-0.1 weight part normally with respect to 100 weight part of aqueous media.

  In addition, a polymerization inhibitor may be used in order to efficiently obtain hollow particles by suppressing the generation of polymer particles consisting only of a monomer mixture in an aqueous system and promoting phase separation. Examples of the polymerization inhibitor include water-soluble polymerization inhibitors such as nitrites, sulfites, hydroquinones, ascorbic acids, water-soluble vitamin Bs, citric acid, and polyphenols. The usage-amount of a polymerization inhibitor is 0.01-1 weight part normally with respect to 100 weight part of aqueous media.

(2) Polymerization conditions The dispersion of the mixed solution in the aqueous medium is not particularly limited, and can be performed by a known method. For example, a method of dispersing a mixed solution by a stirring force such as a propeller blade, a method of dispersing using a homomixer that is a disperser using a high shear force composed of a rotor and a stator, and an ultrasonic disperser Examples thereof include a dispersion method, a method using a high-pressure disperser using a collision force between droplets such as a microfluidizer and a nanomizer, and a collision force against a machine wall. The average maximum particle size of the hollow particles can be appropriately set by adjusting the mixing conditions of the monomer mixture and the aqueous medium, the amount of the dispersion stabilizer, the stirring conditions, the dispersing conditions, and the like.

In order to make the particle diameters of the hollow particles uniform, the diameters of the droplets made of the mixed solution in the aqueous medium may be made uniform. In this case, it is preferable to disperse by a method using a high-pressure disperser utilizing collision between droplets or collision force against the machine wall.
The droplets made of the mixed solution present in the aqueous medium become hollow particles by polymerizing the monomer mixture in the droplets by heating as necessary. The polymerization temperature is preferably 30 to 100 ° C, more preferably 40 to 80 ° C. The time for maintaining the polymerization temperature is generally about 0.1 to 10 hours. Moreover, superposition | polymerization can be performed under a normal pressure or pressurization.

The polymerization is preferably carried out with stirring sufficient to prevent droplets from floating and the resulting hollow particles from settling.
Furthermore, the polymerization is preferably carried out until the amount of residual monomer in the hollow particles is 1% by weight or less.

(Resin composition and display device composition)
The resin composition contains the hollow particles and the base resin, and has excellent light reflectivity and light scattering properties.
As the base resin, a thermoplastic resin is usually used. Examples of the thermoplastic resin include (meth) acrylic resin, (meth) acrylic acid alkyl-styrene copolymer, polycarbonate, polyester, polyethylene, polypropylene, polystyrene. Etc. Among these, when excellent transparency is required, (meth) acrylic resin, (meth) acrylic acid acrylic-styrene copolymer, polycarbonate, polyester, and polystyrene are preferable. These thermoplastic resins can be used alone or in combination of two or more.
The amount of the hollow particles used in the base resin is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the base resin. If it is less than 0.01 parts by weight, it may be difficult to give light diffusibility. When the amount is more than 10 parts by weight, light diffusibility can be obtained, but light transmittance may be lowered. A more preferable usage amount is 0.1 to 5 parts by weight.

  The resin composition is not particularly limited, and the hollow particles and the base resin can be obtained by conventional methods and conditions such as a mechanical pulverization and mixing method. For example, a Henschel mixer, a V-type mixer, a turbula mixer It can be obtained by mixing and stirring the hollow particles and the base resin using a hybridizer, a rocking mixer or the like. Alternatively, the light diffusing resin composition may be obtained by mixing the hollow particles and the transparent base resin with a mixer and kneading the mixture with a melt kneader such as a uniaxial or biaxial extruder. The composition may be formed into a sheet form from a melt kneader through a T die, a roll unit, or the like. Furthermore, a light diffusing resin molded sheet (optical sheet) having an arbitrary shape can be obtained by extruding in a pellet form from a melt kneader and extruding the pellet or performing injection molding after melting.

The optical sheet can be used for, for example, a light diffusion plate of a liquid crystal display device. The configuration of the liquid crystal display device is not particularly limited as long as it includes an optical sheet. For example, the liquid crystal display device includes at least a liquid crystal display panel having a display surface and a back surface, a light guide plate disposed on the back surface side of the panel, and a light source that makes light incident on a side surface of the light guide plate. In addition, a reflection sheet is provided on the side of the light guide plate opposite to the surface facing the liquid crystal display panel. This arrangement of light sources is generally referred to as an edge light type backlight arrangement.
Further, in addition to the edge light type backlight arrangement, there is a direct type backlight arrangement. Specifically, this arrangement is an arrangement in which a light source is arranged on the back side of the liquid crystal display panel and at least a light diffusing plate arranged between the liquid crystal display panel and the light source.

(Coating composition)
The coating composition can be used for applications such as matting, light diffusion, and reflection of light such as a resin substrate, a metal substrate, and an optical film such as a PET film.
The coating composition comprises a solution in which hollow particles and a binder are dispersed or dissolved in a solvent. Here, as the solution in which the binder is dissolved or dispersed, a commercially available solvent type solution in which the binder is dissolved or dispersed in advance can be used. The coating composition may contain a crosslinking agent such as a urethane crosslinking agent.
Examples of the binder include solvent-soluble binders such as acrylic, urethane, polyester, and silicone. The binder may be a thermosetting or ultraviolet curable curable binder.

The solvent is not particularly limited as long as it can dissolve or disperse the binder, and examples thereof include alcohol-based, ester-based, aromatic-based, hydrocarbon-based organic solvents, water, and the like. Specifically, examples of the organic solvent include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), ethyl acetate, butyl acetate, isopropyl alcohol, Examples include acetone and anisole. These media can be used alone or in combination of two or more.
You may add various well-known additives, such as a leveling agent, a surface modifier, a defoaming agent, and a coloring agent like a pigment and dye, to the said coating composition.

The coating composition is prepared by a known method, for example, after the binder is dissolved in an organic solvent, the hollow particles of the present invention are added to the solution, and a sand mill, a ball mill, an attritor, a high-speed rotary stirrer, a triple roll, etc. And can be produced by a method of mixing and dispersing.
The coating method of a coating composition is not specifically limited, For example, well-known methods, such as a spray method, a barcode method, a doctor blade method, a roll coat method, a spin coat method, or a dipping method, can be used. A coating film is obtained by applying the coating composition by these methods and then drying to remove the organic solvent.

(Cosmetics)
Hollow particles can also be used as a raw material for cosmetics. Although the usage-amount of the hollow particle in cosmetics can be suitably set according to the kind of cosmetics, 0.1 to 50 weight% is preferable and 0.2 to 30 weight% is still more preferable.
When the amount of the hollow particles used relative to the total amount of the cosmetic is less than 0.1% by weight, a clear effect due to the inclusion of the hollow particles may not be recognized. On the other hand, if the amount of hollow particles used exceeds 50% by weight, a remarkable effect commensurate with the increase in the amount used may not be observed, which is not preferable in terms of production cost.

  Cosmetics include, for example, pre-shave lotions, body lotions, lotions, creams, emulsions, body shampoos, antiperspirants, etc., soaps, scrubs, and other cosmetics for washing, packs, shaving Cream, funny products, foundation, lipstick, lip balm, blusher, eyebrow cosmetics, nail polish cosmetics, hair washing cosmetics, hair dye, hairdressing, aromatic cosmetics, toothpaste, bath preparation, sunscreen products, suntan products, body powder, baby The thing for bodies, such as powder, is mentioned.

  Moreover, in these cosmetics, the additive generally used can be mix | blended according to the objective in the range which does not impair the effect of this invention. Examples of such additives include water, lower alcohols, fats and waxes, hydrocarbons, higher fatty acids, higher alcohols, sterols, fatty acid esters, metal soaps, moisturizers, surfactants, polymer compounds, and coloring material raw materials. , Fragrances, antiseptic / bactericides, antioxidants, ultraviolet absorbers, silicon-based particles, other resin particles such as polystyrene particles, and special compounding additives.

Specific production methods of the present invention will be described below by way of examples, but the present invention is not limited to these examples.
(Weight average molecular weight)
The weight average molecular weight (Mw) is measured using gel permeation chromatography (GPC). In addition, a weight average molecular weight means a polystyrene (PS) conversion weight average molecular weight. Specifically, the measurement is performed as follows.
A 50 mg sample is dissolved in 10 ml of tetrahydrofuran (THF), filtered through a non-aqueous 0.45 μm chromatographic disk, and measured using a chromatograph. The chromatographic conditions are as follows.
Liquid chromatograph: manufactured by Tosoh Corporation, trade name “Gel Permeation Chromatograph HLC-8020”
Column: manufactured by Tosoh Corporation, trade names “TSK GEL G-1000H, G-2000H, 4000H”
Column temperature: 40 ° C
Carrier gas: Tetrahydrofuran (THF)
Carrier gas flow rate: 1 ml / min Injection / pump temperature: 35 ° C
Detection: RI
Injection amount: 100 microliters Standard polystyrene for calibration curve: manufactured by Showa Denko KK, trade name “shodex” weight average molecular weight: 1030000 and manufactured by Tosoh Corporation, weight average molecular weight: 5480000, 3840000, 355000, 102000, 37900, 9100, 2630, 870

(Measurement of sphere equivalent volume average particle diameter of hollow particles)
The electrolyte solution is filled in pores having a pore diameter of 50 to 280 μm, the volume is obtained from the change in conductivity of the electrolyte solution when the particles pass through the electrolyte solution, and the volume-average particle diameter in terms of sphere is calculated. Specifically, the measured average particle diameter is a volume average particle diameter measured by a Coulter Multisizer II manufactured by Beckman Coulter. In the measurement, calibration is performed using an aperture suitable for the particle diameter of the particle to be measured according to REFERENCE MANUAL FOR THE COULTER MULTISIZER (1987) issued by Coulter Electronics Limited.
Specifically, 0.1 g of particles and 10 ml of 0.1% nonionic surfactant solution were put into a commercially available glass test tube, mixed for 2 seconds with a touch mixer TOUCHMIXER MT-31 manufactured by Yamato Scientific Co., Ltd., and then tested. The tube is pre-dispersed for 10 seconds using a commercially available ultrasonic cleaner, ULTRASONIC CLEANER VS-150 manufactured by VervoCrea. In a beaker, drop gently with a dropper while stirring gently, and adjust the reading of the densitometer on the main screen to about 10%. Next, the aperture size, Current, Gain, and Polarity are input to the Multisizer II main body according to REFERENCE MANUAL FOR THE MULTILIZER MULTISIZER (1987) issued by Coulter Electronics Limited, and measured manually. During the measurement, the beaker is stirred gently to the extent that bubbles do not enter, and the measurement is terminated when 100,000 particles are measured.

(Total light transmittance, haze)
The total light transmittance is measured according to JIS K 7361. Specifically, the measurement is performed using NHD-2000 manufactured by Nippon Denshoku Industries Co., Ltd.
Haze is measured according to JIS K 7136. Specifically, the measurement is performed using NHD-2000 manufactured by Nippon Denshoku Industries Co., Ltd.
The total light transmittance and haze are values obtained by calculating the average value of the number of measurement samples n = 10.

(gross)
In accordance with the method described in JIS 8741, the gloss at 60 ° is measured using a gloss checker (G-331) manufactured by Horiba, Ltd.

(Production example of (meth) acrylic ester resin)
Production Example 1
A polymerization vessel equipped with a stirrer and a thermometer was charged with 500 parts by weight of water in which 0.05 part by weight of sodium lauryl sulfate was dissolved, and 50 parts by weight of calcium triphosphate was dispersed therein. A solution of 60 parts by weight of isobutyl methacrylate and 40 parts by weight of methyl methacrylate and 2 parts by weight of benzoyl peroxide prepared in advance was added to the resulting dispersion. The resulting solution was then transferred to T.W. The mixture was stirred at 3000 rpm for 10 minutes with a K homomixer (manufactured by Tokugi Koki Kogyo Co., Ltd.) to prepare a droplet diameter of approximately 20 μm. Next, the polymerization reactor was heated to 70 ° C., and suspension polymerization was performed with stirring, and then the suspension was cooled to room temperature to obtain a suspension.
The obtained suspension was filtered, washed and dried to obtain a particulate methacrylate ester resin. The weight average molecular weight of the obtained resin was 150,000.

Production Example 2
A methacrylic ester resin was obtained in the same manner as in Production Example 1 except that 60 parts by weight of isobutyl methacrylate and 40 parts by weight of methyl methacrylate were replaced with 90 parts by weight of isobutyl methacrylate and 10 parts by weight of methyl methacrylate. The weight average molecular weight of the obtained resin was 150,000.
Production Example 3
A methacrylate ester-based resin was obtained in the same manner as in Production Example 1 except that isobutyl methacrylate and methyl methacrylate were replaced with isostearyl acrylate and methyl methacrylate. The weight average molecular weight of the obtained resin was 180,000.

Production Example 4 (Comparative Example)
A methacrylate ester-based resin was obtained in the same manner as in Production Example 1 except that 60 parts by weight of isobutyl methacrylate and 40 parts by weight of methyl methacrylate were replaced with 40 parts by weight of isobutyl methacrylate and 60 parts by weight of methyl methacrylate. The weight average molecular weight of the obtained resin was 150,000.

Example 1
A polymerization vessel equipped with a stirrer and a thermometer was charged with 500 parts by weight of water in which 0.05 part by weight of sodium lauryl sulfate was dissolved, and 50 parts by weight of tricalcium phosphate was dispersed therein. In the obtained dispersion, 60 parts by weight of methyl methacrylate, 30 parts by weight of ethylene glycol dimethacrylate, and poly (propylene glycol) monomethacrylate (product name: Blemmer PP-1000 / manufactured by NOF Corporation, formula) 1, R ₁ = CH ₃ , R ₂ = C ₃ H ₆ , R ₄ = H, m = 0, n is a mixture of 4 to 6 on average) 10 parts by weight of monomer mixture 100 A mixed solution in which 5 parts by weight of the methacrylic ester resin obtained in Production Example 1 and 0.5 parts by weight of azobisisobutyronitrile were dissolved was added to parts by weight. The resulting solution was then transferred to T.W. The mixture was stirred at 5000 rpm for 10 minutes with a K homomixer (manufactured by Tokki Kikai Kogyo Co., Ltd.) to prepare a droplet diameter of approximately 5 μm. Next, the polymerization vessel was heated to 65 ° C., and suspension polymerization was performed with stirring, and then the suspension was cooled to room temperature to obtain a suspension.

  The obtained suspension was filtered, washed, and dried to obtain particles having an average particle diameter of 5.5 μm. When the obtained particles were observed with an optical microscope, the outline of the particles was observed twice, and it was found that the particles were hollow particles having voids inside the particles. Moreover, the scanning electron micrograph of the cross section which included the hollow particle with the epoxy resin and sliced the inclusion with a cutter is shown in FIG.

(Example 2)
Particles having an average particle size of 8.2 μm were obtained in the same manner as in Example 1 except that the methacrylate ester resin obtained in Production Example 1 was replaced with the methacrylate ester resin obtained in Production Example 2. . When the obtained particles were observed with an optical microscope, the outline of the particles was observed twice, and it was found that the particles were hollow particles having voids inside the particles.

(Example 3)
Poly (propylene glycol) monomethacrylate is converted to poly (ethylene glycol) monomethacrylate (product name: Bremer PME-400 / manufactured by NOF Corporation, in formula 1, R ₁ = CH ₃ , R ₂ = C ₂ H ₄ , R ₄ = Particles having an average particle diameter of 5.1 μm were obtained in the same manner as in Example 1 except that CH ₃ , m = 9, and n = 0. When the obtained particles were observed with an optical microscope, the outline of the particles was observed twice, and it was found that the particles were hollow particles having voids inside the particles.

Example 4
After weighing 60 parts by weight of methyl methacrylate, 1 part by weight of γ-methacryloxypropyltrimethoxysilane, and 25 parts by weight of titanium oxide (JR600A manufactured by Teica), the mixture was allowed to stand at room temperature for 12 hours. The mixture was dispersed at 5000 rpm for 10 minutes with a K homomixer (manufactured by Tokugi Koki Kogyo Co., Ltd.). In the obtained dispersion, 30 parts by weight of ethylene glycol dimethacrylate, poly (ethylene glycol-propylene glycol) monomethacrylate (product name: Bremer 50PEP-300 / manufactured by NOF Corporation, R 1 ₁ = CH ₃ , R ₂ = C ₂ H ₄ , R ₃ = C ₃ H ₆ , R ₄ = H, m and n are on average a mixture of m = 3.5 and n = 2.5 ) 10 parts by weight, 5 parts by weight of a methacrylic ester resin obtained in Production Example 2, and 0.5 parts by weight of azobisisobutyronitrile were added. The resulting solution was then transferred to T.W. A mixed solution was prepared by dispersing the mixture at 5000 rpm for 5 minutes with a K homomixer (manufactured by Special Machinery Co., Ltd.).

  A polymerization vessel equipped with a stirrer and a thermometer was charged with 500 parts by weight of water in which 0.05 part by weight of sodium lauryl sulfate was dissolved, and 50 parts by weight of calcium triphosphate was dispersed therein. The mixed solution was put into the obtained dispersion. The resulting solution was stirred at 5000 rpm for 10 minutes to prepare a droplet diameter of approximately 8 μm. Next, the polymerization vessel was heated to 65 ° C., and suspension polymerization was performed with stirring, and then the suspension was cooled to room temperature to obtain a suspension.

  The obtained suspension was filtered, washed and dried to obtain particles having an average particle diameter of 7.5 μm. The obtained particles were encapsulated with an epoxy resin, and a scanning electron micrograph of a cross section obtained by slicing the inclusions with a cutter was observed. As a result, it was found that the particles were hollow particles having voids inside the particles.

(Example 5)
Particles having an average particle diameter of 5.8 μm were obtained in the same manner as in Example 1 except that the methacrylic ester resin obtained in Production Example 1 was replaced with the methacrylic ester resin obtained in Production Example 3. . When the obtained particles were observed with an optical microscope, the outline of the particles was observed twice, and it was found that the particles were hollow particles having voids inside the particles.

(Comparative Example 1)
Particles having an average particle size of 6 μm were obtained in the same manner as in Example 1 except that the methacrylic ester resin obtained in Production Example 1 was replaced with the methacrylic ester resin obtained in Production Example 4. When the obtained particles were observed with an optical microscope, it was found that the particle outline was not doubled and was a solid particle without voids inside the particles.

(Comparative Example 2)
Particles having an average particle diameter of 8.3 μm were obtained in the same manner as in Example 1 except that the amount of the methacrylic ester resin obtained in Production Example 1 was 1 part by weight. When the obtained particles were observed with an optical microscope, it was found that the particle outline was not doubled and was a solid particle without voids inside the particles.

(Evaluation of resin composition)
1 part by weight of the particles obtained in Examples 1 to 5 and Comparative Examples 1 and 2 and 100 parts by weight of polymethyl methacrylate resin (Sumipex EXA manufactured by Sumitomo Chemical Co., Ltd.) as a transparent base resin were set at 80 ° C. Dry in oven for 3 hours. These dried products were put into an extruder, melt-kneaded at 250 ° C. in the extruder, and pelletized. The obtained pellets were molded by an injection molding machine (cylinder temperature 270 ° C., residence time 15 minutes) to produce a 2 mm thick, 50 mm × 100 mm molded plate. Table 1 shows the evaluation results of the obtained molded plate.

  From Table 1, the hollow particles of the examples can increase the haze by adding a small amount, and when used as a diffusion plate for a liquid crystal display device or a molded article for a lighting cover, the lamp image can be erased. I understand.

(Evaluation of coating composition)
1 part by weight of the particles obtained in Examples 1 and 2 and Comparative Example 1 and 20 parts by weight of a commercially available aqueous resin binder liquid (Vaironal MD-1200 manufactured by Toyobo Co., Ltd., solid content 34% by weight) are stirred and deaerated. A coating composition was obtained by mixing for 10 minutes and defoaming for 1 minute.
The obtained coating composition was applied to an ABS plate having a thickness of 2 mm using a coating apparatus on which a doctor blade having a clearance of 75 μm was set, and then dried to obtain a coating film.
The gloss of the obtained coating film was measured, and the results are shown in Table 2.

  From Table 2, it can be seen that the hollow particles of the examples are highly effective in increasing the gloss even when the addition amount is the same as the solid particles of the comparative example.

(Examples of cosmetic formulations)
(Prescription Example 1)
Production and blending amount of powder foundation: 10.0 parts by weight of hollow particles obtained in Example 1 3.0 parts by weight of red iron oxide 2.5 parts by weight of yellow iron oxide 0.5 parts by weight of black iron oxide 10.0 parts by weight of titanium oxide 10.0 Parts by weight mica 20.0 parts by weight talc 44.0 parts by weight liquid paraffin 5.0 parts by weight octyldodecyl myristate 2.5 parts by weight petrolatum 2.5 parts by weight preservative appropriate amount perfume appropriate amount / production method hollow particles, red iron oxide , Yellow iron oxide, black iron oxide, titanium oxide, mica and talc are mixed with a Henschel mixer, and liquid paraffin, octyldodecyl myristate, petrolatum and preservative are mixed and added to this and mixed uniformly. After adding a fragrance | flavor to this and mixing, it grind | pulverizes and it passes through a sieve. This is compression molded into a metal pan to obtain a powder foundation.

(Prescription example 2)
Manufacture and blending amount of cosmetic emulsion Hollow particles obtained in Example 10.0 10.0 parts by weight Stearic acid 2.5 parts by weight Cetyl alcohol 1.5 parts by weight Vaseline 5.0 parts by weight Liquid paraffin 10.0 parts by weight Polyethylene ( 10 mol) Monooleate 2.0 parts by weight Polyethylene glycol 1500 3.0 parts by weight Triethanolamine 1.0 part by weight Purified water 64.5 parts by weight Fragrance 0.5 part by weight Preservative Suitable amount / Production method First, stearin Acid, cetyl alcohol, petrolatum, liquid paraffin, and polyethylene monooleate are dissolved by heating, and hollow particles are added and mixed therein, and kept at 70 ° C. (oil phase). Further, polyethylene glycol and triethanolamine are added to purified water, dissolved by heating, and kept at 70 ° C. (aqueous phase). An oil phase is added to the aqueous phase, pre-emulsified, and then uniformly emulsified with a homomixer. After emulsification, the emulsion is cooled to 30 ° C. with stirring to obtain a cosmetic emulsion.

Claims (9)

Derived from a (meth) acrylic acid ester having a branched alkyl group having 4 to 18 carbon atoms in 100 parts by weight of a (meth) acrylic acid ester monomer mixture containing 5 to 50% by weight of a crosslinkable vinyl monomer. A step of obtaining a mixed solution by dissolving 2 to 10 parts by weight of a (meth) acrylic acid ester resin containing 50 to 100% by weight of a component and 0.01 to 10 parts by weight of a polymerization initiator;
A process for producing hollow particles by subjecting the monomer mixture in the mixed solution to suspension polymerization in an aqueous medium to obtain hollow particles. The (meth) acrylic acid ester monomer mixture is represented by the following formula 1
(In the formula, R ₁ is H or CH ₃ , R ₂ and R ₃ are different and have ₂ to 5 carbon atoms selected from C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ , and C ₅ H _10. M is 0 to 50, n is 0 to 50 (where m and n are not 0 at the same time, and R ₄ is H or CH ₃ )
The manufacturing method of the hollow particle of Claim 1 which contains 1-30 weight% of (meth) acrylic acid ester which has an alkylene oxide group shown in.   The method for producing hollow particles according to claim 2, wherein m is 0 to 30 and n is 0 to 30.   The manufacturing method of the hollow particle as described in any one of Claims 1-3 in which the said mixed solution contains 50-120 weight part pigment with respect to 100 weight part of monomer mixtures.   Hollow particles obtained by the production method according to any one of claims 1 to 4.   A resin composition comprising the hollow particles according to claim 5.   A coating composition comprising the hollow particles according to claim 5.   The composition for display apparatuses containing the hollow particle of Claim 5.   A cosmetic comprising the hollow particles according to claim 5.