JPH0860022A - Composite zinc oxide/polymer microparticle, production and use thereof - Google Patents

Abstract

PURPOSE: To obtain microparticles being excellent in dispersibility, having UV intercepting properties and controlled in visible light transmittance and light diffusing properties. CONSTITUTION: This microparticle comprises zinc oxide micro-particles and a polymer, the amount of the zinc oxide microparticles being 50-99wt.% based on the total weight of the zinc oxide microparticles and the polymer. The composite microparticles are precipitated from a mixture containing zinc, a monocarboxylic acid, a polymer and a medium essentially consisting of an alcohol by keeping the mixture at 100 deg.C or higher. These composite microparticles are mixed with a binder component to obtain a coating composition, are mixed with a resin to obtain a resin composition, are mixed with a pulp to form a mixture for paper or are added to cosmetic components to form a cosmetic.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to fine composite particles containing zinc oxide and a polymer, a method for producing the same, a coating composition, a coated product, a resin composition, a resin molded product, paper and cosmetics.

[0002]

[Prior art]

[Prior Art of Zinc Oxide Fine Particles] Zinc oxide fine particles are excellent in ultraviolet ray shielding ability (absorption or scattering), so that they are contained in a coating film or a resin molded article to which ultraviolet ray shielding ability is imparted. However, there is a problem that zinc oxide fine particles have low dispersibility because they are easily aggregated. [Prior Art of Coating Composition / Coated Product / Resin Composition / Resin Molded Product] As a light diffusing composition, inorganic transparent fine particles such as calcium carbonate, silica, barium sulfate, etc. Those dispersed in methacrylic resin are known. This light diffusing composition is used as a coating material for forming a light diffusing layer on the surface of a transparent base material or as a molding material for forming a light diffusing molded article to form a light diffusing body. This light diffuser exhibits light diffusivity by scattering light at the interface between the inorganic transparent fine particles and the binder component based on the difference in refractive index between the inorganic transparent fine particles and the binder component.

However, inorganic transparent fine particles such as calcium carbonate, silica and barium sulfate do not have a function of blocking ultraviolet rays. Further, this light diffuser has low mechanical properties because the inorganic transparent fine particles have a low affinity with the binder component. Moreover, since this light diffuser needs to contain a large amount of inorganic transparent fine particles in order to realize high light diffusivity, the light transmittance is reduced and the mechanical properties are further reduced.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to have an ability to block ultraviolet rays and to control visible light transmittance and light diffusivity,
A zinc oxide-polymer composite fine particle having excellent dispersibility is provided. Another object of the present invention is to provide a production method capable of producing such zinc oxide-polymer composite fine particles with high productivity.

Still another object of the present invention is to provide a coating composition, a coated article, a resin composition, a resin molded article, a paper and a cosmetic, which have an ultraviolet ray-shielding ability and whose visible light transmittance and light diffusion are controlled. Is to provide a fee.

[0006]

[Means for Solving the Problems]

[Zinc Oxide-Polymer Composite Fine Particles] The zinc oxide-polymer composite fine particles of the present invention contain zinc oxide fine particles and a polymer. The zinc oxide fine particles are 50 to 99% by weight based on the total weight of the zinc oxide fine particles and the polymer.

The fine composite particles of the present invention are preferably
It has a number average particle diameter of 0.1 to 10 μm and a coefficient of variation of particle diameter of 30% or less. The composite fine particles of the present invention are
When the number average particle diameter is 1 to 10 μm and the variation coefficient of the particle diameter is 30% or less, the zinc oxide fine particles have 0.0
It is preferable that the zinc oxide fine particles have a number average particle diameter of 05 to 0.1 μm, and the number average particle diameter of the zinc oxide fine particles is 1/10 to 1/1000 of the number average particle diameter of the composite fine particles.

The fine composite particles of the present invention are, for example, spherical and / or elliptic spherical. In order to have high light diffusibility, the composite fine particles of the present invention preferably have an outer shell formed by aggregating zinc oxide fine particles. In this case, if the inside of the outer shell is hollow, the composite fine particles will be more excellent in light diffusion. The polymer contained in the composite fine particles of the present invention has, for example, one or more polar atomic groups. The polar atomic group is, for example, a carboxyl group,
Amino group, quaternary ammonio group, amide group, imide bond,
At least one selected from the group consisting of a hydroxyl group, a carboxylic acid ester bond, a urethane group, a urethane bond, a ureido group, a ureylene bond, an isocyanate group, an epoxy group, a phosphoric acid group, a metal hydroxyl group, a metal alkoxy group and a sulfonic acid group. . [Method for producing fine particles of zinc oxide-polymer composite] The method for producing fine particles of zinc oxide-polymer composite of the present invention comprises a mixture containing zinc, a monocarboxylic acid, a polymer and a medium.
The method includes a precipitation step of precipitating zinc oxide-polymer composite fine particles containing zinc oxide fine particles and a polymer by maintaining the temperature at 00 ° C or higher. The medium can dissolve or disperse zinc, a monocarboxylic acid, and a polymer, and is composed of at least alcohol.

In the manufacturing method of the present invention, the precipitation step is
It includes a first mixing step and a second mixing step. The first mixing step is a step of preparing a first mixture containing zinc and a monocarboxylic acid by mixing a zinc source and a monocarboxylic acid. The second mixing step is a step of preparing a second mixture in which zinc and a monocarboxylic acid are dissolved or dispersed in the medium by mixing the medium containing at least the alcohol and the first mixture.

The first mixing step may be a step of dissolving the zinc source in a mixed solvent of monocarboxylic acid and water. Second
The mixing step may be a step in which the first mixture is added to and mixed with the medium maintained at a temperature of 100 ° C. or higher.
The polymer used in the production method of the present invention is, for example,
It has one or more polar atomic groups. The polar atomic group is, for example, a carboxyl group, an amino group, a quaternary ammonio group, an amide group, an imide bond, a hydroxyl group, a carboxylic acid ester bond, a urethane group, a urethane bond, a ureido group, a ureylene bond, an isocyanate group, an epoxy group, It is at least one selected from the group consisting of a phosphoric acid group, a metal hydroxyl group, a metal alkoxy group, and a sulfonic acid group.

The zinc source used in the production method of the present invention is
Preferred is at least one zinc compound selected from the group consisting of zinc oxide, zinc hydroxide and zinc acetate. Monocarboxylic acid used in the production method of the present invention,
Preferred is a saturated fatty acid having a boiling point of 200 ° C. or lower at 1 atm. The amount of the polymer used in the production method of the present invention is, for example, 0.01 to 1.0 in terms of weight ratio to the amount of zinc oxide in the zinc source converted to zinc oxide. [Use of Zinc Oxide-Polymer Composite Fine Particles] (Coating Composition) The coating composition of the present invention comprises the zinc oxide-polymer composite fine particles of the present invention and a binder component capable of forming a transparent or translucent continuous phase. , A solvent that disperses the composite fine particles and disperses and / or dissolves the binder component.

The coating composition of the present invention can also form a transparent or translucent continuous phase with the zinc oxide-polymer composite fine particles produced by the method for producing zinc oxide-polymer composite fine particles of the present invention. It contains a binder component and a solvent in which the fine composite particles are dispersed and the binder component is dispersed and / or dissolved. In the coating composition of the present invention, for example,
The amount of the composite fine particles is 0.1 to 80% by weight based on the total solid weight of the composite fine particles and the binder component.

The coating composition of the present invention has, for example, a total solid content of the composite fine particles and the binder component of 1 to 80% by weight and an amount of the solvent of 10 with respect to the total amount of the coating composition.
~ 99% by weight. The coated article of the present invention comprises a transparent or semi-transparent base material and a coating film formed on the surface of the base material. This coating comprises the coating composition of the present invention. The substrate is, for example, at least one selected from the group consisting of resin molded products, glass and paper. The resin molded product is, for example, at least one selected from the group consisting of plates, sheets, films, and fibers.

The resin composition of the present invention contains the zinc oxide-polymer composite fine particles of the present invention and a resin capable of forming a transparent or translucent continuous phase. The resin composition of the present invention also comprises zinc oxide-polymer composite particles produced by the method for producing zinc oxide-polymer composite particles of the present invention,
And a resin capable of forming a transparent or translucent continuous phase.

In the resin composition of the present invention, for example, the amount of the fine composite particles is 0.1 to 80% by weight based on the total weight of the solid content of the fine composite particles and the resin. The resin molded product of the present invention is obtained by molding the resin composition of the present invention into a shape selected from the group consisting of plates, sheets, films and fibers. The paper of the present invention comprises paper-made pulp and zinc oxide-polymer composite fine particles of the present invention dispersed in the pulp, and / or zinc oxide-polymer composite fine particles made by the production method of the present invention. The amount of the fine composite particles is 0.01 to 50% by weight based on the pulp.

The cosmetic of the present invention comprises 0.1% of the zinc oxide-polymer composite fine particles of the present invention and / or zinc oxide-polymer composite fine particles produced by the production method of the present invention.
Contains more than wt%.

[0017]

[Explanation of means]

[Zinc Oxide-Polymer Composite Fine Particles] The zinc oxide-polymer composite fine particles of the present invention contain 50 to 99% by weight of zinc oxide fine particles as ZnO and 1 to 100% of the polymer, based on the total weight of the zinc oxide fine particles and the polymer. 50 wt%, preferably 70 to 90 wt% zinc oxide fine particles as ZnO and 5 to 30 wt% polymer. If the amount of zinc oxide fine particles is less than the above range, the ultraviolet ray shielding ability per composite fine particle may be lowered, and if it is more than the above range, the mechanical strength of the fine composite particles may be weak and may be impractical.

The zinc oxide constituting the composite fine particles of the present invention has excellent transparency to visible light, is not colored, and has a wide absorption wavelength of ultraviolet rays, so that it can efficiently block ultraviolet rays and has low toxicity. Is preferred. Zinc oxide crystals usually show an X-ray diffraction pattern of any of a hexagonal crystal (wurtzite structure), a cubic crystal (salt type structure) and a cubic face center structure.

In the fine composite particles of the present invention, if the amount of the fine zinc oxide particles is within the above range, a metal element other than zinc such as an alkali metal or an alkaline earth metal is complexed with the zinc oxide crystal as an atom or an ion. Fine particles, in which inorganic compounds such as oxides, hydroxides, sulfides, nitrides, carbides, and carbonates of metal elements other than zinc are solid-solved in zinc oxide crystals; silane-based, aluminum-based, Fine particles formed by coupling a zirconium-based or titanium-based coupling agent or an organometallic compound such as an organosiloxane or a chelate compound to the surface of a zinc oxide crystal or forming a coating layer on the surface; halogen element, sulfate group, nitrate group, etc. Inorganic acid radicals or organic compounds such as fatty acid radicals, alcohol residues, amine residues and the like may be included in the fine particles inside and / or on the surface thereof. In the composite fine particles of the present invention, the total weight of the zinc oxide fine particles and the polymer is preferably 75-
It is 100% by weight, more preferably 85 to 100% by weight. If the amount is less than the above range, the ultraviolet shielding ability per one composite fine particle may be reduced, or the mechanical strength of the composite fine particle may be weak, resulting in lack of practicality.

The shape and size of the fine composite particles of the present invention are not particularly limited. The composite fine particles of the present invention have a number average particle diameter of 0.1 to 10 μm on the major axis (L) basis.
m, the coefficient of variation of particle diameter is 30% or less, more preferably the number average particle diameter is 0.1 to 2 μm, and the coefficient of variation of particle diameter is 15%.
The following is practically useful. If the number average particle diameter is less than the above range, the dispersibility of the composite fine particles may be deteriorated, and if it exceeds the above range, the dispersion stability of the composite fine particles contained in the coating composition may be deteriorated. If the coefficient of variation of particle diameter exceeds the above range, the dispersibility and / or dispersion stability of the composite fine particles may be reduced, or the surface of the coating film or the molded article may be non-uniform.

The shape of the fine composite particles of the present invention is, for example, spherical, elliptic spherical, cylindrical, columnar, hexagonal columnar, spindle-shaped, quadrangular pyramid (pyramid), cubic or the like.
When the composite fine particles of the present invention have a spherical shape and / or an elliptic spherical shape, they are easy to disperse when blended into a paint or a resin, and are not easily crushed by mechanical shear.
The spherical shape means that the composite fine particles have a rounded shape as a whole, and the length (long diameter (L) / minor diameter (B)) is 1.0 or more and less than 1.2. Is defined as something. Ellipsoidal sphere means that the composite fine particles have a rounded shape as a whole, and the length (L / L)
B) is defined to be in the range of 1.2 or more and 5.0 or less. When the composite fine particles have a length (L / B) of more than 5.0, it is difficult to disperse in the resin,
Alternatively, it may be easily crushed due to mechanical shear. The major axis (L) is the longest length of the triaxial diameter measured for the composite fine particles, and the minor axis (B) is the larger one of the width and the height of the triaxial diameter. Is.

In the composite fine particles of the present invention, the zinc oxide fine particles may be uniformly dispersed throughout, or may be partially aggregated. In particular, when the zinc oxide fine particles aggregate to form the outer shell, the zinc oxide fine particles are localized in the outer shell in the composite fine particles to form a multilayer structure. In addition to light scattering (this corresponds to light scattering on the surface of conventional inorganic transparent fine particles), light scattering on the surface of zinc oxide fine particles in the composite fine particles and the outer shell in the fine particles of the composite Light scattering occurs at the interface with the inner shell, and high diffusivity is exhibited while having high light transmittance. The thickness of the outer shell formed by aggregating zinc oxide fine particles is not particularly limited, but is preferably 0.1 to the number average particle diameter value of the composite fine particles.
It is 0.4. If it is less than the above range, the mechanical strength of the composite fine particles may be lowered, and if it is more than the above range, the above effect due to the multilayer structure may not be sufficiently exhibited.

The shape and size of the zinc oxide fine particles are not particularly limited, but they must be smaller than the composite fine particles. For example, the composite fine particles are 0.1 to 10 μm.
When the number average particle diameter is (preferably 0.1 to 2 μm), the number average particle diameter of the zinc oxide fine particles is 0.00
It is 5 to 0.1 μm, which is 1/10 to 1/1000 of the number average particle diameter of the composite fine particles. If the number average particle diameter of the zinc oxide fine particles is less than the above range, the ultraviolet shielding ability of the zinc oxide fine particles may be reduced, and if it exceeds the above range, the light transmittance may be reduced. If the ratio of the number average particle diameter of the zinc oxide fine particles to the number average particle diameter of the composite fine particles is less than the above range, the ultraviolet shielding ability of the zinc oxide fine particles may be reduced, and if the ratio exceeds the above range, the composite fine particles are practical. May not have sufficient mechanical strength,
The combined effect may not be fully exerted.

In the composite fine particles of the present invention, when the zinc oxide fine particles aggregate to form the outer shell, the polymer is
It may be contained only in the outer shell, only in the inner shell, or in both the outer shell and the inner shell. However, it is preferable that the polymer is also contained only in the outer shell and the fine composite particles are hollow. When the composite fine particles are hollow, the light diffusion function is higher. When the polymer is present in the outer shell and covers the surface layer of the composite fine particles, the composite fine particles are excellent in dispersibility, and the binding property with the matrix polymer in the composition is further enhanced. In addition, when the composite fine particles have a large number of pores between the zinc oxide fine particles and when they are hollow, they function as porous fine particles or microcapsules, such as oil absorption ability, moisture absorption ability, and adsorption ability of harmful metal ions. Adsorption / separation / removal / collection functions such as absorption of toxic gases / odors; heat and sound insulation functions such as heat insulation and sound insulation (heat insulation fillers, sound insulation fillers); metal ion, enzyme / bacterial fixation Immobilization function (catalyst carrier, chromatographic packing material, etc.); Light weight; Sustained release function of liquids, fragrances, etc. held inside.

The polymer contained in the composite fine particles of the present invention is not particularly limited, but for example, the weight average molecular weight is 10
The number is from 0 to 1,000,000, and includes those generally referred to as oligomers and prepolymers. Such a polymer easily dissolves in the first mixture, the second mixture, or a heating process for precipitating the fine particles of the composite, or easily emulsifies or suspends in the finest possible state, so It is easy to obtain uniform composite particles having a uniform particle shape (the coefficient of variation of particle diameter is 30% or less). The polymer contained in the composite fine particles of the present invention is, for example, at least one resin selected from the following resin groups (1) to (14). When these resins are used, composite fine particles having an average particle diameter of 0.1 to 10 μm are easily obtained.

(1) Acrylic resin-based polymer Homopolymer / copolymer of (meth) acrylic monomer such as acrylic acid ester / methacrylic acid ester;
Maleic acid ester, itaconic acid ester-based monomer,
Vinyl-based monomers such as styrene, p-chlorostyrene, vinyltoluene, vinyl acetate, vinyl chloride, vinylmethyl ether, vinyl butyral, olefins such as ethylene and propylene, dienes such as butadiene, trienes, etc. (meth) acrylic Thermoplastic acrylic resins such as copolymers of polymerizable monomers having no functional group other than the system monomers and the (meth) acrylic monomers, modified products thereof, derivatives thereof (such as those having a substituent introduced), etc. Functional groups such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, (meth) acrylic acid hydroxyalkyl ester, (meth) acrylic acid glycidyl ester, (meth) acrylic acid aminoalkyl ester A polymerizable monomer having A polymerizable monomer having a functional group; serial copolymer of (meth) acrylic monomer
A thermosetting acrylic resin such as a copolymer of the (meth) acrylic monomer and a polymerizable monomer having no functional group, a modified product thereof, a derivative thereof (having a substituent introduced, a functional group of Etc.) etc.

(2) Alkyd resin type polymer Phthalic anhydride, isophthalic acid, terephthalic acid, benzoic acid, rosin, adipic acid, maleic anhydride, succinic acid,
Polybasic acids such as sebacic acid, fumaric acid anhydride, trimellitic acid, pyromellitic acid, and ethylene glycol, propylene glycol, neopentyl glycol, 1,6-hexanediol, glycerin, trimethylolethane,
Pentaerythritol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polycondensation products with polyhydric alcohols such as hydrogenated bisphenol A (oil-free alkyd resin); Modified products (alkyd resins) modified by, for example, natural resins such as rosin, synthetic resins such as phenolic resins, epoxy resins, urethane resins, silicone resins, amino resins, etc., above (1) Modified products modified with the listed monomers (rosin modified alkyd resin, phenol modified alkyd resin, epoxy modified alkyd resin, styrenated alkyd resin, acrylated alkyd resin, urethane modified alkyd resin, silicone modified alkyd resin, amino resin Modified alkyd resins such as modified alkyd resins); the polycondensates, the alkyd resins, derivatives of the modified alkyd resins (neutralized some or all of functional groups such as carboxyl groups, introduced with substituents, etc.) ).

(3) Amino resin type polymer Melamine resin such as melamine formaldehyde resin, butylated melamine resin, methylated melamine resin and benzoguanamine resin; urea resin such as urea formaldehyde resin, butylated urea resin and butylated urea melamine resin;
Amino resin-modified alkyd resin obtained by modifying the alkyd resin of the above (2) by a co-condensation reaction using a melamine resin or a urea resin; a modified product of the melamine resin, the urea resin, or the amino resin-modified alkyd resin (for example, methylation Methylol melamine, addition product of methylol melamine initial condensation product and polyhydric alcohol, condensation product of melamine or urea and polyhydric amine, butylated melamine with hydrophilic group introduced, benzoguanamine with hydrophilic group introduced, etc. Amino resin) etc.

(4) Vinyl resin type polymers Homopolymers / copolymers of vinyl type monomers such as vinyl chloride, vinyl acetate, vinyl propionate, vinylidene chloride, vinyl butyral, styrene, p-chlorostyrene and vinyltoluene (polyvinyl chloride). Vinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, ethylene-vinyl acetate copolymer, modified ethylene-vinyl acetate copolymer, polyvinyl butyral, polyvinyl alcohol, polystyrene, etc.); vinyl monomers and ethylene. Copolymers of olefins such as propylene, dienes such as butadiene, and other unsaturated monomers such as trienes; copolymers of vinyl-based monomers with the (meth) acrylic-based monomers and / or other unsaturated monomers Polymers; derivatives of those polymers.

(5) Epoxy resin type polymer Bisphenol A type epoxy resin, phenoxy resin (high molecular weight of bisphenol A type epoxy resin (molecular weight ≧ 3
10,000) type resin), phenol novolac type epoxy resin, orthocresol novolac type epoxy resin,
Glycidyl ether type epoxy resin such as bisphenol A novolac type epoxy resin, brominated phenol novolac type epoxy resin, tetraphenylolethane type epoxy resin; glycidyl ester type epoxy resin; glycidyl amine type epoxy resin; epoxidized polybutadiene; these epoxy resins A compound having active hydrogen such as an amino group, a carboxyl group, an amide group, a thiol group and / or a (pre) polymer (an aliphatic (poly) amine, an aromatic (poly)) capable of undergoing a crosslinking reaction with an epoxy group.
Polymers reacted with amines, diethylaminopropylamine, alicyclic amines, polymercaptans, etc.).

(6) Polyamide resin-based polymer Nylon resin (for example, nylon 66) obtained by polycondensation of diamine and dicarboxylic acid, nylon resin (for example, nylon 6) obtained by ring-opening polymerization of lactam, and polycondensation of amino acid The resulting polypeptide (eg, polyglycine, poly (α-L-alanine))
Etc.), a polyamine amide which may have an amino group, which is obtained by dehydration condensation of a polycarboxylic acid represented by a polymerized fatty acid (dimer acid) which is a polymer of a vegetable oil fatty acid and a polyamine such as ethylenediamine / diethylenepolyamine. Derivatives etc.

(7) Polyimide resin type polymer Polycondensation reaction of dianhydride of tetracarboxylic acid such as pyromellitic anhydride and aromatic diamine, bismaleimide such as bishexamethylene maleimide and biscyclopentadienyl compound Diels-Alder with 2,5-dimethyl-3,4-diphenylcyclopentadienone (Di
les-Alder) Polyimide polymer obtained by polymerization reaction.

(8) Polyurethane resin-based polymer Any resin having a urethane bond in the molecule may be used, for example, an alkyd resin in which a dibasic acid is replaced with a diisocyanate; a hydroxyl group such as methacrylic acid hydroxyester ( A polymer obtained by reacting an acrylic polymer obtained by polymerizing a monomer containing a (meth) acrylic monomer with an isocyanate compound; a polymer obtained by reacting a polyester polymer composed of a dibasic acid and an excess polyhydric alcohol with an isocyanate compound A polymer obtained by reacting an isocyanate compound with a polyalkylene glycol obtained by addition-polymerizing propylene oxide or ethylene oxide with a polyhydric alcohol; a polymer obtained by reacting an isocyanate compound with an epoxy resin having a hydroxyl group; Polyurethane resins conventionally used for paints such as urethane resins, heat-curable polyurethane resins, and catalyst-curable polyurethane resins; phenylglycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer, phenylglycidyl ether acrylate isophorone diisocyanate urethane prepolymer, Phenylglycidyl ether acrylate Tolylene diisocyanate urethane prepolymer / glycerin dimethacrylate hexamethylene diisocyanate urethane prepolymer / glycerin dimethacrylate isophorone diisocyanate urethane prepolymer / pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer / pentaerythritol triacrylate Prepolymers containing urethane bonds such as sophorone diisocyanate urethane prepolymers / pentaerythritol triacrylate tolylene diisocyanate urethane prepolymers and having a polymerizable double bond, homopolymers / copolymers of these prepolymers, Prepolymers and other polymerizable monomers (for example, (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylonitrile, (meth) acryl-based monomers such as (acrylamide); maleic acid, maleic acid ester, styrene , Styrene-based monomers such as p-chlorostyrene and vinyltoluene; olefins such as ethylene and propylene; dienes and trienes such as butadiene; vinyl acetate, vinyl chloride, vinyl methyl ether, vinyl alcohol, Vinyl monomers such as butyral)
Copolymers with; urethane acrylate polymers obtained by reacting polyisocyanates such as hexamethylene diisocyanate and toluylene diisocyanate with (meth) acrylic acid or (meth) acrylic acid oligomers.

(9) Polyester resin type polymers: Aliphatic glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, hydroquinone, resorcin, etc. At least one glycol selected from the group consisting of aromatic diols, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, and aromatic dicarboxylic acids such as (anhydrous) phthalic acid / isophthalic acid / terephthalic acid / naphthalenedicarboxylic acid, adipine Aliphatic dicarboxylic acid such as acid and sebacic acid,
Obtained by polycondensation with at least one dicarboxylic acid selected from the group consisting of alicyclic dicarboxylic acids such as cyclohexane-1,4-dicarboxylic acid and unsaturated dicarboxylic acids such as (anhydrous) maleic acid and fumaric acid. A saturated or unsaturated polyester polymer; a polymer obtained by polymerizing an unsaturated polyester with a polymerizable monomer such as styrene or (meth) acrylic acid ester.

(10) Phenol resin-based polymer A phenol resin generally obtained by polycondensing phenol such as phenol, alkyl-substituted phenol, allyl-substituted phenol and bisphenol A with formaldehyde, which is generally referred to as novolac type or resol type, and Derivatives obtained by modifying or substituting these phenolic resins.

(11) Organopolysiloxane polymer A polymer having a siloxane bond as a skeleton and an organic group containing a carbon atom directly bonded to a silicon atom in the siloxane bond (eg, an alkyl group) (eg, polydimethylsiloxane). , Polyalkyl siloxanes such as polymethylphenyl siloxane, etc.); those in which some of the organic groups in these polymers are bonded to silicon atoms through oxygen atoms, modifications in which some of the organic groups in these polymers have been modified Silicone (for example, alkyd-modified silicone, epoxy-modified silicone, polyester-modified silicone, acrylic-modified silicone, urethane-modified silicone, etc.) and the like.

(12) Acrylic Silicone Resin Polymer An organosilicon compound having a polymerizable double bond such as methacryloxypropyltrimethoxysilane and vinyltrimethoxysilane is copolymerized with an unsaturated monomer such as an acrylic monomer. The resulting polymer (for example, an acrylic copolymer containing an alkoxysilyl group) and the like.

(13) Fluororesin-based polymer Homopolymers / copolymers of fluorine-containing polymerizable monomers such as ethylene fluoride, vinylidene fluoride and vinyl fluoride, fluorine-containing polymerizable monomers, and other Copolymers with vinyl-based, olefin-based, acrylic-based, etc. polymerizable monomers.

(14) Other resin-based polymers Conventionally known resins such as xylene resin, petroleum resin, ketone resin, liquid polybutadiene, rosin-modified maleic acid resin and coumarone resin, and derivatives of these resins. A preferred polymer is because the composite fine particles have excellent chemical stability and mechanical properties such as solvent resistance and chemical resistance.
It has one or more polar atomic groups. Preferred polar atomic groups are carboxyl group, amino group (primary amino group, secondary amino group, tertiary amino group, imino group, imino bond), quaternary ammonio group, amide group, imide bond, hydroxyl group (alcoholic , Phenolic), carboxylic acid ester bond, urethane group, urethane bond, ureido group, ureylene bond, isocyanate group, epoxy group, phosphoric acid group, metal hydroxyl group, metal alkoxy group and sulfonic acid group. Is one. The reason is that not only the chemical stability of the composite fine particles is further enhanced, but also the mechanical strength such as crushing strength is excellent, and fine zinc oxide fine particles (average particle size 0.005 to 0.1 μm) are easily obtained. This is because it is easy to obtain composite fine particles having a uniform diameter (the coefficient of variation of particle diameter is 30% or less) and having a uniform particle shape. Examples of the polymer having one or more carboxyl groups include (meth) acrylic acid and 2-
Homopolymers / copolymers of carboxyl group-containing polymerizable monomers such as (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid, and maleic acid; A carboxyl group-containing polymerizable monomer,
(Meth) acrylic monomers such as (meth) acrylic acid ester / (meth) acrylamide / (meth) acrylonitrile, and (meth) such as α-chloromethyl methacrylate
Substituted acrylic monomer, maleic acid ester, styrene monomer such as styrene / p-chlorostyrene / vinyltoluene, olefins such as ethylene / propylene, diene or triene such as butadiene, vinyl acetate / vinyl chloride / vinyl methyl ether Copolymers with vinyl-based monomers such as vinyl butyral and vinyl alcohol, and polymerizable monomers such as polymerizable organosilicon compounds such as vinyltrimethoxysilane and methacryloxytrimethoxysilane; the alkyd resin-based polymers and polyester resin-based polymers Of the above, a polymer having a carboxyl group at the terminal or side chain; a carboxyl group having a carboxyl group at the terminal and / or side chain such as polydimethylsiloxane having carboxypropyl at the terminal or side chain Etc. Le-modified organopolysiloxane polymer is exemplified.

Polymers having one or more amino groups and / or quaternary ammonio groups include primary amino groups,
Any polymer having at least one selected from the group consisting of a secondary amino group, a tertiary amino group, an imino group, an imino bond and a quaternary ammonio group may be used, and examples thereof include dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate. , 4-vinylpyridine, p-
Homopolymers / copolymers of aminostyrene, imino group, ammonio group-containing polymerizable monomers such as aminostyrene, 3-vinylaniline, 4-vinylimidazole, vinylpyrrole, and dimethyldiallylammonium chloride; ) Acrylic acid, (meth) acrylic acid ester, (meth) acrylamide, (meth) acrylonitrile and other (meth) acrylic monomers, α-chloromethyl methacrylate and other (meth) acrylic monomer substitution products, maleic acid, maleic acid Acid ester, styrene
Styrene-based monomers such as p-chlorostyrene / vinyltoluene, olefins such as ethylene / propylene, dienes or trienes such as butadiene, vinyl-based monomers such as vinyl acetate / vinyl chloride / vinyl methyl ether / vinyl butyral / vinyl alcohol, Copolymer with a polymerizable monomer such as a polymerizable organosilicon compound such as vinyltrimethoxysilane / methacryloxytrimethoxysilane; a polymer having an amino group in the polyamide resin-based polymer; the amino resin-based polymer; Amino-modified organopolysiloxane-based polymers having amino groups at the terminal and / or side chains, such as polydimethylsiloxane having a dimethylamino group or aminopropyl group in the side chain; polyethyleneimine,
Polymers of alkyleneimines such as polypropyleneimine;
Polymers such as pyrrolidine and piperidine; halogenated polydiallylammonium; ionene compounds; chitosan;
Examples thereof include porphines such as tetramethylporphine and tetraphenylporphine.

Examples of the polymer having one or more amide groups include homopolymers / copolymers of amide group-containing polymerizable monomers such as (meth) acrylamide and 2-acrylamido-2-methylpropanesulfonic acid; And a (meth) acrylic acid / (meth) acrylic acid ester / (meth) acrylonitrile etc., (meth) acrylic monomer substitution product such as α-chloromethyl methacrylate, maleic acid, Maleic acid esters, styrene-based monomers such as styrene / p-chlorostyrene / vinyltoluene, olefins such as ethylene / propylene, dienes or trienes such as butadiene, vinyl acetate / vinyl chloride / vinyl methyl ether / vinyl butyral / vinyl alcohol. Vinyl monomers such as vinyl Copolymer with a polymerizable monomer such as a polymerizable organosilicon compound such as trimethoxysilane / methacryloxytrimethoxysilane; the above polyamide resin-based polymer; an amide-modified organopolysiloxane having an amide group at the terminal and / or side chain Examples include polymer-based polymers.

Examples of the polymer having one or more imide bonds include the above-mentioned polyimide resin polymers and the like. Examples of the polymer having one or more alcoholic hydroxyl groups include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, glycerin dimethacrylate, glycerol monomethacrylate, 3-chloro-2-hydroxypropyl methacrylate, 2-acryloyloxyethyl-
2-hydroxyethylphthalic acid, pentaerythritol triacrylate, 2-hydroxy-3-phenoxypropyl acrylate, bisphenol A-diepoxy-
(Meth) acrylic acid adducts, homopolymers / copolymers of hydroxyl group-containing polymerizable monomers such as vinyl alcohol; these monomers, and (meth) acrylic acid / (meth) acrylic acid ester / (meth) acrylonitrile / ( (Meth) acryl-based monomers such as (meth) acrylamide, (meth) acryl-based monomer substitution products such as α-chloromethyl methacrylate, maleic acid, maleic acid ester, styrene-based monomers such as styrene / p-chlorostyrene / vinyltoluene , Olefins such as ethylene and propylene, dienes and trienes such as butadiene, vinyl-based monomers such as vinyl acetate, vinyl chloride, vinyl methyl ether, vinyl butyral, and polymerizable organics such as vinyltrimethoxysilane and methacryloxytrimethoxysilane. Polymerizability of silicon compounds Copolymer with Nomer; Cellulose-based Polymers such as Hydroxypropyl Cellulose / Methyl Cellulose / Hydroxyethyl Methyl Cellulose; Polyamide Resin-based Polymers Obtained by Condensation Reaction of Polyamines with Polybasic Acids such as Aliphatic Dicarboxylic Acids; Examples thereof include polydimethylsiloxane which is hydroxypropyl, polydimethyl-hydroxyalkylene oxide methylsiloxane, and other organopolysiloxane polymers having an alcoholic hydroxyl group at the terminal and / or side chain.

Examples of the polymer having one or more phenolic hydroxyl groups include the above-mentioned phenol resin-based polymers. Examples of the polymer having one or more carboxylic acid ester bonds include, for example, methyl methacrylate / ethyl methacrylate / butyl methacrylate / isobutyl methacrylate / isoamyl acrylate / 2-ethylhexyl methacrylate / isodecyl methacrylate / n-lauryl (meth) acrylate /
Benzyl acrylate / tridecyl methacrylate / n
-Stearyl (meth) acrylate, isooctyl acrylate, isostearyl methacrylate, behenyl methacrylate, butoxyethyl acrylate, methoxydiethylene glycol methacrylate, n-butoxyethyl methacrylate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol acrylate, methoxypolyethylene glycol methacrylate.
Cyclohexyl methacrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, benzyl methacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,
6-hexanediol dimethacrylate / trimethylolpropane tri (meth) acrylate / glycerin dimethacrylate / trifluoroethyl methacrylate / pentaerythritol triacrylate / pentaerythritol tetraacrylate / dipentaerythritol hexaacrylate / neopentyl glycol acrylic benzoate ester / 3 -(Meth) acrylic acid esters such as acryloyloxyglycerin monomethacrylate / propylene oxide modified bisphenol A diacrylate / hydrogenated dicyclopentadienyl diacrylate / perfluorooctylethyl acrylate, methyl maleate
Homopolymers / copolymers of maleic acid esters such as butyl maleate, vinyl acetate, carboxylic acid ester-containing polymerizable monomers such as methacryloxypropyltrimethoxysilane; these monomers and other monomers ((meth) acrylic) Acid / (meth) acrylonitrile / (meth)
(Meth) acrylic monomers such as acrylamide, maleic acid, styrene monomers such as styrene / p-chlorostyrene / vinyltoluene, olefins such as ethylene / propylene, dienes or trienes such as butadiene, vinyl chloride / vinyl methyl ether Copolymers with vinyl monomers such as vinyl alcohol and vinyl butyral, and polymerizable monomers such as polymerizable organosilicon compounds such as vinyltrimethoxysilane; the above polyester resin polymers; polydimethylsiloxanes such as acetoxy and stearyloxy at the ends. Examples thereof include organopolysiloxane-based polymers having an ester bond at the terminal and / or side chain.

Examples of the polymer having one or more urethane groups and / or urethane bonds include the above-mentioned polyurethane resin-based polymers. Examples of the polymer having one or more ureido groups and / or ureylene bonds include polyurea obtained by a polycondensation reaction of nonamethylenediamine and urea.

Examples of the polymer having one or more isocyanate groups include polymethylene polyphenyl polyisocyanate; polyol-modified isocyanate; polyfunctional aromatic or polyfunctional aliphatic isocyanate compounds such as hexamethylene diisocyanate and toluylene diisocyanate. React with a (pre) polymer containing a functional group having active hydrogen such as amino group, carboxyl group and hydroxyl group (a part of the isocyanate group contained in the isocyanate compound reacts with a functional group having active hydrogen)
Examples thereof include polymers obtained.

Examples of the polymer having one or more epoxy groups include glycidyl methacrylate and N-.
Homopolymers / copolymers of epoxy group-containing polymerizable monomers such as epoxy group-containing (meth) acrylic monomers such as [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide; Monomers, which do not react with epoxy groups in the polymerization process, for example, (meth) acrylic monomers such as (meth) acrylic acid esters, (meth) acrylic monomer substitution products such as α-methyl chloromethacrylate, maleic acid esters,
Styrene-based monomers such as styrene / p-chlorostyrene / vinyltoluene, olefins such as ethylene / propylene, dienes or trienes such as butadiene, vinyl acetate / vinyl chloride / vinyl methyl ether / vinyl butyral / vinyl alcohol, etc. Monomers, copolymers with polymerizable monomers such as polymerizable organosilicon compounds such as vinyltrimethoxysilane and methacryloxytrimethoxysilane; the above epoxy resin-based polymers; polydimethylsiloxane having glycidoxypropyl at the end, poly Examples thereof include organopolysiloxane-based polymers having a glycidoxy group at the terminal and / or side chain such as glycidoxypropylmethylsiloxane and polyglycidoxypropylmethyl-dimethylsiloxane copolymer.

Examples of the polymer having one or more phosphoric acid groups include phosphorus such as mono (2-methacryloyloxyethyl) acid phosphate, mono (2-acryloyloxyethyl) acid phosphate, and 2-acryloyloxyethyl acid phosphate. Homopolymers / copolymers of acid group-containing polymerizable monomers; these monomers and (meth) acrylic monomers such as (meth) acrylic acid / (meth) acrylic acid ester / (meth) acrylonitrile / (meth) acrylamide , (Meth) acrylic monomer substitution products such as α-chloromethyl methacrylate, maleic acid, maleic acid ester, styrene / p-
Styrene-based monomers such as chlorostyrene and vinyltoluene, olefins such as ethylene and propylene, dienes and trienes such as butadiene, vinyl-based monomers such as vinyl acetate, vinyl chloride, vinyl methyl ether, vinyl alcohol, vinyl butyral, and vinyl triene. Examples thereof include copolymers with polymerizable monomers such as polymerizable organic silicon compounds such as methoxysilane and methacryloxytrimethoxysilane.

Examples of the polymer having one or more metal hydroxyl groups and / or metal alkoxy groups include a silicon compound having a polymerizable double bond such as methacryloxypropyltrimethoxysilane, and (meth) acrylic acid. ( (Meth) acrylic acid ester, (meth) acrylonitrile, (meth) acrylamide and other (meth) acrylic monomers, α-chloromethacrylate and other (meth) acrylic monomer substitution products, maleic acid, maleic acid ester, styrene Styrene-based monomers such as p-chlorostyrene / vinyltoluene, olefins such as ethylene / propylene, dienes or trienes such as butadiene, vinyl-based monomers such as vinyl acetate / vinyl chloride / vinyl methyl ether, vinyltrimethoxysilane / methacryloxy. Copolymers with polymerizable monomers such as polymerizable organosilicon compounds such as remethoxysilane; and polymers obtained by (partly) hydrolyzing the alkoxysilyl groups in these copolymers; polydimethyl having silanol at the end Siloxane, silanol-terminated polydiphenylsiloxane, silanol-terminated polydimethyl-diphenylsiloxane, silanol-containing organopolysiloxanes such as polytetramethyl-p-silphenylene siloxane; (N-trimethoxysilylpropyl) polyethylene Imines, (N-trimethoxysilylpropyl) -o-polyethylene oxide urethane, triethoxysilyl modified poly (1,2-butadiene) and polymers obtained by (partial) hydrolysis of alkoxysilyl groups in these polymers; Acry Examples include silicone resin-based polymers.

Examples of the polymer having one or more sulfonic acid groups include acrylamide group-containing polymerizable monomers such as acrylamidomethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and their sodium salts. Polymers / copolymers; these monomers, and (meth) acrylic acid / (meth) acrylic acid ester / (meth) acrylonitrile / (meth) acrylamide and other (meth) acrylic monomers, α-chloromethyl methacrylate, etc. (Meth) acrylic monomer substitution product, maleic acid, maleic acid ester, styrene p-
Styrene-based monomers such as chlorostyrene and vinyltoluene, olefins such as ethylene and propylene, dienes and trienes such as butadiene, vinyl-based monomers such as vinyl acetate, vinyl chloride, vinyl methyl ether, vinyl alcohol, vinyl butyral, and vinyl triene. Copolymers with polymerizable monomers such as polymerizable organosilicon compounds such as methoxysilane and methacryloxytrimethoxysilane;
Examples thereof include sulfonic acid group-containing polymers obtained by reacting a styrene-based polymer with a sulfonating agent such as concentrated sulfuric acid, chlorosulfonic acid and sulfuric anhydride.

Examples of polymers having other polar atomic groups include poly-N-formylethyleneimine and poly-N-acetylethyleneimine obtained by ring-opening polymerization of oxazoline, 2-methyloxazoline and the like. (2-) Ring-opening compounds of cyclic imino ethers such as (2) substituted oxazoline and / or (2-substituted) oxazine; Among polymers having at least one functional group, such as ring copolymers, polymers having a structure used for a chelate resin having a coordination group (functional group) capable of coordinating a metal ion (for example, polyvinyl alcohol, polyvinyltriene). Acrylic methane, polyvinyl methacryloylacetone, poly (4
-Hydroxystyrene), pyrogallol phenol formaldehyde resin, salicylic acid formaldehyde resin,
Polyvinyl salicylic acid, polyacrylic acid, polymethacrylic acid, polyitaconic acid, aminophenol formaldehyde resin, poly (8-hydroxy-5-vinylquinoline), polyvinylamine, polyethyleneimine, poly (4-aminostyrene), poly (3-vinyl) (Aniline), poly (4-vinylpyridine), poly (4-vinylbipyridine), poly (4-vinylimidazole), polyvinylpyrrole, polyglycine, poly (α-L-alanine), etc.) with metal ions partially Or a polymer formed by adsorption coordination with all coordination groups (functional groups); carboxyl groups, sulfonic acid groups, etc., of metal salts such as alkali metals such as sodium and potassium, alkaline earth metals such as magnesium and calcium Examples include shaped polymers and the like.

Among the polymers exemplified in the above (1) to (14), (meth) acrylic type, styrene type, vinyl type,
At least one main chain selected from the group consisting of copolymerization system, alkyd system, polyester system, and polyamide system, and a group consisting of carboxyl group, amino group, amide group, silanol group, and alkoxysilyl group. A polymer having at least one polar atomic group is preferable because it is easy to obtain hollow, spherical composite fine particles having a multilayer structure. However, it is preferable to appropriately select the amount of the polymer to be used, the equivalent of the polar atomic group, the composition of the reaction liquid (solvent composition, etc.) at the time of forming the composite fine particles, depending on the kind of the polymer.

Since the composite fine particles of the present invention have excellent heat resistance, they can be blended with a resin having a high molding temperature, such as polyester and polycarbonate. After forming the film, it is possible to heat at a high temperature, and the particles are not thermally limited. [Method for producing zinc oxide-polymer composite fine particles] The method for producing the composite fine particles of the present invention is not particularly limited. The composite fine particles of the present invention can be produced with good productivity by the production method of the present invention.

According to the production method of the present invention, zinc oxide fine particles and a polymer are contained by maintaining a mixture containing zinc, a monocarboxylic acid, a polymer and a medium containing at least an alcohol at a temperature of 100 ° C. or higher. Precipitate zinc oxide-polymer composite particles. The zinc used in the present invention is supplied from at least one zinc source selected from the group consisting of metallic zinc and zinc compounds. The zinc source is not particularly limited, but includes metallic zinc (zinc dust), zinc oxide (zinc white, etc.), zinc hydroxide, basic zinc carbonate, and a mono- or di-carboxylic acid salt which may have a substituent (for example, Zinc acetate, zinc octylate, zinc stearate,
Zinc oxalate At least one selected from the group consisting of zinc lactate, zinc tartrate and zinc naphthenate) is preferred. When these zinc sources are used, the desalting step is unnecessary, and the number of steps is smaller than when zinc chloride, zinc nitrate or zinc sulfate, which requires the desalting step, is used.

Among them, at least one zinc source selected from the group consisting of metallic zinc (zinc dust), zinc oxide (zinc white), zinc hydroxide, basic zinc carbonate and zinc acetate is
It is preferable because it is inexpensive and easy to handle. At least one zinc source selected from the group consisting of zinc oxide, zinc hydroxide and zinc acetate is more preferable because it easily controls the size and shape of the zinc oxide fine particles.

Zinc oxide and / or zinc hydroxide are particularly preferable because they are available at a low price and the kind of monocarboxylic acid can be arbitrarily selected. The amount of zinc source is
The amount is, for example, 0.1 to 95% by weight, preferably 0.5 to 50% by weight, and more preferably 1 to 30% by weight, calculated as ZnO, based on the total charged amount of the medium composed of the monocarboxylic acid and the at least alcohol. is there. If it is less than the above range, the productivity may be lowered, and if it is more than the above range, secondary agglomeration of the composite fine particles may easily occur, and it may be difficult to obtain the composite fine particles having good dispersibility and uniform particle size distribution.

The monocarboxylic acid used in the present invention is a compound having only one carboxyl group in the molecule.
Specific examples of the compound include saturated fatty acids (saturated monocarboxylic acids) such as formic acid, acetic acid, propionic acid, isobutyric acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, and stearic acid; acrylic acid, methacrylic acid. Unsaturated fatty acids (unsaturated monocarboxylic acids) such as crotonic acid, oleic acid, and linolenic acid; cyclic saturated monocarboxylic acids such as cyclohexanecarboxylic acid; benzoic acid, phenylacetic acid,
Aromatic monocarboxylic acids such as toluic acid; the above monocarboxylic acid anhydrides such as acetic anhydride; halogen-containing monocarboxylic acids such as trifluoroacetic acid, monochloroacetic acid and o-chlorobenzoic acid. Any of these compounds may be used alone, or two or more compounds may be used in combination.

The preferred monocarboxylic acid is 20 at 1 atmosphere.
It is a saturated fatty acid having a boiling point of 0 ° C or lower. Specifically, formic acid, acetic acid, propionic acid, butyric acid, and isobutyric acid are preferable. The reason is that it is easy to control the content of the monocarboxylic acid in the reaction system during the heating process from the preparation process of the mixture, and thus it is easy to strictly control the precipitation reaction of zinc oxide crystals. The saturated fatty acid is preferably used in the range of 60 to 100 mol%, more preferably 80 to 100 mol% based on the total amount of monocarboxylic acid. If it is less than the above range, the crystallinity of zinc oxide in the obtained composite fine particles may be lowered.

The monocarboxylic acid also includes a monocarboxylic acid salt of zinc such as zinc acetate, and when the zinc salt is used, it is not always necessary to separately add the monocarboxylic acid as a raw material. The amount of the monocarboxylic acid used (or charged) in order to obtain the first mixture is, for example, 0.5 to 50, preferably 2.2 to 10, in a molar ratio with respect to the amount of Zn atoms in the zinc source. Within the above range, it is preferable from the viewpoints of economical efficiency, easiness of formation of composite fine particles, and ease of obtaining composite fine particles which are hard to aggregate and have excellent dispersibility. If it is less than the above range, it may be difficult to obtain zinc oxide fine particles having good crystallinity and complex fine particles having high uniformity in shape and particle diameter, and if it exceeds the above range, not only the economical efficiency is deteriorated,
It may be difficult to obtain composite fine particles having good dispersibility.

The alcohol used in the present invention includes aliphatic monohydric alcohols (methanol, ethanol, isopropyl alcohol, n-butanol, t-butyl alcohol, stearyl alcohol, etc.) and aliphatic unsaturated monohydric alcohols (allyl alcohol, chloro alcohol). Chill alcohol, propargyl alcohol, etc.), alicyclic monohydric alcohol (cyclopentanol, cyclohexanol, etc.), aromatic monohydric alcohol (benzyl alcohol, cinnamyl alcohol, methylphenylcarbinol, etc.), heterocyclic monohydric Monohydric alcohols such as alcohols (furfuryl alcohol, etc.); alkylene glycols (ethylene glycol, propylene glycol, trimethylene glycol, 1,4
-Butanediol, 1,5-pentanediol, 1,6
-Hexanediol, 1,8-octanediol, 1,
10-decanediol, pinacol, diethylene glycol, triethylene glycol, etc., aliphatic glycols having an aromatic ring (hydrobenzoin, benzpinacol, phthalyl alcohol, etc.), alicyclic glycols (cyclopentane-1,2-diol) , Cyclohexane-
1,2-diol, cyclohexane-1,4-diol, etc.), glycols such as polyoxyalkylene glycol (polyethylene glycol, polypropylene glycol, etc.); ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, triethylene glycol monomethyl ether, Monoethers and monoesters of the above glycols such as ethylene glycol monoacetate; aromatic diols such as hydroquinone, resorcinol, 2,2-bis (4-hydroxyphenyl) propane and their monoethers and monoesters; glycerin and the like 3 Examples thereof include polyhydric alcohols and their monoethers, monoesters, diethers and diesters. Any one of these alcohols may be used alone, or two or more may be used in combination.

The amount of alcohol in the medium containing at least alcohol is not particularly limited, but in order to carry out the zinc oxide fine particle formation reaction in a short time, the molar ratio of alcohol to Zn atoms derived from the zinc source is preferably. It is 1 to 100, more preferably 5 to 80. If it is less than the above range, it may be difficult to obtain zinc oxide fine particles having good crystallinity, or it may be difficult to obtain composite fine particles excellent in dispersibility, uniformity of shape and particle diameter, and if it exceeds, it is economically disadvantageous. There is a possibility.

The medium is a medium consisting only of the above alcohol, a mixed solvent of the above alcohol and water, the above alcohol and an organic solvent other than alcohol such as ketones, esters, aromatic hydrocarbons and ethers. A mixed solvent of the above, and the ratio of the above alcohol to another solvent is the second
5-100 wt% alcohol, preferably 40-1 in terms of the amount of charge (used) used for preparing the mixture
It is 00% by weight, more preferably 60 to 100% by weight. If the amount of alcohol is less than the above range, it may be difficult to obtain fine composite particles having good crystallinity, shape / particle size uniformity, and dispersibility.

The polymer used in the production method of the present invention is the same as that described for the polymer contained in the composite fine particles of the present invention. The amount of the polymer used is not particularly limited, but is in the range of 0.01 to 1.0 in terms of weight ratio to the amount of zinc atoms in the zinc source (that is, in the second mixture) converted to zinc oxide. Done in. If it is less than the above range, it is difficult to obtain the composite fine particles, and if it is more than the above range, the precipitation reaction of the zinc oxide crystals may be difficult to occur, so that the desired composite fine particles are not easily obtained. Depending on the type of polymer and other reaction conditions, in order to obtain composite fine particles having the above-mentioned multi-layer structure and having a uniform particle shape and particle size and good dispersibility, the amount of the polymer should be the above-mentioned oxidation. 0.05 ~ for zinc equivalent
A weight ratio of 0.8 is preferred.

In the manufacturing method of the present invention, it is preferable that the precipitation step has a first mixing step and a second mixing step. First
The mixing step is a step of mixing the zinc source and the monocarboxylic acid to produce a first mixture containing zinc and the monocarboxylic acid. The second mixing step is a step of preparing a second mixture in which zinc and monocarboxylic acid are dissolved or dispersed in the medium by mixing the medium containing at least the alcohol and the first mixture.

In the production method of the present invention, the polymer is the first
It is added in any one of the mixing step, the second mixing step, and the temperature holding step of holding the second mixture at a temperature of 100 ° C. or higher, or two or more steps. The addition of the polymer is performed at any time until the fine composite particles are deposited. For example, in the first mixing step, it is added and mixed in the first mixture, in the second mixing step, it is added and mixed in the second mixture, and in the step of maintaining the second mixture at a temperature of 100 ° C. or higher, it is added and mixed. The method of doing is illustrated.

In the manufacturing method of the present invention, the first mixing step is
The step of dissolving the zinc source in a mixed solvent of monocarboxylic acid and water is preferable. By this first mixing step, a solution-like first mixture is obtained. In the manufacturing method of the present invention,
It is preferable that the second mixing step is a step in which the first mixture is added to and mixed with the medium maintained at a temperature of 100 ° C. or higher. A second mixture is produced by this second mixing step.

When the first mixture of the zinc source and the monocarboxylic acid is added to the medium of at least the alcohol, it is preferred that the first mixture is a solution. When the first mixture is a solution, it is desirable that the zinc source and the monocarboxylic acid are compatible with each other or that they are dissolved in a solvent having high compatibility with them. The solvent used for that purpose is a zinc source and a monocarboxylic acid at room temperature to 100 ° C.
It can be easily dissolved at temperatures up to a certain level, and
Water, alcohols, ketones, and esters are preferable because they have high compatibility with a medium containing at least alcohol. The alcohols mentioned here include all of the above-mentioned alcohols.

The addition and mixing of the first mixture may be carried out under normal pressure, elevated pressure or reduced pressure, but it is preferable to be conducted under ordinary pressure in view of production cost. When adding and mixing under normal pressure,
When it is desired to obtain a dispersion of fine composite particles which is highly uniform in particle size, shape and the like and which is excellent in dispersibility, a medium consisting of at least alcohol during addition and mixing is used at a temperature of 60 ° C. or higher, particularly 100 ° C. or higher 300 It is preferable to keep the temperature below ℃. The temperature of the medium during addition and mixing is 6
If the temperature is lower than 0 ° C., the viscosity of the second mixture may rapidly increase during or after the addition and mixing, and the second mixture may become a gel. In such a case, stirring is impossible and uniform mixing cannot be achieved, or heat transfer is insufficient during the next step, that is, heating, which causes a problem such as temperature distribution.
It is difficult to obtain uniform composite fine particles in terms of crystallinity, particle diameter, particle shape and the like. Such a problem is related to the zinc concentration in the second mixture and is more likely to occur when the zinc concentration is higher. The lower limit temperature of these optimum temperatures differs depending on the pressure of the system, and when performing under reduced pressure or increased pressure, it is necessary to appropriately select the temperature of the medium according to the pressure. When the first mixture is added while maintaining the medium at a temperature within the above range, a part of the monocarboxylic acid and / or a part of the alcohol may be distilled out of the system by evaporation.

The method of adding the first mixture to the medium is, for example, a method of adding and mixing the first mixture to the medium all at once, a method of dropping the first mixture into the medium, or a first method. A method of spraying the mixture onto the medium can be adopted. Above all, the method of continuously or intermittently dropping the first mixture onto or in the medium is preferable because it is easy to obtain the composite fine particles having high productivity and excellent dispersibility.

The first mixture prepared as described above is treated, for example, at 60 ° C. or higher, preferably 100 ° C. or higher, 30
A second mixture is obtained by adding and mixing to the medium heated and maintained at a temperature below 0 ° C. When obtaining the second mixture by adding the first mixture to the medium, the volatile components (monocarboxylic acid, alcohol, water, etc.) in the first mixture and / or the second mixture are added while distilling off some of them. It is preferable to employ (dropping, etc.).

It is particularly preferable that the medium composed of at least alcohol is agitated in order to obtain a uniform mixture when the first mixture is added and mixed. In the production method of the present invention, the polymer may be added in any of the above steps as long as it is a stage before the formation of the composite fine particles. The polymer is preferably dissolved in the alcohol used for the medium in advance or dissolved in any solvent and added to the reaction system because the polymer can be rapidly spread in the reaction system. The solvent used for dissolving the polymer is not particularly limited as long as it is a liquid capable of dissolving the polymer, and examples thereof include alcohols (described above), aliphatic and aromatic carboxylic acids, aliphatic and aromatic carboxylic acid esters. At least one selected from the group consisting of water, mineral oils, vegetable oils, wax oils, and silicone oils, organic solvents such as water, ketones, ethers, ether esters, aliphatic and aromatic hydrocarbons, and halogenated hydrocarbons. Is one.

The second mixture may be obtained by mixing three components of zinc, a monocarboxylic acid and an alcohol as essential components, and the polymer may be obtained before the zinc oxide-polymer composite fine particles are formed. If necessary, components other than the three components, for example, water; organic solvents such as ketones, esters, (cyclo) paraffins, ethers, aromatic compounds; components such as additives described below; It may contain a metal component other than zinc (for example, an inorganic salt such as a metal acetate, nitrate or chloride, or an organic metal alkoxide such as a metal alkoxide). Water and an organic solvent are usually contained as solvent components.

The state of the second mixture is not particularly limited and may be, for example, a solution, a sol, an emulsion or a suspension. The second mixture obtained as described above is 100 ° C. or higher, preferably 100 to 300 ° C., more preferably 150 to 2
By maintaining the temperature in the range of 00 ° C. for 0.1 to 30 hours, preferably 0.5 to 10 hours, the composite fine particles of the present invention depending on the kind of raw material and the composition ratio can be produced with practical productivity. can get. That is, the zinc dissolved or dispersed in the medium is converted into crystalline zinc oxide by X-ray diffraction when the second mixture is maintained at the temperature within the above range for the time within the above range. . Since the polymer is also dissolved or dispersed in the medium, a nucleus containing zinc oxide crystals is deposited, and the polymer is compounded in the process of crystallization, so that a dispersion containing zinc oxide-polymer composite fine particles is formed. Is obtained. The type of polymer used, the type of raw material such as the type of alcohol contained in the medium, the composition of the starting material, and the reaction liquid composition when the composite fine particles are formed based on the temperature history until the formation of the composite fine particles By controlling the temperature and the like, it is possible to control the internal structure, particle shape and particle diameter of the composite fine particles, the particle diameter of the zinc oxide fine particles contained, and the like.

The form of existence of each component in the second mixture is not particularly limited. In the above reaction process, zinc dissolved or dispersed in the medium may pass through one or more zinc oxide precursors in the process of being converted into zinc oxide crystals. For example, there is a case where zinc oxide or the like is used for zinc or its compound. The zinc oxide precursor means a state of an ion or compound containing at least a zinc atom other than zinc oxide, such as zinc (hydrate)
Ion (Zn ²⁺ ), polynuclear hydroxide ion of zinc, (basic) zinc acetate, (basic) zinc salicylate, (basic)
The case where it exists as a (basic) carboxylic acid salt such as zinc lactate and the like can be mentioned. A case where a part or all of the precursor is present as a complex composition such as a complex salt with a monocarboxylic acid and / or alcohol is also included.

By setting the temperature of the second mixture within the above range, the composition of the reaction system including the rate and amount of evaporation and removal of excess or unnecessary components is strictly controlled in order to obtain zinc oxide fine particles. Therefore, there is an advantage that it is easy to control the particle diameter and the like of the resulting composite fine particles. For example, when the second mixture having a temperature of 100 ° C. or higher is obtained by adding and mixing the first mixture to the medium having a temperature of 100 ° C. or higher, as it is,
The temperature may be maintained, or the temperature may be raised or lowered to 100 ° C. or higher and then heated, or the first mixture may be added to and mixed with the medium having a temperature lower than 100 ° C. to obtain a second mixture. In that case, the temperature may be raised to 100 ° C. or higher.

In the process of converting zinc in the second mixture into fine particles of zinc oxide, the monocarboxylic acid in the second mixture does not change, or part or all of it is a part of the alcohol in the second mixture. Alternatively, an esterification reaction is caused with all of them to form an ester compound. In the process for obtaining the dispersion, alcohol, the ester compound produced by heating, or, if necessary, a part of the solvent present in the mixture may be removed by evaporation.

When the second mixture contains water, distillation is carried out until the amount of free water in the obtained dispersion is preferably 5% by weight or less, more preferably 1% by weight or less. It is preferable. When the amount of water exceeds the above range, the crystallinity of the zinc oxide crystals in the composite fine particles becomes low and the function as zinc oxide is sufficiently exhibited depending on the type of other components such as alcohol contained in the dispersion. It may not be done.

As the final composition in the produced composite fine particle dispersion, the amount of the monocarboxylic acid is based on the total amount of zinc atoms contained in the produced dispersion in terms of zinc atom.
It is preferably 0.5 times or less mol. The reason is,
This is because when the amount is more than 0.5 times by mole, the crystallinity of the zinc oxide fine particles becomes low and the function as zinc oxide may not be sufficiently exhibited. Therefore, when the amount of the monocarboxylic acid present in the second mixture exceeds 0.5 times the total amount of zinc atoms contained in the resulting dispersion in terms of zinc atoms, the heating step is performed. Therefore, it is necessary to distill at least the excess amount. Of course, even if the above ratio is 0.5 times or less, the distillation may be carried out in the process of heating.

The particle diameter of the finally obtained composite fine particles,
A long-chain saturated fatty acid (for example, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid or the like having 6 to 20 carbon atoms) among monocarboxylic acids is used for the purpose of controlling particle shape, surface polarity, and the like. It is also possible that a fatty acid) and / or a specific additive coexist during the heating process. The timing of addition of the additive is not particularly limited, and may be any of the step of preparing the first mixture or the second mixture or the step of heat treatment, and is appropriately selected according to the purpose and the kind of the additive. For the purpose of surface treatment, it is preferably added after the composite fine particles of the present invention are formed.

The specific additives include aliphatic amines such as octadecylamine and stearylamine, methyltrimethoxysilane, phenyltrimethoxysilane, benzyltriethoxysilane, γ-aminopropyltriethoxysilane, N-β (amino). Ethyl) γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, stearyltrimethoxysilane, etc. Silane coupling agents: isopropyltriisostearoyl titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, tetraoctyl bis (ditridecyl phosphite) titanate, isopropyl Titanate coupling agents such as tri (N-aminoethylaminoethyl) titanate; various coupling agents such as aluminum coupling agents such as ethyl acetoacetate aluminum diisopropylate, and partial hydrolysis products thereof, trimethyl phosphate. , Triethyl phosphate, tributyl phosphate, tris (2-chloroethyl) phosphate, (polyoxyethylene) bis [bis (2-chloroethyl) phosphate] and other phosphates; methyl acid phosphate, propyl acid phosphate,
Lauryl acid phosphate, stearyl acid phosphate, bis-2-ethylhexyl phosphate,
Acidic phosphoric acid esters such as diisodecyl phosphate; Phosphorous acid esters such as trimethyl phosphite; Organic phosphorus compounds such as thiophosphoric acid esters such as dimethyldithiophosphoric acid and diisopropyldithiophosphoric acid, sodium lauryl sulfate, dodecylbenzene sulfonic acid (sodium),
Sodium polyoxyethylene lauryl ether sulfate,
Anionic surfactants such as sodium dialkylsulfosuccinate, calcium stearate, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene alkylamine, polyethylene glycol monolaurate, glycerol monostearate,
Examples include cationic surfactants such as lauryldimethylamine and stearyltrimethylammonium chloride, amphoteric surfactants such as laurylbetaine and stearylamine acetate, and metallic soaps such as calcium stearate. Any one of these may be used alone. It is used, or two or more are used together.

According to the production method of the present invention, the zinc oxide fine particles and the polymer are contained, and the number average particle diameter of 0.1 to 10 μm and the variation coefficient of the particle diameter of 30% or less (preferably,
Zinc oxide-polymer composite fine particles having a number average particle diameter of 0.1 to 2 μm and a variation coefficient of particle diameter of 15% or less) are dispersedly contained in the range of 1 to 80% by weight, and an alcohol and / or the ester compound is used. And / or a dispersion having an organic solvent as a solvent is obtained.

The dispersion of the composite fine particles obtained by the production method of the present invention can be used as it is, but if necessary, the composite fine particles may be added to the composite fine particle powder or other solvent by solvent substitution. It can be easily converted into a dispersed dispersion or the like. The powder of the composite fine particles is obtained by separating the composite fine particles from the dispersion medium by a commonly used method such as filtration, centrifugation, solvent evaporation of the dispersion, or drying, or
It can be obtained by baking the dried product, if necessary. A powdering method by a solvent evaporation method using a vacuum flash evaporator after performing a concentration operation of a dispersion as needed is a method in which secondary aggregation of composite fine particles, which tends to occur in a drying process, is suppressed. Therefore, it is preferable as a method for pulverizing composite fine particles having excellent dispersibility.

As a method for obtaining a dispersion in which the fine composite particles are dispersed in a solvent different from the dispersion containing the fine composite particles obtained by the production method of the present invention, the powder obtained according to the above-mentioned method is treated with water. After mixing with a solvent such as
A known method of dispersing by mechanical energy such as a ball mill, a sand mill, an ultrasonic homogenizer or the like, or by heating or heating the dispersion to evaporate or distill off part or all of the solvent in the dispersion, the solvent to be replaced is A so-called heating solvent substitution method of mixing can be adopted. The solvent component constituting the dispersion is not particularly limited, and alcohols, aliphatic and aromatic carboxylic acid esters, ketones, ethers, ether esters, aliphatic and aromatic hydrocarbons, halogenated carbonized Organic solvents such as hydrogen,
Water, mineral oil, vegetable oil, wax oil, silicone oil and the like are exemplified, and may be appropriately selected according to the purpose of use. [Uses of Zinc Oxide-Polymer Composite Fine Particles] Examples of uses of the composite fine particles of the present invention and the composite fine particles obtained by the production method of the present invention will be described below.

The fine composite particles of the present invention and the fine composite particles obtained by the production method of the present invention can be used in various industrial applications or industrial applications, for example, as a composition containing the same. Film, sheet, fiber, resin board,
A resin composition constituting a film, a sheet, a fiber, a resin plate or the like for increasing the added value of glass, paper, cosmetics or the like; a coating composition applied to the film, the fiber, the resin plate, the glass, the paper or the like; The fine composite particles of the present invention are added to paper or cosmetics.

The composite fine particles of the present invention and the composite fine particles obtained by the production method of the present invention have a multi-layered structure having an outer shell layer in which the zinc oxide fine particles are aggregated. Since it has high properties, a coated product obtained by coating a coating material containing the composite fine particles on a transparent or translucent substrate (glass, plastic, etc.), or molding a resin composition containing the composite fine particles The goods are
Covers for general lighting equipment, emergency lights, guide lights, indicator lights, etc .;
Useful as a light diffuser applicable to members that require light diffusion, such as display plates, display panels; translucent covers; signboards, signs, screens for video equipment; backlight diffuser plates for liquid crystal display (LCD). Among the coating materials containing the composite fine particles, the printing ink composition is particularly useful as an offset printing ink because the composite fine particles effectively act as a matting agent. Further, a light diffuser having improved visible light transmittance and visible light diffusivity by containing the composite fine particles is useful for downsizing or thinning of devices such as liquid crystal displays and lighting fixtures. (Coating composition and coated article) The coating composition of the present invention can form a transparent or semitransparent continuous phase with the composite fine particles of the present invention and / or the composite fine particles obtained by the production method of the present invention. It contains a binder component and a solvent in which the fine composite particles are dispersed and the binder component is dispersed and / or dissolved. The amount of the composite fine particles is, for example, 0.1 to 8 with respect to the total solid content of the composite fine particles and the binder component.
It is 0% by weight, preferably 0.5 to 50% by weight.

The coated article of the present invention comprises a base material and a coating film formed on the surface of the base material. The base material is, for example, one selected from the group consisting of resin molded products, glass and paper. The resin molded product is, for example, at least one selected from the group consisting of plates, sheets, films, and fibers. The base material is preferably transparent and / or translucent in material, and synthetic resin such as (meth) acrylic resin, polycarbonate resin, polyester resin, polyimide resin, vinyl chloride resin, polystyrene resin, polyolefin resin; glass or the like. It is illustrated. The coating film contains the composite fine particles of the present invention and / or the composite fine particles obtained by the production method of the present invention, and a binder component which forms a transparent or translucent continuous phase in which the composite fine particles are dispersed. The amount of the composite fine particles is, for example, 0.1 to 80% by weight, preferably 0.5 to 50% by weight, based on the total solid content of the composite fine particles and the binder component.

When the amount of the composite fine particles exceeds the above range, there is a problem that the adhesion of the coating film to the substrate, the scratch resistance and abrasion resistance of the coating film itself are insufficient, and when the amount is less than the above range, the composite body is insufficient. There is a problem that the effect of adding fine particles becomes insufficient. In the coating composition of the present invention, for example, the total solid content of the composite fine particles and the binder component is 1 with respect to the entire coating composition.
˜80% by weight, the amount of solvent is 10 to 99% by weight. The balance of the coating composition is an additive such as a pigment used as necessary.

The binder component that can be used in the coating composition is not particularly limited, and examples thereof include (meth) acrylic resins and
Thermoplastic or thermosetting synthetic resin such as vinyl chloride type, silicone type, melamine type, urethane type, styrene type, alkyd type, phenol type, epoxy type, polyester type; ethylene-propylene copolymer rubber, polybutadiene rubber, styrene- Organic binders such as synthetic rubber or natural rubber such as butadiene rubber and acrylonitrile-butadiene rubber, and inorganic binders such as silica sol, alkali silicate, silicon alkoxide and phosphate can be used. These binder components are appropriately selected according to the required performance such as heat resistance and scratch resistance for the film obtained by coating and drying the coating composition on the substrate and the purpose of use such as the type of substrate, and any one of them is selected. One is used alone, or two or more are used as a mixture.

In the coating composition of the present invention, the binder component may be dissolved, emulsified or suspended in a solvent. The solvent of the binder component is appropriately selected according to the purpose of use of the coating composition, the type of binder component, etc., and examples thereof include alcohols, aliphatic and aromatic carboxylic acid esters, ketones, ethers, ether esters. , Organic solvents such as aliphatic and aromatic hydrocarbons and halogenated hydrocarbons; water; mineral oils, vegetable oils, wax oils, silicone oils and the like are exemplified, and may be appropriately selected according to the purpose of use. If necessary, two or more may be mixed and used at an arbitrary ratio. As the solvent of the binder component, the solvent of the composite fine particles of the present invention and / or the dispersion of the composite fine particles obtained by the production method of the present invention can be used.

The method for producing the coating composition of the present invention is not particularly limited. For example, the composite fine particles of the present invention and / or
Alternatively, the powder of the composite fine particles obtained by the manufacturing method of the present invention, a method of adding and mixing in a solvent containing a binder component to disperse, a dispersion of the composite fine particles in a solvent and a solvent containing a binder component. A method of mixing, a method of adding a binder component to a dispersion obtained by dispersing fine composite particles in a solvent, and mixing the same can be employed. The dispersion method is not particularly limited, and a conventionally known method using, for example, a stirrer, a ball mill, a sand mill, an ultrasonic homogenizer, or the like can be adopted.

The coating composition of the present invention can also be obtained by directly adding and mixing a binder component or a solvent containing a binder component to the composite fine particle dispersion obtained by the method for producing composite fine particles. According to the method for producing a coating composition described above, at least composite fine particles,
A coating composition containing a binder component and a solvent can be obtained.

The coating composition of the present invention comprises any substrate such as a plastic film or sheet such as polyester film; fibers such as natural fibers and synthetic fibers; vinyl chloride resin, polycarbonate resin, acrylic resin, polyethylene terephthalate resin and the like. A transparent or semi-transparent synthetic resin plate; glass; paper or the like can be applied and dried to form a film containing composite fine particles.

To form the film, heating may be performed at a temperature not higher than the deformation temperature of the substrate, if necessary. In addition to removing the solvent, heating is performed, for example, by using an inorganic binder such as a silicon alkoxide as a binder component to sufficiently promote the intermolecular condensation reaction of the binder component to form a tough film, or the binder component. A thermosetting resin is used for forming a cured film by sufficiently promoting the curing reaction of the thermosetting resin, and at least a part of the binder component has two or more active hydrogen atoms such as polyether and / or polyester. This is because the crosslinking reaction can be efficiently carried out when the crosslinking reaction is carried out, such as when the resin to be used and a crosslinking agent such as isocyanates are finally used to form a polyurethane film.

The binder component in the coated article of the present invention is a film formed by cooling and solidifying, cooling and solidifying and hardening (crosslinking), dry solidifying or dry hardening (dry crosslinking) of the above organic and / or inorganic binder. The method for applying the coating composition of the present invention is not particularly limited, and a dipping method,
Conventionally known methods such as a spray method, a screen printing method, a roll coater method and a flow coating method can be used.

The coating film formed from the coating composition of the present invention as described above, and the coated article of the present invention obtained as described above have the composite fine particles of the present invention and / or Alternatively, the composite fine particles obtained by the production method of the present invention are dispersed and contained. Therefore, the coating film and the coated article have a function reflecting the characteristics of the composite fine particles, that is, (1) a property in which the light diffusivity and the light transmittance of the composite fine particles are controlled according to the purpose of use. And (2) UV blocking properties, (3) uniformity of the coating film due to the fine dispersion of the composite particles in the binder component, and (4) antibacterial and antifungal properties.

The fine composite particles have the same shape and have a number average particle diameter of 0.1 to 10 μm and a coefficient of variation of particle diameter of 30% or less (preferably the number average particle diameter of 0.1 to 2 μm and the variation of particle diameter. When the coefficient is 15% or less), the coating film formed from the coating composition of the present invention and the coated article of the present invention have the characteristics (1) to (5) described above and impair the surface flatness. It has excellent lubricity and anti-blocking property.

When the fine composite particles have an outer shell formed by aggregating fine zinc oxide particles, the fine composite particles also cause light scattering at the interface between the outer shell and the inside thereof, so that a film having excellent light diffusion properties. And it becomes a painted product. When the polymer is also present in the outer shell and the fine composite particles are hollow, their properties are further enhanced. (Resin composition and resin molded product) The resin composition of the present invention is used, for example, as a molding material.

The resin composition of the present invention contains the fine composite particles of the present invention and / or the fine composite particles obtained by the production method of the present invention, and a resin capable of forming a transparent or translucent continuous phase. The amount of the composite fine particles is, for example, 0.1 to 80% by weight, preferably 0.1 to 20% by weight, based on the total solid content of the composite fine particles and the resin. The resin molded product of the present invention is obtained by molding the resin composition of the present invention into a shape selected from the group consisting of plates, sheets, films and fibers. This resin molded product contains the composite fine particles of the present invention and / or the composite fine particles obtained by the production method of the present invention, and a resin in which the composite fine particles are dispersed to form a transparent or translucent continuous phase. The amount of the composite fine particles is, for example, 0.1 to 80% by weight, preferably 0.1 to 20% by weight, based on the total solid content of the composite fine particles and the resin.

If the amount of the composite fine particles exceeds the above range, it is difficult to obtain a molded product, and even if it is obtained, there is a problem that the molded product has insufficient mechanical strength. There is a problem that it is not exhibited. The type of resin that can be used in the resin composition and the resin molded product of the present invention is not particularly limited, but is appropriately selected according to the purpose of use. Examples of the resin include polyolefin resins such as polyethylene and polypropylene; polystyrene resins; vinyl chloride resins; vinylidene chloride resins; polyvinyl alcohol; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polyamide resins; polyimide resins; polymethyl (meth) acrylate. (Meth) acrylic resin, phenol resin; urea resin, melamine resin, unsaturated polyester resin, polycarbonate resin, thermoplastic resin such as epoxy resin, ethylene-propylene copolymer rubber, polybutadiene rubber, styrene-butadiene resin Examples of the rubber include synthetic rubbers such as acrylonitrile-butadiene rubber and natural rubbers. Any one of them may be used alone, or two or more may be used in combination. Preferred resins are methacrylic resins, acrylic resins, polycarbonate resins, vinyl chloride resins, because of their excellent transparency.
It is at least one selected from the group consisting of polyester resins and polystyrene resins. A more preferable resin is a methacrylic resin because it is excellent in transparency and weather resistance.

The method for producing the resin composition of the present invention is not particularly limited. In the resin, the composite fine particles of the present invention and / or
Alternatively, the target resin composition can be obtained by mixing and dispersing the composite fine particles obtained by the production method of the present invention. For example, when melt-kneading the resin in the form of pellets or powder, the composite fine particles are obtained. A conventionally known method such as a master batch method in which powder is added and mixed, a method in which composite fine particles are mixed and dispersed in a solution in which a resin is dissolved, and then the solvent is removed can be adopted. Alternatively, a method of mixing and dispersing the composite fine particles in the process of producing the resin, for example, when the resin is a polyester resin, any time of a series of steps in the polyester production process, that is, in the transesterification reaction to the polymerization reaction. A method of adding and mixing a powder of composite fine particles, preferably a dispersion obtained by dispersing the composite fine particles in glycol, which is a polyester raw material, can also be used.

According to the above method, a resin composition in which the composite fine particles of the present invention and / or the composite fine particles obtained by the production method of the present invention are dispersed and contained in a resin can be obtained. The resin composition may be in the form of a usual molding material such as pellet. By molding the obtained resin composition into a plate shape, a sheet shape, a film shape, a fiber shape, or by laminating a sheet / film of the resin composition on the above-mentioned substrate, the composite fine particles of the present invention It is possible to obtain a resin molded product that contains the composite fine particles obtained by the production method of the present invention and / or has the following functions at the same time. (1) Characteristics in which the light diffusivity and light transmittance of the composite fine particles are controlled according to the purpose of use (2) UV shielding property (3) Due to the fine dispersion of the composite particles in the resin component Uniformity of molded products (4) Antibacterial and antifungal properties The composite fine particles have the same shape and the number average particle diameter of 0.
1 to 10 μm, particle diameter variation coefficient of 30% or less (preferably number average particle diameter 0.1 to 2 μm, particle diameter variation coefficient 1
5% or less), the resin molded product of the present invention has excellent slipperiness and antiblocking property without impairing the surface flatness. When the resin molded product is formed into a film, particularly a film stretched by a stretching operation or the like, irregularities due to the presence of the composite fine particles are formed. When the composite fine particles obtained according to the preferred embodiment of the present invention are contained, since the particle size distribution of the composite fine particles is uniform and highly dispersed, the unevenness of the film surface becomes uniform and fine, The film is excellent in slipperiness and anti-blocking property while being extremely excellent in flatness. For example, the polyester film thus obtained is useful as a base film for magnetic tape, a packaging film, a capacitor film, and the like.

When the composite fine particles have an outer shell formed by aggregating zinc oxide fine particles, the composite fine particles also cause light scattering at the interface between the outer shell and the inside thereof, so that the resin molded article has a light diffusing property. Will be excellent. When the polymer is also present in the outer shell and the fine composite particles are hollow, their properties are further enhanced. The resin composition sheet / film is formed, for example, by uniformly dispersing the composite fine particles of the present invention and / or the composite fine particles obtained by the production method of the present invention in a resin, and mixing the composite fine particles and the resin. Made by The mixing / molding method is, for example, an injection molding method, an extrusion molding method, a cast polymerization (molding) method, a calender method, a casting method, or the like. The obtained sheet film can be used as it is as a light diffusing sheet film. Also, a sheet or film may be laminated on the above-mentioned substrate. The laminating method includes, for example, a hot pressing method, an extrusion laminating method, a method of integrating a film during cast polymerization, a method of attaching with an adhesive, and the like.

The method for obtaining a molded product having a desired shape from the resin composition of the present invention is not particularly limited, and a conventionally known method can be employed as it is. An example will be described below. When it is desired to obtain a polycarbonate resin plate in which the composite fine particles of the present invention and / or the composite fine particles obtained by the production method of the present invention are dispersed and contained, for example, a polycarbonate resin pellet or powder and a predetermined amount of the composite fine particle powder are used. After obtaining a composition in which the composite fine particles are uniformly mixed in the resin by kneading the resin in a molten state, continuously or once pelletizing the composition, injection molding, extrusion molding, compression molding, etc. Depending on the method, a method of processing into a flat plate or a curved plate is adopted. Of course, it is also possible to form the flat-plate shaped body into an arbitrary shape such as a corrugated plate shape by further post-processing. A resin plate such as an acrylic resin plate, a vinyl chloride resin plate, or a polyester resin plate can be obtained in the same manner.

Fibers such as nylon fiber and polyester fiber, films such as polyolefin film, polyamide film and polyester film, in which the composite fine particles of the present invention and / or the composite fine particles obtained by the production method of the present invention are dispersed and contained, When it is desired to obtain, for example, a composite fine particle powder and a resin pellet or a powder is melt-kneaded to obtain a composition in which the composite fine particle is uniformly mixed in the resin, and then continuously or once pelletized. After that, a conventionally known fiberizing method such as melt spinning, or a conventionally known (stretching) film manufacturing method in which a sheet is formed by extrusion and then a uniaxially or biaxially stretching operation is performed if necessary. do it.

In order to obtain a polyester fiber or a polyester film in which the fine composite particles of the present invention and / or the fine composite particles obtained by the production method of the present invention are contained, the following other conventionally known methods are also adopted. obtain. That is, as a method for obtaining a polyester fiber, during the production process of polyester, that is, transesterification reaction ~ at any time of a series of steps in the polymerization reaction, composite fine particles,
For example, a dispersion obtained by dispersing in glycol in a proportion of 0.1 to 50% by weight is added and mixed to complete the polymerization reaction of polyester, thereby obtaining a polyester polymer in which composite fine particles are dispersed and contained in polyester. After
A method of melt spinning according to a conventionally known method may be adopted.

On the other hand, in order to obtain a polyester film, a polyester polymer in which composite fine particles are dispersed and contained in a polyester is obtained in the same manner and then extruded into a sheet by extrusion molding, and then uniaxially if necessary. Or 2
A method of performing stretching treatment in the axial direction can be adopted. (Paper) The paper of the present invention has a pulp made into paper, and the composite fine particles of the present invention dispersed in the pulp and / or the composite fine particles obtained by the production method of the present invention. The amount of the composite fine particles is 0.01 to 5 with respect to the pulp.
It is 0% by weight, preferably 0.1 to 20% by weight. Below the range, there is a problem that the effect of adding the composite fine particles is insufficient, and above the range, there is a problem that the mechanical properties of the paper are deteriorated.

The paper may be any as long as it contains the composite fine particles of the present invention and / or the composite fine particles obtained by the production method of the present invention, for example, internally added paper, coated paper, impregnated paper, film. Examples include processed paper such as laminated paper. Internally added paper is obtained by adding and mixing composite fine particles at any time in the process from beating of pulp to papermaking. The composite fine particles are dispersed on the inner and / or outer surface of the paper. It means the contained paper. The method of adding and mixing the composite fine particles is not particularly limited, and usually, the composite fine particles can be used as a powder or in the state of a dispersion liquid dispersed in water or the like. Further, the steps of papermaking and drying may be carried out according to a conventionally known papermaking method. As the raw material used, conventionally known materials can be used as they are. For example, a pulp slurry is prepared by beating pulp with a pulper or the like. After adding and mixing an aqueous dispersion liquid of the composite fine particles to the slurry, a paper containing a dispersion of the composite fine particles can be obtained through a papermaking process and a drying process. At this time, if necessary, a sizing agent, a sulfuric acid band, a paper strengthening agent and the like may be added at any stage.

The coated paper is a paper on which a film containing composite fine particles is formed by applying a coating material containing the composite fine particles on a paper base material and drying it. The impregnated paper means that the composite fine particles are fixed on the inner and outer surfaces of the paper by impregnating the paper base material into an aqueous or organic solvent dispersion liquid or the like containing or not containing a binder in which the fine composite particles are dispersed and contained. Means to become.

The method for producing these coated papers and impregnated papers is not particularly limited, and is conventionally known except that the composite fine particles of the present invention and / or the composite fine particles obtained by the production method of the present invention are used. Using the paper obtained by the general production method of 1. as a base material, the conventionally known coating method and impregnation method can be applied as they are. The coating composition containing the composite fine particles to be used, the composition of the dispersion liquid, the solvent to be used, the type of the binder component, and the preparation method thereof can be the conventionally known raw materials as they are, and can be prepared according to the conventionally known preparation method. Good.

The content of the fine composite particles in the coating composition and the dispersion is not particularly limited as long as it is in the range of 0.1 to 100% by weight in the solid content, and is appropriately selected depending on the purpose of use and the like. The solid content here means the total amount of the zinc oxide-polymer composite fine particles and the binder component contained in the coating composition and the dispersion liquid. Examples of the coating composition used for making coated paper include those containing a solvent among the coating compositions of the present invention described above. Examples of the dispersion medium of the dispersion liquid used for making the coated paper include the solvents that can be used in the coating composition of the present invention described above. Additives other than these, such as pigments, waterproofing agents, lubricants, defoamers, flow modifiers, and water retention agents may be mixed in the coating composition depending on the purpose of use.

The film-laminated paper means a paper laminated with a polymer film containing the composite fine particles obtained by the above-mentioned method in a dispersed state. As the polymer film, the resin molded product of the present invention described above can be used. The paper obtained by the above manufacturing method is useful as a paper having an excellent appearance. The use of the obtained paper is arbitrary, and it can be used in various uses such as art paper and wallpaper.

The composite fine particles of the present invention and / or the composite fine particles obtained by the production method of the present invention have the same shape, the number average particle diameter is 0.1 to 10 μm, and the variation coefficient of the particle diameter is 30% or less. (Preferably, the number average particle size is 0.1
When it is 2 μm and the variation coefficient of particle diameter is 15% or less), it is possible to obtain a paper having improved surface flatness, gloss and printability. (Cosmetic) The cosmetic of the present invention contains 0.1% by weight or more of the composite fine particles of the present invention and / or the composite fine particles obtained by the production method of the present invention. The amount of the composite fine particles is usually 0.1 to 0.1 based on the total weight of the solid content of the cosmetic.
It is 50% by weight. In addition to the above essential ingredients, depending on the purpose,
Oils such as liquid oils, solid oils, waxes, and hydrocarbons,
At least one selected from the group consisting of polyhydric alcohols such as polyethylene glycol and propylene glycol, a surfactant, a thickener, a fragrance, a drug, an antioxidant, a chelating agent, a dye, water, antiseptic / antifungal. Ingredients usually used in cosmetics, such as at least one selected from the group consisting of agents, are blended within a range that does not impair the effects of the present invention. Further, extenders such as kaolin, talc and mica, inorganic coloring pigments such as iron oxide and TiO ₂ and red 2
No. 02, yellow 4, etc., and / or at least one selected from the group consisting of organic UV absorbers such as benzoic acid, cinnamic acid, salicylic acid, and benzophenone. At least one
It can be used in combination with the composite fine particles.

The cosmetics of the present invention are more flexible than before and can shield ultraviolet rays. That is, the purpose of blending the composite fine particles in the cosmetic of the present invention is mainly for sunscreen. The use of the cosmetic of the present invention is not particularly limited, and it is used as a powdery, creamy or oily foundation, lotion, emulsion, cosmetic oil, facial cosmetics such as cream, makeup cosmetics such as lipstick and eye shadow, etc. be able to.

The composition of the cosmetic is not particularly limited as long as it contains the composite fine particles of the present invention and / or the composite fine particles obtained by the production method of the present invention. In the conventional cosmetic composition, the composite fine particles are contained. Therefore,
Raw materials generally used in cosmetics can be used as they are.

Therefore, the method for producing the cosmetic of the present invention is not particularly limited, and the composite fine particles are added at any time to produce a conventionally known cosmetic composition according to the application (type) of the cosmetic. The necessary amount may be added, mixed, and dispersed. The composite fine particles of the present invention and / or the composite fine particles obtained by the production method of the present invention are less likely to aggregate and can be easily dispersed in an ordinary cosmetic composition. Therefore,
As the method for dispersing the composite fine particles, the mixing and dispersing method generally used for cosmetic powders can be applied as it is, and according to the method, a cosmetic in which the composite fine particles are highly dispersed can be obtained. When the composite fine particles are added and mixed, the fine particles may be added and mixed as they are, but if necessary, for example, anionic, cationic, nonionic and amphoteric surfactants, metal soaps, silicones, etc. A surface treatment method for making lipophilic or hydrophilic, which is generally used for cosmetic powders, may be performed. The surface treatment may be performed prior to the addition and mixing, or may be performed in the addition and mixing process.

The cosmetic containing the fine composite particles according to the present invention has (1) a property in which the light diffusivity and the light transmission by the fine composite particles are controlled according to the purpose of use, and (2) an ultraviolet shielding property. (3) high dispersibility in a cosmetic composition,
(4) It has antibacterial and antifungal properties (bactericidal properties).

When the composite fine particles have an outer shell formed by aggregating zinc oxide fine particles, the polymer is also present in the outer shell, and the composite fine particles are hollow, the cosmetic of the present invention has a moisturizing property, It can have a moist feeling, and by holding the fragrance or the like in the fine particles, it is possible to provide a sustained release function of the fragrance or the like. However, the use of the composite fine particles according to the present invention is not limited to those described above.

[0117]

EXAMPLES Examples of the present invention and comparative examples outside the scope of the present invention will be shown below, but the present invention is not limited to the following examples. Regarding the composite fine particles obtained in Examples and Comparative Examples, crystallinity, particle size and shape, dispersibility, fine particle composition, physical properties or physical property values such as size and shape of zinc oxide fine particles, a film containing the composite fine particles The optical properties of the formed film, glass and the like were analyzed and evaluated by the following methods. When it is necessary to pulverize the powder prior to analysis and evaluation, the powder obtained after pulverizing according to the following method was used as a measurement sample.

After pulverizing the (crystalline) composite fine particles,
The type of crystal was identified by powder X-ray diffraction measurement. (Average particle diameter of composite fine particles, variation coefficient of particle diameter) The particle diameter (major axis) of 100 arbitrary particles in a scanning electron microscope image of 10,000 times is measured, and the number average particle diameter of the composite fine particles is calculated. Calculated from the following formula.

[0119]

[Equation 1] Here, d _n is the number average particle diameter, D _i is the major axis of each particle, and n is the number of particles.

[0120]

[Equation 2] Here, CV is the coefficient of variation of the particle size, and σ _n-1 is the standard deviation of the particle size distribution. The particle size distribution standard deviation is calculated by the following formula.

[0121]

(Equation 3) (Particle shape) The particle size was evaluated by a scanning electron microscope with a magnification of 10,000 times based on the major / minor ratio (major axis / minor axis ratio) obtained by the following formula per 100 particles.

[0122]

[Equation 4] Here, Li is the major axis of each particle, and Bi is the minor axis of each particle. The criterion is that the length is 1.0 or more, 1.2
Less than 1 is spherical, and 1.2 or more and 5.0 or less is elliptical. (Size and shape of zinc oxide fine particles) It was determined by a scanning electron microscope or a transmission electron microscope with a magnification of 10,000 to 100,000 times.

A cross-sectional image of composite fine particles was obtained from a transmission electron microscope image by embedding the composite fine particle powder in a resin and cutting out a thin piece. (Fine particle composition: Zinc oxide concentration) A powder sample was placed in the air at 60
It was calcined at 0 ° C. for 2 hours, and the ash content was determined as zinc oxide on a weight basis.

(Optical Characteristics of Film Containing Fine Particles) Regarding the spectral characteristics, a self-recording spectrophotometer (UV-3100,
Irradiation wavelength of 800-200 nm by Shimadzu Corporation
The transmittance in the visible region was measured, and the transmittance in the visible region (total light), the ultraviolet shielding ability, etc. were evaluated. The total light transmittance and haze were measured and evaluated by a turbidimeter (NDH-1001 DP Nippon Denshoku Industries Co., Ltd.).

(Example 1) In a glass reactor equipped with a stirrer, a dropping port, a thermometer and a reflux condenser, 0.3 kg of commercially available zinc oxide powder was added to 1.5 kg of acetic acid and 1.
After adding and mixing to 5 kg of mixed solvent, the mixture was heated to 80 ° C. with stirring to dissolve zinc oxide in the mixed solvent to obtain a uniform zinc-containing solution.

Next, 12 kg of 2-butoxyethanol was charged into a 20-liter glass reactor equipped with a stirrer, a dropping port, a thermometer, and a distillation gas outlet and capable of heating a heat medium from the outside, and the internal temperature was raised to 154 ° C. The temperature was raised and maintained at that temperature. To this, a zinc-containing solution 3.3k kept at 80 ° C
g was added dropwise with a metering pump over 30 minutes and mixed. This drop mixing lowered the bottom temperature from 154 ° C to 134 ° C. After finishing the dropping, raise the internal temperature to 1
When the temperature reached 67 ° C., a methyl methacrylate-acrylic acid copolymer (a weight ratio of methyl methacrylate / acrylic acid = 9/1, a weight average molecular weight of 7,5) was added to the mixture.
A solution of 53 g of 00) in 2-butoxyethanol was added and mixed, and after reaching 170 ° C., the temperature was maintained for 2 hours to obtain 10.65 kg of a fine particle dispersion.

The fine particles contained in the dispersion are separated from the dispersion medium by centrifugation, the separated fine particles are washed with isopropyl alcohol, and then vacuum dried (10 Torr) at 50 ° C. for 24 hours to obtain a fine particle powder. P
Got 1. The fine particle powder P1 has a number average particle diameter of 2.0 μm obtained from a scanning electron microscope image, and a particle diameter of 8 to 3
It was confirmed by transmission electron microscope observation that 0 nm zinc oxide fine particles (number average particle diameter 20 nm) are fine particles having a multilayer structure localized in the outer shell layer. Furthermore, after crushing the fine particle powder P1 and observing the crushed material as a sample with a scanning electron microscope, it was confirmed that the fine particles were hollow. The ZnO content in the fine particle powder P1 was 87.7% by weight. In addition, it was confirmed by X-ray diffraction measurement that it was a ZnO crystal, and elemental analysis, F
It was confirmed by T-IR and the like that a methyl methacrylate-acrylic acid copolymer was contained. From these results, it was confirmed that the fine particle powder P1 was zinc oxide-polymer composite fine particles.

FIG. 1 shows a sectional image of the fine particles by a transmission electron microscope, and FIG. 2 shows a transmission electron microscope image of the ZnO ultrafine particles contained in the outer shell layer. In FIG. 1, the length from end to end of the lower right three lines of the screen is 1.0 μm. It can be seen in FIG. 1 that the small black dots are zinc oxide fine particles, and a large number of small black dots aggregate to form the outer shell of the lump-shaped composite fine particles. In FIG. 2, the length from end to end of the lower right three lines of the screen is 20 nm. In FIG. 2, the gray to black image is zinc oxide fine particles. Many zinc oxide fine particles are aggregated.

(Examples 2 to 5) In Example 1, except that the polymer shown in Table 1 was used in place of the methyl methacrylate-acrylic acid copolymer, and that the reaction conditions shown in Table 1 were adopted. In the same manner as in Example 1, a dispersion of zinc oxide-polymer composite fine particles was obtained, and composite fine particle powders P2 to P5 were obtained. Table 2 shows various physical properties of the obtained composite fine particle powders P1 to P5.

[0130]

[Table 1]

[Table 2] (Examples 6 to 8) Using the fine particle powder P1 obtained in Example 1, coating materials (1) to (3) having the following compositions were prepared. Example 6 Example 7 Example 8 Paint (1) Paint (2) Paint (3) Paint composition: Fine particle powder P1 10 parts by weight 20 parts by weight 30 parts by weight Acrylic resin-based polymer solution * 200 parts by weight 178 parts by weight 156 Parts by weight Toluene 250 parts by weight 222 parts by weight 194 parts by weight *: Nippon Shokubai Co., Ltd., Aroset 5247, solid content 45% by weight Paints (1) to (3) are applied on a glass plate using a bar coater, respectively. On the glass plate by
A coating film having the thickness described in the table is formed, and coated products (1) to
(3) was obtained. The optical properties of the coated products (1) to (3) are shown in the table below.

Coated Product Coating Film Thickness Number of Total Light Transmission Haze [μm] Rate [%] [%] Example 6 (1) 21 87 74 Example 7 (2) 19 78 86 86 Example 8 (3) 18 70 90 Glass plate-none 91 0.3 As seen in the table above, the coated article of the present invention has a haze, which is a measure of light diffusivity, much larger than that of the glass plate as the base material, and The total light transmittance is almost the same as that of the glass plate or about 75% thereof, and the light transmittance is good.

(Comparative Examples 1 and 2) In Example 6,
Instead of the fine particle powder P1, ZnO ultrafine particles having an average particle diameter of 0.02 μm (Comparative Example 1) and zinc oxide fine particles obtained by the French method (Zinc Hua No. 1 (special), manufactured by Sakai Chemical Co., Ltd.) were used. Except for the above, comparative paints (1) and (2) were prepared in the same manner as in Example 6, coated on a glass plate and dried to form a coating film. (2) was obtained. The obtained comparative coated products (1) and (2)
The optical properties of are shown in the table below.

Comparative Coating Film Thickness Total Light Transmission Haze Product No. [μm] Rate [%] [%] Comparative Example 1 (1) 25 89 60 Comparative Example 2 (2) 25 71 78 Examples 6 to 8 From the comparison with Comparative Examples 1 and 2, the composition containing the specific composite fine particles of the present invention has excellent light diffusivity (diffusive transmittance = total light transmittance) while having high light transmittance (total light transmittance). It is clear that the composition has a light transmittance × haze) and that excellent light diffusivity is exhibited even when the amount of the composite fine particles contained in the composition is small.

(Examples 9 to 10) Using the fine particle powder P1 obtained in Example 1, a coating material (4) having the following composition
Was prepared. Composition of paint (4) Fine particle powder P1 10 parts by weight Acrylic resin-based polymer solution 200 parts by weight (Nippon Shokubai Co., Ltd., Aroset 5247, Solid content 45)
% By weight) Toluene 250 parts by weight Polyester film using the bar coater,
The coated products (4) and (5) were obtained by coating on a methacrylic resin plate and drying. The optical properties of these coated products are shown in the table below.

Coated product Coating thickness Total light transmission haze Number of ultraviolet ray blocking ability [μm] Rate [%] [%] Example 9 (4) 5 88 20 Yes Example 10 (5) 33 86 77 Yes (Example 11) 2 of fine particle powder P4 obtained in Example 4
0.2 parts by weight of fine particles are obtained by mixing 1 part by weight and 998 parts by weight of the polycarbonate resin pellets and melt-kneading.
Was uniformly dispersed, and extrusion molding was performed to obtain a polycarbonate plate having a thickness of 5.0 mm. The obtained polycarbonate plate was highly dispersed with composite fine particles and had a total light transmittance of 85% or more, which was excellent in visible light transmittance and was excellent in the effect of preventing ultraviolet rays.

(Example 12) 25 parts by weight of the fine particle powder P1 obtained in Example 1 and methacrylic resin pellets 475.
By mixing 1 part by weight and melt-kneading, a melt in which 5% by weight of fine particles were uniformly dispersed was obtained, and subsequently extrusion molding was performed to obtain a methacrylic resin sheet having a thickness of 2 mm. The obtained sheet has high dispersion of fine particles, total light transmittance of 83%, haze of 86%, high visible light transmittance, excellent light diffusivity, and excellent ultraviolet ray prevention effect. there were.

(Comparative Example 3) In Example 12, except that 25 parts by weight of zinc oxide fine particles (Zinc Hua No. 1, manufactured by Sakai Chemical Industry Co., Ltd.) obtained by the French method were used in place of the fine particle powder P1. A methacrylic resin sheet containing 5% by weight of fine particles and having a thickness of 2 mm was obtained in the same manner as in Example 12. The obtained sheet was contained in a non-uniform state in which fine particles were secondarily aggregated and had no transparency and was cloudy.

Example 13 2 parts by weight of the fine particle powder P2 obtained in Example 2 and 98 parts by weight of polyester resin pellets were mixed and melt-kneaded to obtain fine composite particles 2
A polyester composition in which the weight% was uniformly dispersed was obtained, molded into a sheet by extrusion molding, and further stretched to obtain a polyester film having a thickness of 40 μm. The film was a film in which fine particles were uniformly and highly dispersed, was excellent in visible light transmittance and light diffusivity, and was excellent in the effect of preventing ultraviolet rays.

(Comparative Example 4) In Example 13, zinc oxide fine particles (Zinc Hua No. 1, manufactured by Sakai Chemical Industry Co., Ltd.) obtained by the French method were used in place of the fine particle powder P1 obtained in Example 1. A polyester film having a thickness of 40 μm and containing 2% by weight of the zinc oxide fine particles was obtained in the same manner as in Example 13. The obtained film contained fine particles in a state of secondary agglomeration, and therefore had a low ultraviolet ray preventing effect, and had no transparency and became cloudy.

The surface of the film obtained in each of Example 13 and Comparative Example 4 was observed by a transmission electron microscope. As a result, the surface of the film obtained in Example 13 was a uniform fine projection due to the presence of fine particles. In contrast to being covered, the surface of the film obtained in Comparative Example 4 was inferior in that it had uneven protrusions such as coarse protrusions due to the aggregation of fine particles.

(Example 14) The fine particle powder P obtained in Example 4 in place of the fine particle powder P2 in Example 13 was used.
In the same manner as in Example 13 except that No. 4 was used, a polyester composition containing 2% by weight of the fine particle powder P4 was obtained, and then melt-spun to obtain a polyester fiber. The fiber is a fiber in which fine particles are uniformly and highly dispersed,
It was transparent and had an excellent effect of preventing ultraviolet rays.

Comparative Example 5 Example 1 was repeated except that zinc oxide fine particles (Zinc Hua No. 1, manufactured by Sakai Chemical Industry Co., Ltd.) obtained by the French method were used in place of the fine particle powder P4 in Example 14.
In the same manner as in 4, a polyester fiber containing the zinc oxide fine particles was obtained. The obtained fiber contained fine particles in a state of secondary agglomeration, and therefore had a low ultraviolet ray preventing effect, and was not transparent and clouded.

Example 15 From the dispersion obtained in Example 4, the solvent contained in the dispersion was removed by centrifugation. The obtained composite fine particles containing a small amount of solvent were dispersed in ion-exchanged water and centrifuged again. After repeating this operation several times, the composite fine particles were dispersed in ion-exchanged water to obtain 50 parts by weight of an aqueous dispersion containing 20% by weight of the fine particles.

50 parts by weight of the aqueous dispersion, acrylic emulsion as a binder resin (Akriset RES-285E manufactured by Nippon Shokubai Co., Ltd., solid content 50% by weight) 20
A coating material was prepared by mixing 1 part by weight, and polyester fiber was dipped in the coating material and dried to obtain a polyester fiber having a fine particle areal weight of 7.0 g / m ² . The fiber was excellent in transparency, which effectively cuts ultraviolet rays.

(Comparative Example 6) 10 parts by weight of zinc oxide fine particles (Zinka No. 1: manufactured by Sakai Chemical Industry) obtained by the French method were added to 40 parts by weight of ion-exchanged water, mixed and dispersed by an ultrasonic homogenizer. Thus, 50 parts by weight of an aqueous dispersion containing 20% by weight of fine particles was obtained. Using the aqueous dispersion, the same operation as in Example 15 was carried out to obtain a polyester fiber having a fine particle areal weight of 6.8 g / m ² . The obtained fiber had an ultraviolet ray-preventing effect, but was cloudy.

Example 16 A cosmetic composition (O / W) having the following composition containing the fine particle powder P4 obtained in Example 4 was blended.
Type cream) was produced. <Composition> (Aqueous phase part) (a) Fine particle powder P4 6 parts by weight (b) Propylene glycol 5 parts by weight (c) Glycerin 10 parts by weight (d) Potassium hydroxide 0.2 parts by weight (e) Ion-exchanged water 45 parts by weight (oil phase part) (f) Cetanol 5 parts by weight (g) Liquid paraffin 5 parts by weight (h) Stearic acid 3 parts by weight (i) Isostearyl myristate 2 parts by weight (j) Glycerin monostearate 2 parts by weight The components (a) to (e) were mixed with stirring to maintain the temperature at 80 ° C to prepare an aqueous phase. On the other hand, mix the components (f) to (j) uniformly and
The oil phase was prepared by maintaining The oil phase was added to the water phase, the mixture was stirred, emulsified with a homomixer, and then cooled to room temperature to produce a cream. The obtained cream had a transparent feeling and was excellent in the effect of preventing ultraviolet rays.

Example 17 In Example 16, instead of the fine particle powder P4, the fine particle powder P obtained in Example 1 was used.
A cream was produced in the same manner as in Example 16 except that 1 was used. The obtained cream was excellent in the effect of preventing ultraviolet rays. (Comparative Example 7) In Comparative Example 7, except that zinc oxide fine particle powder (Zinc Hua No. 1: manufactured by Sakai Chemical Industry Co., Ltd.) obtained by the French method is used instead of the fine particle powder P4 obtained in Example 4. A cream was produced in the same manner as in Example 16.

The obtained cream had a poor dispersibility of fine particles, and therefore had insufficient touch and spread, and had high whiteness and high opacity. (Example 18) By adding and mixing the fine particle powder P2 obtained in Example 2 to ion-exchanged water, the fine particle concentration becomes 1
A 0% by weight aqueous dispersion was prepared.

Next, a quantitative filter paper (manufactured by Toyo Paper Co., Ltd .: product number 5C) was beaten with a Niagara type beater to prepare 400 ml of Canadian Standard Freeness, and the aqueous dispersion was added to the pulp to give a fine particle weight to the pulp. The mixture was added and mixed so that the ratio was 1% by weight. Next, the obtained pulp slurry was diluted to a solid content concentration of 0.1% by weight, dehydrated by a tapping sheet machine, and pressed to make paper having a basis weight of 75 g / m ² . Subsequently, it was dried at 100 ° C. in a rotary dryer to obtain a paper containing 1% by weight of fine particles. The obtained paper has a good fine particle dispersion state, and therefore has excellent ultraviolet shielding properties,
The surface flatness was excellent.

(Comparative Example 8) In Example 18, instead of the fine particle powder P2 obtained in Example 2, zinc oxide fine particle powder obtained by the French method (Zinc Hua No. 1: manufactured by Sakai Chemical Co., Ltd.)
A paper was produced in the same manner as in Example 17 except that was used. The obtained paper contains fine particles in a secondary agglomerated state, and therefore has a low UV protection effect and has poor surface properties such as the presence of coarse projections due to agglomerated particles on the surface. It was

[0151]

The composite fine particles of the present invention contain zinc oxide fine particles and a polymer, and the zinc oxide fine particles account for 50 to 99% by weight based on the total weight of the zinc oxide fine particles and the polymer. It has a shielding ability, visible light transmittance and light diffusion are controlled, and it has excellent dispersibility.

The composite fine particles of the present invention have a particle size of 0.1 to 10 μm.
When it has a number average particle diameter of m, it has a further advantage that it has slipperiness and antiblocking property without impairing the surface flatness because the coating film and the molded article containing it have fine surface irregularities. The composite fine particles of the present invention,
The zinc oxide fine particles have a number average particle diameter of 0.1 to 10 μm, the zinc oxide fine particles have a number average particle diameter of 0.005 to 0.1 μm, and the zinc oxide fine particles have a number average particle diameter of the composite fine particles. When it is 1/1000 to 1/10 of the diameter,
Further, it has an advantage of exhibiting high ultraviolet ray shielding ability and high visible light transmittance.

When the composite fine particles of the present invention have a spherical shape and / or an elliptic spherical shape, the composite fine particles further have the advantage of being more easily dispersed in a resin or a coating solvent. The composite fine particles of the present invention have further excellent light diffusibility when they have an outer shell formed by aggregating zinc oxide fine particles. When the composite fine particles of the present invention are hollow,
Not only is the light diffusivity particularly high, but it can also have the function of porous fine particles or microcapsules.

When the polymer has one or more polar atomic groups, the fine composite particles of the present invention have further advantages of excellent chemical stability and mechanical properties. In the composite fine particles of the present invention, the polar atomic group possessed by the polymer is a carboxyl group, amino group, quaternary ammonio group, amide group, imide bond, hydroxyl group, carboxylic acid ester bond, urethane group, urethane bond, ureido group, When it is at least one selected from the group consisting of a ureylene bond, an isocyanate group, an epoxy group, a phosphoric acid group, a metal hydroxyl group, a metal alkoxy group and a sulfonic acid group, the chemical stability is further enhanced, and among the mechanical properties, It has the advantage of being excellent in mechanical strength such as crush strength.

The method for producing the fine composite particles of the present invention is carried out at 100 ° C. with a mixture containing zinc, a molcarboxylic acid, a polymer, and a medium capable of dissolving or dispersing a zinc / monocarboxylic acid / polymer and comprising at least an alcohol. By including the precipitation step of precipitating zinc oxide-polymer composite fine particles containing zinc oxide fine particles and a polymer by holding at the above temperature, it has an ultraviolet shielding ability, visible light transmittance and light diffusivity. This is a highly practical production method capable of producing zinc oxide-polymer composite fine particles that are controlled and have excellent dispersibility with high productivity and in a simple process.

In the production method of the present invention, the precipitation step comprises a first mixing step of preparing a first mixture containing zinc and a monocarboxylic acid by mixing a zinc source and a monocarboxylic acid, and at least an alcohol. And a second mixing step of preparing a second mixture in which zinc and a monocarboxylic acid are dissolved or dispersed in the medium by mixing the medium and the first mixture, the composite fine particles further excellent in dispersibility. It has the advantage of being easy to obtain.

In the production method of the present invention, when the first mixing step is a step of dissolving the zinc source in a mixed solvent of monocarboxylic acid and water, the particle size is further reduced (number average particle diameter 0.1 μm). It has an advantage that composite fine particles containing the following zinc oxide fine particles are easily obtained.
When the second mixing step is a step of adding the first mixture to the medium held at a temperature of 100 ° C. or higher and mixing, further, composite fine particles having high uniformity in particle diameter, particle shape, particle structure, etc. It has the advantage of being easily obtained.

In the production method of the present invention, when the polymer has one or more polar atomic groups, fine zinc oxide fine particles having a number average particle diameter of 0.005 to 0.1 μm can be easily obtained, and This has an advantage that it is easy to obtain composite fine particles having a uniform particle shape with a particle diameter variation coefficient of 30% or less. In the production method of the present invention, the polar atomic group possessed by the polymer is a carboxyl group, an amino group, a quaternary ammonio group, an amide group, an imide bond, a hydroxyl group, a carboxylic acid ester bond, a urethane group, a urethane bond, a ureido group, a ureylene. Bond, isocyanate group,
When it is at least one selected from the group consisting of an epoxy group, a phosphoric acid group, a metal hydroxyl group, a metal alkoxy group, and a sulfonic acid group, the chemical stability is further enhanced, and among mechanical properties, particularly crush strength and the like. It has an advantage that composite fine particles having excellent mechanical strength can be easily obtained.

In the production method of the present invention, when at least one zinc compound selected from the group consisting of zinc oxide, zinc hydroxide and zinc acetate is used as the zinc source, impurities that interfere with the reaction for producing flaky zinc oxide crystals are substantially eliminated. Not included, and it is easy to control the size and shape of crystals and fine particles. In the production method of the present invention, when a saturated fatty acid having a boiling point of 200 ° C. or less at 1 atm is used as the monocarboxylic acid, the amount of the monocarboxylic acid in the reaction system can be easily controlled, so that the precipitation reaction of zinc oxide crystals can be strictly controlled. Easy to control.

In the production method of the present invention, when the amount of the polymer is 0.01 to 1.0 in terms of weight ratio with respect to the amount of zinc oxide in the zinc source converted to zinc oxide, the particle size and This has an advantage that composite fine particles having a highly uniform particle shape can be easily obtained. The composite fine particles of the present invention and the composite fine particles obtained by the production method of the present invention, various films, fibers, resin molded articles such as sheets, glass products,
When blended in paints, cosmetics, etc., it can be easily dispersed uniformly in a medium such as a binder component, resin, solvent, etc., and can be used in resin molded products, glass products, paints, cosmetics, etc., for UV shielding ability, antibacterial properties, and fungicides. And the function of controlling light diffusivity and light transmittance in the visible region to the infrared region can be imparted.

By incorporating the composite fine particles of the present invention and the composite fine particles obtained by the production method of the present invention into base materials such as films and papers, good slipperiness is imparted to these base materials. You can also The coating composition of the present invention comprises the composite fine particles of the present invention, a binder component capable of forming a transparent or translucent continuous phase, and a solvent in which the composite fine particles are dispersed and the binder component is dispersed and / or dissolved. Therefore, it has the ability to block ultraviolet rays, and the visible light transmittance and light diffusivity are controlled.

The coating composition of the present invention comprises the composite fine particles obtained by the production method of the present invention, a binder component capable of forming a transparent or translucent continuous phase, and a composite fine particle dispersed to form a binder component. Since it contains a solvent that disperses and / or dissolves the above, it has an ultraviolet shielding ability, and has a visible light transmittance and a light diffusivity controlled. The coated article of the present invention comprises a transparent or translucent substrate and the coating composition of the present invention,
Since it has a coating film formed on the surface of the base material,
It has an ability to block ultraviolet rays and has a controlled visible light transmittance and light diffusivity.

Since the resin composition of the present invention contains the fine composite particles of the present invention and a resin capable of forming a transparent or translucent continuous phase, it has an ultraviolet shielding ability and a visible light transmitting property. The light diffusivity is controlled. The resin composition of the present invention,
Since it contains the composite fine particles obtained by the production method of the present invention and a resin capable of forming a transparent or semitransparent continuous phase,
It has an ability to block ultraviolet rays and has a controlled visible light transmittance and light diffusivity.

Since the resin molded article of the present invention is obtained by molding the resin composition of the present invention into a shape selected from the group consisting of plates, sheets, films and fibers, it has ultraviolet ray shielding ability and visible light The transparency and light diffusivity are controlled. The paper of the present invention comprises a paper pulp and the composite fine particles of the present invention dispersed in the pulp, and since the amount of the composite fine particles is 0.01 to 50% by weight with respect to the pulp, the ultraviolet light The shielding ability and the visible light transmittance are excellent, and the visible light diffusivity is controlled.

The paper of the present invention comprises paper made into paper, and the composite fine particles obtained by the production method of the present invention dispersed in the pulp. Since the content is 01 to 50% by weight, the ultraviolet ray shielding ability and the visible light transmitting property are excellent and the visible light diffusing property is controlled. The cosmetic of the present invention comprises 0.1% of the composite fine particles of the present invention.
Since it is contained in an amount of not less than wt%, it has excellent ultraviolet ray shielding ability and visible light transmittance, and the visible light diffusivity is controlled.

Since the cosmetic of the present invention contains 0.1% by weight or more of the composite fine particles obtained by the production method of the present invention, it has excellent ultraviolet ray shielding ability and visible light transmittance, and the visible light diffusibility is controlled. It becomes a thing.

[Brief description of drawings]

FIG. 1 is a transmission electron microscope image of powder P1 obtained in Example 1.

FIG. 2 is a transmission electron microscope image of zinc oxide fine particles in powder P1 obtained in Example 1.

Claims (32)

[Claims] 1. Zinc oxide-polymer composite fine particles containing zinc oxide fine particles and a polymer, wherein the zinc oxide fine particles are 50 to 99% by weight based on the total weight of the zinc oxide fine particles and the polymer. . 2. A number average particle diameter of 0.1 to 10 μm,
The composite fine particles according to claim 1, wherein the coefficient of variation in particle diameter is 30% or less. 3. The zinc oxide fine particles are 0.005-0.1
The number average particle diameter of μm, and the number average particle diameter of the zinc oxide fine particles is 1/10 to 1/1000 of the number average particle diameter of the composite fine particles. Composite fine particles. 4. The composite fine particles according to any one of claims 1 to 3, which are spherical and / or elliptical spherical. 5. The composite fine particles according to any one of claims 1 to 4, wherein the zinc oxide fine particles have an outer shell formed by aggregating. 6. The fine composite particles according to claim 5, wherein the inner side of the outer shell is hollow. 7. The fine composite particles according to claim 1, wherein the polymer has one or more polar atomic groups. 8. The atomic group is a carboxyl group, an amino group, a quaternary ammonio group, an amide group, an imide bond, a hydroxyl group, a carboxylic ester bond, a urethane group, a urethane bond, a ureido group, a ureylene bond, an isocyanate group,
The composite fine particle according to claim 7, which is at least one selected from the group consisting of an epoxy group, a phosphoric acid group, a metal hydroxyl group, a metal alkoxy group, and a sulfonic acid group. 9. Zinc, a monocarboxylic acid, a polymer,
A zinc oxide containing fine particles of zinc oxide and a polymer is obtained by maintaining a mixture containing zinc, the monocarboxylic acid, and a medium capable of dissolving or dispersing the polymer and containing at least an alcohol medium at a temperature of 100 ° C. or higher. Including a precipitation step of precipitating polymer composite fine particles,
A method for producing zinc oxide-polymer composite fine particles. 10. The depositing step comprises: a first mixing step of forming a first mixture containing the zinc and the monocarboxylic acid by mixing a zinc source and the monocarboxylic acid; and at least the alcohol. Mixing the medium with the first mixture to produce a second mixture in which the zinc and the monocarboxylic acid are dissolved or dispersed in the medium, a second mixing step. Production method. 11. The manufacturing method according to claim 10, wherein the first mixing step is a step of dissolving the zinc source in a mixed solvent of the monocarboxylic acid and water. 12. The manufacturing method according to claim 10, wherein the second mixing step is a step of adding the first mixture to the medium maintained at a temperature of 100 ° C. or higher and mixing. 13. The method according to claim 9, wherein the polymer has one or more polar atomic groups. 14. The atomic group is a carboxyl group, an amino group, a quaternary ammonio group, an amide group, an imide bond, a hydroxyl group, a carboxylic ester bond, a urethane group, a urethane bond, a ureido group, a ureylene bond, an isocyanate group,
The production method according to claim 13, wherein the production method is at least one selected from the group consisting of an epoxy group, a phosphoric acid group, a metal hydroxyl group, a metal alkoxy group, and a sulfonic acid group. 15. The method according to claim 10, wherein the zinc source is at least one zinc compound selected from the group consisting of zinc oxide, zinc hydroxide and zinc acetate. 16. The monocarboxylic acid is 200 at 1 atm.
The production method according to any one of claims 9 to 15, which is a saturated fatty acid having a boiling point of 0 ° C or lower. 17. The method according to claim 9, wherein the amount of the polymer is 0.01 to 1.0 in terms of a weight ratio with respect to the amount of zinc atom in the zinc source converted to zinc oxide. The manufacturing method described in. 18. The zinc oxide-polymer composite fine particles according to claim 1, a binder component capable of forming a transparent or translucent continuous phase, and the binder containing the composite fine particles dispersed therein. A coating composition containing a solvent that disperses and / or dissolves the components. 19. A zinc oxide-polymer composite fine particle produced by the production method according to claim 9, a binder component capable of forming a transparent or semitransparent continuous phase, and the composite. A coating composition comprising a solvent in which fine particles are dispersed and the binder component is dispersed and / or dissolved. 20. The amount of the fine composite particles is 0. 0 based on the total solid content of the fine composite particles and the binder component.
The coating composition according to claim 18 or 19, which is 1 to 80% by weight. 21. The total solid content of the composite fine particles and the binder component is 1 to 80% by weight, and the amount of the solvent is 1.
The coating composition according to claim 20, which is 0 to 99% by weight. 22. A coated article comprising a transparent or translucent base material and a coating film formed on the surface of the base material, comprising the coating composition according to any one of claims 18 to 21. . 23. The coated article according to claim 22, wherein the substrate is at least one selected from the group consisting of resin molded articles, glass and paper. 24. The coated article according to claim 23, wherein the resin molded article is at least one selected from the group consisting of plates, sheets, films and fibers. 25. A resin composition comprising the zinc oxide-polymer composite fine particles according to any one of claims 1 to 8 and a resin capable of forming a transparent or translucent continuous phase. 26. A resin composition comprising zinc oxide-polymer composite fine particles produced by the production method according to claim 9 and a resin capable of forming a transparent or translucent continuous phase. . 27. The resin composition according to claim 25 or 26, wherein the amount of the composite fine particles is 0.1 to 80% by weight based on the total solid content of the composite fine particles and the resin. 28. A resin molded product obtained by molding the resin composition according to claim 25 into a shape selected from the group consisting of plates, sheets, films and fibers. 29. A pulp produced by papermaking, and the zinc oxide-polymer composite fine particles according to claim 1, which are dispersed in the pulp, wherein the amount of the composite fine particles is the pulp. 0.01 to
Paper that is 50% by weight. 30. A composite comprising: a pulp made into paper; and zinc oxide-polymer composite fine particles produced by the production method according to any one of claims 9 to 17, dispersed in the pulp. The amount of fine particles is 0.01 to the above pulp.
Paper that is 50% by weight. 31. A cosmetic material containing 0.1% by weight or more of the zinc oxide-polymer composite fine particles according to any one of claims 1 to 8. 32. A cosmetic containing 0.1% by weight or more of zinc oxide-polymer composite fine particles produced by the production method according to any one of claims 9 to 17.