JPH0959591A - Composition for shielding infrared ray and heat ray, and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition simultaneously cutting both infrared rays and heat rays, achieving a heat ray-cutting degree having not been achieved, and giving a transparent product capable of arbitrarily controling cutting performances such as cutting length, cutting amount, etc., in response to needs. SOLUTION: A composition for shielding infrared rays and heat rays comprises (A) the fine particles of the oxide coprecipitates of metals comprising (i) 80-99.9atom% of zinc and (ii) 20-0.1atom% of a IIIB group metal element, (b) a heat ray-adsorbing agent (e.g. octafluoro-octakisanilinozinc phthalocyanine) and, if necessary, (C) a dispersing medium comprising a (meth)acrylic acid resin, etc. The composition can be formed into plates, sheets, films or fibers.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a composition for shielding ultraviolet rays and heat rays, and its use.

[0002]

2. Description of the Related Art Zinc oxide fine particles can transmit visible light,
Compared with titanium oxide fine particles, the wavelength range of ultraviolet rays is wider toward the long wavelength side, and the ultraviolet ray cutting effect lasts for a long time. Therefore, zinc oxide fine particles are contained in a resin to be used as a resin molded product such as a film, fiber and resin plate, or zinc oxide fine particles are contained in an organic or inorganic binder to form a film, fiber, resin plate, glass and It is used as a paint to be applied to a base material such as paper, and transparent products having an ultraviolet shielding effect are produced.

[0003]

The transparent product is required to have not only an ultraviolet ray shielding effect but also a heat ray shielding effect. However, zinc oxide fine particles do not have a heat ray shielding property. An object of the present invention is to provide a composition capable of transmitting visible light and simultaneously blocking ultraviolet rays and heat rays.

Another object of the present invention is to transmit visible light,
It is an object of the present invention to provide a resin molded product capable of simultaneously blocking ultraviolet rays and heat rays. Still another object of the present invention is to provide a coated article having a coating film capable of transmitting visible light and simultaneously blocking ultraviolet rays and heat rays.

[0005]

The ultraviolet and heat ray shielding composition of the present invention comprises 80 to 99.9 atomic% zinc and
It contains fine particles of a metal oxide coprecipitate composed of a Group IIIB metal element of 0.1 to 20 atomic% and a heat ray absorbent. The composition of the present invention may further include a dispersion medium regardless of whether or not the heat ray absorbent is a phthalocyanine compound. The dispersion medium disperses the fine particles and the heat ray absorbent.

The resin molded product of the present invention is made of zinc 80-99.
From a plate, a sheet, a film and a fiber, a composition containing 9 atom% and a fine particle of an oxide coprecipitate of a metal consisting of 0.1 to 20 atom% of a Group IIIB metal element, a heat ray absorbent and the dispersion medium is prepared. It is molded into at least one shape selected from the group consisting of: Here, the dispersion medium is a resin. The coated article of the present invention includes a base material and a coating film formed on the surface of the base material. The substrate is at least one selected from the group consisting of resin molded products, glass and paper. The coating film comprises a composition containing fine particles of a metal oxide coprecipitate composed of 80 to 99.9 atomic% of zinc and 0.1 to 20 atomic% of a Group IIIB metal element, a heat ray absorbent, and the dispersion medium. Comprises. Here, the dispersion medium is a binder component.

In the composition of the present invention, the resin molded product of the present invention, and the coated product of the present invention, the heat ray absorbent is an organic dye having absorption in the near infrared region, for example, a phthalocyanine compound.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION

[UV and heat ray-shielding composition] The UV ray and heat ray-shielding composition of the present invention is a metal oxide coprecipitate comprising 80 to 99.9 atomic% zinc and 0.1 to 20 atomic% IIIB metal element. It contains fine particles of the body and a heat ray absorbent.

Fine particles of a metal oxide coprecipitate consisting of 80 to 99.9 atomic% zinc and 0.1 to 20 atomic% Group IIIB metal element (hereinafter sometimes referred to as "zinc oxide fine particles"). Is capable of transmitting visible light, has a wider UV cut wavelength range to the long wavelength side than titanium oxide fine particles, has a long-lasting UV cut effect, and has infrared rays over a wide wavelength range including infrared rays including heat rays. It has a cutting ability. The heat ray absorbent has a selective cutting ability in a specific wavelength region of near infrared. Therefore, by combining the zinc oxide-based fine particles and the heat ray absorbent, a heat ray cutting ability which has not been available in the past can be achieved, and the cutting performance (cutting wavelength, cutting amount, etc.) can be arbitrarily controlled according to needs.

The organic dye used in the present invention may have any structure as long as it is an organic compound having absorption in the near infrared region (heat ray region). Representative examples of such organic dyes include cyanine dyes, pyrylium dyes, squalium dyes, dithiol nickel complex dyes, azo dyes,
Examples thereof include naphthoquinone, anthraquinone dye, triphenylmethane dye, aminium dye, diimonium dye, phthalocyanine dye (the above phthalocyanine compound), and naphthalocyanine dye.

The dye used in the present invention preferably has solubility and weather resistance in a dispersion medium. Therefore, among the dyes listed above, a soluble phthalocyanine dye (that is, a soluble phthalocyanine compound among the above dyes) is used. )
Is preferred. Such a soluble phthalocyanine dye,
JP-A-6-107663 and JP-A-6-25548.
Japanese Patent Laid-Open Publication No. 5-345861, Japanese Laid-Open Patent Publication No. 5-25861
No. 22301, No. 5-222047, No. 4-39361, No. 4-23868, No. 2-175763, and No. 64-45.
No. 474 (above, Nippon Shokubai Co., Ltd.), JP-A-61
-152769, JP 61-152689, JP 61-152685 (above, TD
K), JP-A-7-70129, JP-A-4-273.
No. 879, No. 60-209583, No. 63-308073 (above, ICI and / or Zeneca), No. 5-25177, No. 5-25177.
-1272, JP-A-3-62878, JP-A-3-31247, JP-A-63-270765 (above, Mitsui Toatsu) and the like. Specifically, for example, the compounds shown below and compounds having such a structure can be used. Octafluoro-octakisanilino zinc phthalocyanine Octafluoro-octakisanilinooxy vanadium phthalocyanine (hereinafter referred to as ph-1) Octafluoro-octakis-p-ethoxycarbonylcobalt phthalocyanine Octafluoro-octakis-n- Octylaminodichlorotin phthalocyanine, octafluoro-octakisphenylthiozinc phthalocyanine, octafluoro-octakis-m-tetrahydrofurfuryloxycarbonylphenoxyoxyvanadium phthalocyanine, dodecafluoro-tetrakistorzino dichlorotin phthalocyanine (hereinafter referred to as ph-4. ) Dodecafluoro-tetrakis-1-naphthylaminodichlorotin phthalocyanine Dodecafluoro-tetrakisbenzylamino Phthalocyanine-dodecafluoro-tetrakiscyclohexylaminopalladium phthalocyanine-dodecafluoro-tetrakisphenylthiodichlorotin phthalocyanine-octafluoro-tetrakisphenylenedithiozinc phthalocyanine-octakisanilino-octakisphenylthiooxyvanadium phthalocyanine (hereinafter referred to as ph-2) ) ・ Octakisanilino-octa-o-methoxyphenylthiocopper phthalocyanine (hereinafter referred to as ph-5) ・ Octakis-o-ethoxyanilino-octakis-n
-Octylthiocobalt phthalocyanine-Octakisanilino-octakisphenoxyzinc phthalocyanine (hereinafter referred to as ph-3) -Tetrakis-n-butylamino-octanaphthylthioiron phthalocyanine-Tetrakisanilino-dodeca-m-methylphenylthio Copper phthalocyanine-Octakis-n-butoxy-octakis-o-ethoxyphenyldichlorotin phthalocyanine-Octakisphenylthio-octakis-n-butylthiocobalt phthalocyanine-Octa-3,6-isopentyloxy-octa-4,
5-dichlorooxy vanadium phthalocyanine octa-3,6-n-octyloxy-octa-4,
5-bisphenylthiocopper phthalocyanineocta-3,6-isohexyloxy-octa-4,
5-bis-p-tert-butylphenylthiocopper phthalocyanine Tetrakis-3- (2,4-dimethyl) pentyloxypalladium phthalocyanine Tetrabromo-tetrakis-2- (3-methyl) pentyloxynickel phthalocyanine Mono (phenylamino) ) Tetradeca (4-methylphenylthio) copper phthalocyaninePenta (4-aminophenylamino) deca (2-methylphenylthio) copper phthalocyanineDi (4-methoxyphenylamino) deca (4-methylphenylthio) copper phthalocyanine Octa-3,6- (4-methylphenylthio) -copper phthalocyanine Phenyl-1,4-diylenethio-bis (hepta-
3,6-Phenylthio) copper phthalocyanine.Pentadeca (4-carboxyphenylthio) copper phthalocyanine The type of dispersion medium that can be used in the composition for shielding ultraviolet rays and heat rays of the present invention is not particularly limited, but may be appropriately selected depending on the purpose of use. To be selected. 1. When the composition of the present invention is a resin composition and a resin molded article When the composition of the present invention is a resin composition and a resin molded article, the dispersion medium contains zinc oxide-based fine particles and a heat ray absorbent. And a resin capable of forming a continuous phase that is dispersed.
The dispersion medium is a resin, a resin solution, a resin dispersion liquid, or the like.
Examples of the resin include (1) 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) acrylic resin such as (meth) acrylate, phenol resin; urea resin, melamine resin, unsaturated polyester resin, polycarbonate resin, thermoplastic or thermosetting resin such as epoxy resin,
(2) Synthetic rubber or natural rubber such as ethylene-propylene copolymer rubber, polybutadiene rubber, styrene-butadiene rubber, and acrylonitrile-butadiene rubber are exemplified, and any one of them is used alone, or
Two or more are used together. Among them, (meth) acrylic resin, polycarbonate resin, polyester resin, vinyl chloride resin and the like are preferably used because of their excellent transparency.

When the composition of the present invention is a resin composition or a resin molded article, the amounts of the zinc oxide type fine particles, the heat ray absorbent and the resin (dispersion medium) are, for example, in the composition of the present invention. 0.01 to 99% by weight of zinc oxide type fine particles, 0.00 of a heat ray absorbent, based on the total weight of solids of the three parties.
The proportions are 05 to 20% by weight and 0.1 to 99.9% by weight of resin (preferably 5 to 99.9% by weight). If the proportion of the zinc oxide-based fine particles is less than the above range, the thickness of the molded article must be increased in order to obtain sufficient ultraviolet shielding properties, and if it exceeds the above range, the dispersibility of the fine particles decreases and the molded article with respect to visible light. Transparency may decrease. If the proportion of the heat ray absorbent is less than the above range, it may be difficult to obtain sufficient heat ray shielding property, and if it exceeds the above range, the transparency of the molded product to visible light may be lowered or the price may be increased. When the proportion of the resin as the dispersion medium is less than the above range, the dispersibility of the fine particles is lowered and the transparency of the molded product to visible light is lowered, or the physical properties of the molded product such as mechanical properties and chemical resistance are poor. In some cases, the thickness of the molded product must be increased in order to obtain sufficient ultraviolet light shielding properties. 2. When the composition of the present invention is a coating composition When the composition of the present invention is a coating composition, the dispersion medium contains, for example, a binder component capable of forming a film that binds the zinc oxide based fine particles. The dispersion medium is a binder component, a solution of the binder component, or an emulsion or suspension of the binder component. Although the binder component is not particularly limited, for example, (1) (meth) acrylic, vinyl chloride, silicone, melamine, urethane, styrene, alkyd, phenol, epoxy, polyester, etc. Plastic or thermosetting synthetic resin; ethylene-propylene copolymer rubber, polybutadiene rubber, styrene-butadiene rubber, synthetic rubber such as acrylonitrile-butadiene rubber or organic binder such as natural rubber, (2) silica sol, alkali silicate, silicon Inorganic binders such as alkoxides and phosphates 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 alone, or
Two or more are mixed and used.

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, and the like. For example, alcohols, aliphatic and aromatic carboxylic acid esters, ketones, ethers,
Organic solvents such as ether esters, aliphatic and aromatic hydrocarbons, halogenated hydrocarbons; water; mineral oils, vegetable oils, wax oils, silicone oils, etc. are exemplified, and may be appropriately selected according to the purpose of use. Well, if necessary, two or more may be mixed and used in an arbitrary ratio. As the solvent of the binder component, the solvent of the zinc oxide type fine particle dispersion can be used.

When the composition of the present invention is a coating composition,
In the composition of the present invention, zinc oxide fine particles, heat ray absorbent,
And, the amount of the binder component (dispersion medium) is, for example, 0.1 to 99% by weight of zinc oxide type fine particles and 0.0005 to 500% of the heat ray absorbent based on the total weight of the solid contents of these three parties.
20 wt%, binder component 0.1 to 99.9 wt%, preferably zinc oxide fine particles 10 to 79.9 wt%, heat ray absorber 0.1 to 10 wt%, binder component 20 to 89. The ratio is 9% by weight. If the proportion of zinc oxide-based fine particles is less than the above range, the thickness of the coating film must be increased in order to obtain sufficient ultraviolet shielding properties, and if it exceeds the above range, the dispersibility of the fine particles is reduced and the coating film against visible light. Transparency may decrease. If the proportion of the heat ray absorbent is less than the above range, it may be difficult to obtain sufficient heat ray shielding property, and if it exceeds the above range, the transparency of the coating film to visible light may be lowered or the cost may be increased. When the proportion of the binder component as the dispersion medium is less than the above range, the dispersibility of the fine particles is lowered and the transparency of the coating film to visible light is lowered, and the physical properties of the coating film such as mechanical properties and chemical resistance are In some cases, the thickness of the coating film must be increased in order to obtain sufficient ultraviolet light shielding properties.

When the composition of the present invention is a coating composition,
The total amount of solid contents of the zinc oxide fine particles, the heat ray absorbent, and the binder component is 1 to 80 based on the total weight of the composition.
The proportion by weight is preferably 5 to 50% by weight. If it is less than the above range, it may be difficult to obtain a uniform film or it may be difficult to control the film thickness. It may be difficult to form a film. The balance is a solvent that disperses the zinc oxide type fine particles and dissolves or disperses the van der component, or the solvent and an additive such as a pigment used depending on the purpose of use of the coating composition.

When the composition of the present invention is a resin composition, a resin molded product, or a coating composition, the mixing ratio of the zinc oxide type fine particles and the heat ray absorbing agent is such that the zinc oxide type fine particles are mixed with the heat ray absorbing agent. The solid content weight ratio is 0.05 to 30% by weight, preferably 0.3 to 20% by weight. If it is less than the above range, the effect of adding the heat ray absorbent may be lowered, and if it is more than the above range, the visible light transmittance may be lowered.

The method for producing the composition of the present invention is not particularly limited. When the composition of the present invention is a resin composition and a resin molded article, the desired composition can be obtained by mixing and dispersing zinc oxide type fine particles and a heat ray absorbent in a resin which is a dispersion medium. For example, when melt-kneading a pellet-shaped or powdered resin, a masterbatch method in which zinc oxide-based fine particle powder and a heat ray absorbent are added and mixed, a zinc oxide-based fine particle and a heat ray absorbent are mixed in a resin solution. A conventionally known method such as a method of removing the solvent after dispersion can be adopted. Alternatively, a method of mixing and dispersing zinc oxide-based fine particles and a heat ray absorber in the process of producing a resin, for example, when the resin is a polyester resin, a series of steps in the polyester production process, that is, in the transesterification reaction to the polymerization reaction is performed. It is also possible to employ a method in which a zinc oxide-based fine particle powder and a dispersion prepared by dispersing a heat ray absorbent in glycol, which is a polyester raw material, are added and mixed at an arbitrary stage of the process.

According to the above-mentioned method, a resin composition containing zinc oxide type fine particles and a heat ray absorbent dispersedly contained in the resin can be obtained. The resin composition may be in the form of a usual molding material such as pellet. The method for producing the composition of the present invention as a coating composition is not particularly limited. For example, a method of adding a powder of zinc oxide-based fine particles to a solvent containing a heat ray absorbent and a binder component and dispersing the powder, a dispersion of zinc oxide-based fine particles in a solvent and a solvent containing a heat ray absorbent and a binder component. And the like, a method of adding a heat ray absorbent and a binder component to a dispersion prepared by dispersing fine particles of zinc oxide in a solvent, and mixing them. 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.

When the composition of the present invention is obtained as a coating composition, a binder component or a solvent containing a binder component is directly added to and mixed with the fine particle dispersion obtained by the above-mentioned method for producing zinc oxide type fine particles. Can also be obtained by According to the above-described method for producing a coating composition, a coating composition containing at least zinc oxide type fine particles, a heat ray absorbent, a binder component and a solvent can be obtained.

The zinc oxide-based fine particles used in the composition of the present invention contain zinc as a metal component and at least one additive element selected from the group consisting of Group IIIB metal elements, and the content of zinc is equal to that of the metal. The ratio of the number of zinc atoms to the total number of atoms of the component is 80 to 99.9%, and at least a metal oxide coprecipitate showing zinc oxide (ZnO) crystallinity as a result of X-ray diffraction It is a zinc oxide-based fine particle as a constituent component. Here, the crystal form of zinc oxide is not particularly limited, and for example, hexagonal crystal (wurtzite structure), cubic crystal (salt type structure), cubic crystal face center structure, etc. are known, and any of these is known. Any X-ray diffraction pattern may be used. In the zinc oxide-based fine particles of the present invention, the zinc content of the metal oxide coprecipitate is 80 to 99.9%, preferably 90 to 9 in terms of the ratio of the number of zinc atoms to the total number of metal components.
It is 9.5%. If it is less than the above range, it becomes difficult to form fine particles having a controlled uniformity of particle shape, particle diameter, higher order structure, etc., and if it exceeds the above range, the function as a coprecipitate, that is, the infrared ray shielding property including heat rays becomes insufficient.

The zinc oxide type fine particles referred to in the present invention are, for example, as long as they are as described above, and therefore, for example, a coupling agent such as a silane coupling agent or an aluminum coupling agent or an organic compound such as an organosiloxane or a chelate compound. The metal compound is a fine particle formed by binding to the surface of the zinc oxide crystal or forming a coating layer on the surface, an inorganic acid such as a halogen element, a sulfate group, a nitrate group, or an organic compound such as a fatty acid, an alcohol, an amine, etc. And / or particles contained on the surface are also included in the zinc oxide-based fine particles of the present invention.
At least one selected from the group consisting of Group IIIB metal elements
As the additive element of the seed and the metal element other than zinc, it is not preferable that the alkali metal and the alkaline earth metal exist in the form of a solid solution in the ZnO crystal, and the group IIIB metal element forming the coprecipitate. It is preferably 1/10 or less, and more preferably 1/100 or less, with respect to the total number of atoms of at least one additional element selected from the group consisting of

In the zinc oxide type fine particles of the present invention, the group IIIB metal element as an additional element constituting the metal oxide coprecipitate is, for example, boron, aluminum (Al), gallium (Ga), indium (In) or thallium. It is at least one selected from (Tl), and among these, indium and / or aluminum is most preferable.

The zinc oxide type fine particles of the present invention include the following first
There are cases such as ~ 3. 1. Single particles of the metal oxide coprecipitate, that is, when the crystallites are dispersed in a single crystal state without secondary aggregation,
Partially or wholly loosely secondary aggregated (more than
In the first case). 2. The single particles are aggregated as primary particles and exist as secondary particles having a higher-order structure such as spherical particles (second case).

3. In the cases 1 and 2 above, the coprecipitate is a complex with a polymer (case 3). In any of the first to third cases, excellent transparency,
Preferred embodiments of the zinc oxide based fine particles for obtaining the resin molded product or coated product of the present invention will be described below. That is, the zinc oxide based fine particles have an average crystallite size of 0.001 to 0.05 μm.
It is preferable that the average particle diameter is m and the average dispersed particle diameter is 0.001 to 0.2 μm, because the composition, the resin molded article and the coating film of the present invention containing the fine particles have excellent transparency. More preferably, the average crystallite size is 0.005 to 0.
Range of 03 μm, average dispersed particle size is 0.005 to 0.1
The average crystallite size is in the range of 0.005 to 0.03 μm, and the average dispersed particle size is in the range of 0.005 to 0.03 μm. This is because if the average crystallite size is less than 0.005 μm or the average dispersed particle size is less than 0.005 μm, the UV absorption edge may blue-shift to the short wavelength side. When the average crystallite size is larger than 0.03 μm, visible light is scattered, so that the transparency of a coating film containing the fine particles may be deteriorated. If the average dispersed particle size is larger than 0.1 μm, the transparency of a coating film containing the fine particles may be decreased,
The dispersion stability of the paint may be reduced.

The average crystallite diameter is a value D (μm) obtained by using the Scherrer formula (the following formula) from the diffraction angle θ and the diffraction line width β (radian) obtained by X-ray diffraction measurement. is there. K is the Scherrer constant and λ is the used X
The wavelength of the line (μm). D = Kλ / β cos θ The average dispersed particle diameter means the weight or number average value of the dispersed particle diameter of the fine particles in the medium in which the fine particles are dispersed and contained. For example, the average dispersed particle size of the fine particles in the coating composition refers to the average dispersed particle size of the fine particles in the coating composition. Usually, when the medium is liquid, it is measured by a dynamic light scattering method or centrifugal sedimentation method, and when the medium is a solid (resin molded article etc.), it is measured by a transmission electron microscope. However, when the crystallite is flaky, the length in the thickness direction is 0.05 μm or less, preferably 0.03.
If the flaky crystals are dispersed in a state in which secondary aggregation is suppressed, a transparent resin molded product or coated product can be obtained.

In the present invention, the shape of the metal oxide coprecipitate / zinc oxide type fine particles is arbitrary. For example,
Flake shape, flaky shape such as (hexagonal) plate shape; needle shape, columnar shape, rod shape, cylindrical shape; granular shape such as cubic shape and pyramid shape; spherical shape and the like. In the second case, the secondary particles of the zinc oxide-based fine particles may be hollow ones that are composed only of the outer shell. When it is hollow, it has excellent light diffusion and transmission properties. In this case, the relationship between the size of the zinc oxide-based fine particles of the single particles and the secondary particles as an aggregate thereof is that the ratio of the particle diameter of the shortest part of the single particles to the particle diameter of the shortest particle is 1/10 or less. Preferably there is.

In the third case, the form of the composite is arbitrary, but, for example, first, the surface of (A) polymer is the surface of one single particle and / or the aggregate of a plurality of single particles. There is a form in which (B)
There is a form in which a polymer binds the single particles to each other, and finally, (C) the polymer constitutes a matrix, and the single particles are not aggregated in the matrix and / or the single particles are plural. There is a form in which a collection of pieces is dispersed. In this case as well, the single particle and the polymer may be hollow in which only the outer shell portion is constituted, and if the hollow shape is obtained, the light diffusion and transmission properties are excellent, as in the second case. is there. In this case, the content of the polymer is not particularly limited, but is in the range of 1 to 90% by weight based on the total amount of the single particles and the polymer.

In the third case, the polymer used for the compounding is an acrylic resin polymer, an alkyd resin polymer, an amino resin polymer, a vinyl resin polymer, an epoxy resin polymer, a polyamide resin polymer, a polyimide resin. -Based polymers, polyurethane resin-based polymers, polyester resin-based polymers, phenol resin-based polymers, organopolysiloxane-based polymers, acrylic silicone resin-based polymers, polyalkylene glycols, etc., as well as polyolefin-based polymers such as polyethylene and polypropylene, polystyrene-based polymers, etc. Thermoplastic or thermosetting resin; ethylene-propylene copolymer rubber, polybutadiene rubber, acrylonitrile-butadiene rubber, and other synthetic rubber and natural rubber.

The preferred polymer is one having one or more polar atomic groups because the zinc oxide type fine particles are excellent in chemical stability such as solvent resistance and chemical resistance and mechanical properties. 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 zinc oxide-based fine particles is further enhanced, but also the mechanical strength such as crushing strength is excellent, and moreover, fine particles (average particle diameter 0.001 to 0.1 μm) are used.
m) This is because it is easy to obtain a single particle, and the particle diameter is uniform (the variation coefficient of the particle diameter is 30% or less), and it is easy to obtain the zinc oxide type fine particles having a uniform particle shape.

Among the polymers exemplified above as the polymer used for the compounding, it is selected from the group consisting of (meth) acrylic type, styrene type, vinyl type, their copolymerization type, alkyd type, polyester type, and polyamide type. At least one main chain, a carboxyl group, an amino group,
Composite particles with a polymer having at least one polar atomic group selected from the group consisting of an amide group, a silanol group, and an alkoxysilyl group are preferable because they have particularly excellent affinity and dispersibility for a transparent resin.

In both the second and third cases, the average particle diameter of the zinc oxide type fine particles is not particularly limited,
Usually, it is in the range of 0.001 to 10 μm. For example,
In the case (A) of the third case, 0.001 to 0.05 μm is preferable in terms of high transparency as described above, and in the case of a hollow body shape, it is 0.1 in terms of high light diffusion and transmission ability. ~ 5
μm is preferred.

The zinc oxide type fine particles of the present invention may be used as a dispersion prepared by dispersing them in a solvent. In this case, as the medium, water, alcohols, ketones,
In addition to aliphatic and aromatic carboxylic acid esters, ethers, ether esters, aliphatic and aromatic hydrocarbons and halogenated hydrocarbons, there are mineral oil, vegetable oil, wax oil, silicone oil and the like. Further, these solvents may contain other components, for example, an organic binder or an inorganic binder used as a binder for paints. As the organic binder,
(Meth) acrylic, vinyl chloride, silicone, melamine, urethane, styrene, alkyd, phenol, epoxy, polyester or other thermoplastic or thermosetting resin; ethylene-propylene copolymer rubber, There are synthetic rubbers and natural rubbers such as polybutadiene rubber and acrylonitrile-butadiene rubber, and examples of the above-mentioned inorganic binders include silica sol, alkali silicates, silicon alkoxides and phosphates.

The zinc oxide type fine particles used in the present invention include, for example, a zinc source and a monocarboxylic acid in a medium containing at least an alcohol and at least one additive element selected from the group consisting of Group IIIB metal elements. It is made by a manufacturing method of maintaining a temperature of 100 ° C. or higher in the presence of a compound containing In this case, for example, the above-mentioned ones are exemplified as the group IIIB metal element, and among these additional elements,
Similarly, indium and / or aluminum is preferable.

Specifically, the above-mentioned production method is, for example, a first step of producing a first mixture containing a zinc source and a monocarboxylic acid, and the first mixture is mixed with a medium containing at least alcohol. And a second step of making a second mixture,
A third step of maintaining the second mixture at a temperature of 100 ° C. or higher, and in any of the first, second and third steps, the first and / or second step A compound containing at least one additional element selected from the group consisting of Group IIIB metal elements is added to and mixed with the mixture. At this time, the compound containing the additional element may be added alone, or may be dissolved in a medium containing at least alcohol and added. In the first step, the zinc source is
It is preferable to dissolve the monocarboxylic acid in a mixed solvent in which water is dissolved.

In the above-mentioned production method, a mixture of a zinc source and a monocarboxylic acid is mixed with water, and the mixture is added to a medium which is heated to 100 ° C. or higher and which is composed of at least alcohol. It is preferable to include a step of removing at least a part of the acid by evaporation. The zinc source and the monocarboxylic acid are preferably dissolved in water before use, but the crystallinity of the fine particles is prevented from being impaired and secondary agglomeration is prevented to ensure uniformity of the size and shape of the fine particles. This is because it is preferable to remove water or monocarboxylic acid out of the system as much as possible in order to obtain it. In addition,
The formation of fine particles may occur during the addition of the mixture to the heating medium, but the formation usually occurs after that by keeping the reaction system at a temperature of 100 ° C. or higher. During this period, water and monocarboxylic acid are usually removed by evaporation.

The zinc source is, for example, at least one selected from the group consisting of zinc oxide, zinc hydroxide and zinc acetate. The monocarboxylic acid has a boiling point of 200 ° under normal pressure.
It is preferably a saturated fatty acid of C or less. In the above production method, the zinc source and the monocarboxylic acid are treated at 100 ° C. or higher in a medium containing at least alcohol and in the presence of a compound containing at least one additive element selected from the group consisting of Group IIIB metal elements. When the temperature is maintained at this temperature, a polymer is allowed to coexist in this system, or a carboxyl group, amino group, quaternary ammonio group, amide group, imide bond, alcoholic and / or phenolic hydroxyl group in the molecule,
Carboxylate bond, urethane group, urethane bond,
It has one or more atomic groups of at least one selected from the group consisting of ureido group, ureylene bond, isocyanate group, epoxy group, phosphoric acid group, metal hydroxyl group, metal alkoxy group and sulfonic acid group. , The molecular weight is 100
An additive compound of less than 0 may coexist, a carbon dioxide and / or carbonic acid source may coexist, or a lactic acid source may coexist.

When a polymer is allowed to coexist when the system is maintained at a temperature of 100 ° C. or higher, zinc oxide type fine particles in which the single particles are combined with the polymer can be obtained. Suitable polymers used in this case include the above-mentioned acrylic resin-based polymers, alkyd resin-based polymers, amino resin-based polymers, vinyl resin-based polymers, epoxy resin-based polymers, polyamide resin-based polymers, polyimide resin-based polymers, polyurethanes. In addition to resin-based polymers, polyester resin-based polymers, phenol resin-based polymers, organopolysiloxane-based polymers, acrylic silicone resin-based polymers, polyalkylene glycols, etc., polyolefin-based polymers such as polyethylene and polypropylene, and thermoplastics such as polystyrene-based polymers Thermosetting resin: Synthetic rubber such as ethylene-propylene copolymer rubber, polybutadiene rubber, acrylonitrile-butadiene rubber and natural rubber. When the polymer has the above-described specific functional group, the fine particles can be surface-treated and the particle size can be controlled.

When the system is kept at a temperature of 100 ° C. or higher, the surface treatment of the fine particles becomes possible and the particle diameter can be controlled by coexisting with the above-mentioned compound having a specific functional group. When carbon dioxide and / or a carbonic acid source are allowed to coexist when the system is maintained at a temperature of 100 ° C. or higher, fine particles of fine (0.05 μm or less) excellent in water dispersibility are easily obtained. In this case, the carbonic acid source can be replaced by using (basic) zinc carbonate as a part of the zinc raw material. However, it is appropriate that the amount of the carbonic acid source is 0.1 to 20 mol% in terms of molar ratio with respect to zinc. This is because if the amount is too large, the crystallization of zinc oxide may be hindered, and the heat treatment temperature needs to be increased. Examples of the carbonic acid source include compounds such as ammonium carbonate, ammonium hydrogencarbonate and urea which generate carbonate ions or carbon dioxide gas by heating; yttrium carbonate, cadmium carbonate,
Metal carbonates such as silver carbonate, samarium carbonate, zirconium carbonate, cerium carbonate, thallium carbonate, lead carbonate, bismuth carbonate, basic zinc carbonate, basic cobalt carbonate (1I), basic copper carbonate (II), basic lead carbonate (II), basic carbonates of metals such as basic nickel (II) carbonate, etc. are exemplified, and they may be used alone or in combination of two or more.

One effective method for obtaining the zinc oxide type fine particles in the form of secondary particles formed by aggregating single particles composed of coprecipitates of metal oxides is as follows.
An example is a method in which a lactic acid source is allowed to coexist when the system is maintained at a temperature of 100 ° C. or higher. The lactic acid source used in the present invention is
Lactic acid; ammonium lactate, sodium lactate, lithium lactate, calcium lactate, magnesium lactate, zinc lactate, aluminum lactate, manganese lactate, iron lactate, nickel lactate, silver lactate, and other metal lactates; methyl lactate, ethyl lactate,
Lactic acid ester compounds such as n-butyl lactate that can generate lactic acid by hydrolysis and the like, and any one of them may be used alone, or two or more thereof may be used in combination.

In the second and third cases, when the secondary particles have a large number of pores between the primary particles and when they are hollow, the function as porous fine particles or microcapsules, for example, Adsorption, separation, removal and collection functions such as oil absorption, moisture absorption, adsorption of harmful metal ions, absorption of toxic gases and malodors; insulation of heat and sound such as heat insulation and sound insulation (insulation filler, Sound-insulating filler); Immobilizing function such as metal ion, enzyme / bacterial immobilization (catalyst carrier, chromatographic packing material, etc.); Light weight; it can.

One example of the method for producing the zinc oxide type fine particles used in the present invention will be described in detail below. This manufacturing method, for example,
A mixture (m) obtained by dissolving or dispersing the zinc source and the monocarboxylic acid in a medium containing at least alcohol is used to prepare at least one additive element (hereinafter, referred to as a group IIIB metal element) A compound containing a “metal (M)” (this compound is a concept that also includes a metal such as a simple metal or an alloy. Hereinafter, it may be referred to as a “metal (M) compound”) 100 in coexistence
The crystallinity of the metal oxide containing 80 to 99.9% of zinc and 0.1 to 20% of metal (M) in terms of the ratio of the number of atoms to the total number of atoms of the metal element by maintaining the temperature at ℃ or higher. Precipitate zinc oxide-based fine particles composed of a coprecipitate.

By heating the mixture (m) containing the monocarboxylic acid and alcohol, the zinc source is converted into crystalline zinc oxide by X-ray diffraction, and at this time, the metal (M The coexistence of the compound makes it possible to obtain a dispersion containing the zinc oxide-based fine particles of the present invention. At that time, if any one of the three components of the zinc source, the monocarboxylic acid, and the alcohol is missing as a starting material, the precipitation reaction of zinc oxide crystals does not occur, and if the metal (M) does not exist, the present invention No zinc oxide-based fine particles can be obtained.

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,
Metallic zinc (zinc dust), zinc oxide (zinc white, etc.), zinc hydroxide, basic zinc carbonate, optionally substituted mono- or di-carboxylic acid salts (eg, zinc acetate, zinc octylate, stearin). At least one selected from the group consisting of zinc acidate, zinc oxalate, zinc lactate, zinc tartrate and zinc naphthenate) is preferable. 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 inexpensive and easy to handle. It is preferable because it is easy. Zinc oxide,
At least one zinc source selected from the group consisting of zinc hydroxide and zinc acetate is substantially free of impurities that hinder the reaction of forming zinc oxide crystals during the heating process, and It is more preferable because the size and shape of the fine particles can be easily controlled.

Zinc oxide and / or zinc hydroxide are not only inexpensively available, but the type of monocarboxylic acid can be arbitrarily selected, and in addition, by using these raw materials, fine particles whose shape or particle diameter is controlled can be obtained. It is particularly preferable because it can be easily obtained. The amount of the zinc source is, for example, 0.1 to 95% by weight, preferably 0.5, in terms of ZnO with respect to the total amount of the zinc source, the monocarboxylic acid and the medium.
-50% by weight, more preferably 1-30% by weight.
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 fine particles is likely to occur, and fine particles having good dispersibility and uniform particle size distribution may be difficult to obtain.

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; and lactic 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 the amount is less than the above range, the crystallinity of zinc oxide in the obtained fine particles may be low.

The monocarboxylic acid also includes a zinc monocarboxylic acid salt 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 the production method of the present invention is, for example, 0.5 to 50, and preferably 2.2 to 10, in terms of molar ratio with respect to the amount of Zn atoms in the zinc source. Economical within the above range,
It is preferable in terms of the ease of forming fine particles, the ease of obtaining fine particles that are less likely to aggregate, and have excellent dispersibility. If it is less than the above range, it may be difficult to obtain zinc oxide type fine particles having good ZnO crystallinity and fine particles having a high uniformity in shape and particle diameter, and if it exceeds the above range, not only the economical efficiency is deteriorated but also the fine particles having good dispersibility are obtained. Can be difficult to obtain.

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 reaction for producing zinc oxide type fine particles in a short time, the molar ratio of alcohol to Zn atoms derived from the zinc source is, for example, 1-100, preferably 5-80, more preferably 1
0 to 50. When it is less than the above range, it is difficult to obtain zinc oxide type fine particles having good ZnO crystallinity, or dispersibility,
It may be difficult to obtain fine particles excellent in uniformity of shape and particle diameter, and if it exceeds the above range, it may be economically disadvantageous.

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. And the like, and the ratio of the alcohol to the other solvent is 5 to 100% by weight of alcohol, preferably 40 to 40%, in terms of the charge (used) used for preparing the mixture (m).
It is 100% by weight, more preferably 60 to 100% by weight. If the amount of alcohol is less than the above range, fine particles having good crystallinity, shape / particle size uniformity, and dispersibility may be difficult to obtain.

Examples of the metal (M) compound used in the production method of the present invention include, for example, metal (M) such as a simple metal and an alloy; oxide; hydroxide; (basic) carbonate and nitrate. Inorganic salts such as halides such as sulfates, chlorides and fluorides; carboxylates such as acetates, propionates, butyrates and laurates; metal alkoxides; β-diketones, hydroxycarboxylic acids, ketoesters , All compounds containing trivalent or tetravalent metal (A), such as metal chelate compounds with keto alcohol, amino alcohol, glycol, quinoline, etc .; multiple valences such as In, Tl, etc. are possible In the case of a metal element, at least one compound selected from the group consisting of compounds containing a low-valent metal that can finally change to trivalent or tetravalent in the process of forming fine particles (this Gobutsu is a concept including a metal such as an elemental metal or an alloy) is used.

When aluminum is used as the Group IIIB metal element, examples of compounds containing aluminum include aluminum, aluminum hydroxide, aluminum oxide, aluminum chloride, aluminum fluoride, aluminum nitrate, aluminum sulfate, and basic acetic acid. Aluminum, aluminum trisacetylacetonate, aluminum trimethoxide, aluminum triethoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, acetoalkoxyaluminum diisopropylate, aluminum laurate, aluminum stearate, diisopropoxyaluminum. Stearate, ethyl acetoacetate aluminum diisopropylate, etc. are used.

When boron is used as the group IIIB metal element, examples of compounds containing boron include boron trioxide, boric acid, boron oxalate, boron trifluoride diethyl ether complex, boron trifluoride monoethylamine complex, and trimethyl. Borate,
Triethyl borate, triethoxy borane, tri-n-
Butyl borate is used.

When gallium is used as the group IIIB metal element, the compound containing gallium is, for example,
Gallium, gallium hydroxide, gallium oxide, gallium (III) chloride, gallium (III) bromide, gallium (III) nitrate,
Gallium (III) sulfate, gallium ammonium sulfate, triethoxygallium, tri-n-butoxygallium and the like are used.

When indium is used as the group IIIB metal element, compounds containing indium include, for example, indium, indium (III) oxide, indium (III) hydroxide, indium (III) sulfate, and indium chloride (I).
II), indium (III) fluoride, indium iodide (II
I), indium isopropoxide, indium acetate (II
I), triethoxyindium, tri-n-butoxyindium and the like are used.

When thallium is used as the group IIIB metal element, the compound containing thallium is, for example,
Thallium, thallium (I) oxide, thallium (III) oxide,
Basic thallium hydroxide (I), thallium chloride (I), thallium iodide (I), thallium nitrate (I), thallium sulfate (I), thallium hydrogen sulfate (I), basic thallium sulfate (I), acetic acid Thallium (I), thallium formate (I),
Thallium (I) malonate, Thallium (III) chloride, Thallium (III) nitrate, Thallium (III) carbonate, Thallium sulfate (II)
I), thallium (III) hydrogen sulfate, etc. are used.

The metal (M) oxide or hydroxide may be in the form of powder, but an aqueous sol of colloidal metal oxide and / or metal hydroxide such as alumina sol or alcohol sol may also be used. . The production method of the present invention has, for example, the following Steps I to III as essential steps, and in any one or two or more of Step I, Step II and Step III, the metal (M) compound is used. Can be added.

(I) A first step for preparing a mixture (n) consisting of a zinc source and a monocarboxylic acid. (II) A second step of preparing a mixture (m) in which zinc and a monocarboxylic acid are dissolved or dispersed in a medium containing at least alcohol by mixing the mixture (n) with a medium containing at least alcohol. (III) By maintaining the mixture (m) at a temperature of 100 ° C. or higher, the ratio of the number of atoms to the total number of metal elements is 80 to 99.9% zinc and 0.1 to 20% metal (M).
A third step of depositing zinc oxide-based fine particles composed of a crystalline coprecipitate of a metal oxide containing and.

In the production method of the present invention, step I is preferably a step of producing a mixture (n) further containing water. By this step, the mixture (n) in the form of solution is easily obtained. The zinc source, the monocarboxylic acid and water may be added in any order. For example, the mixture (n) is prepared by dissolving the zinc source in the mixed solvent of the monocarboxylic acid and water. In the production method of the present invention, it is preferable that step II and step III are constituted by a step in which the mixture (n) is added to and mixed with a medium composed of at least alcohol which is maintained at a temperature of 100 ° C. or higher. By this step, the mixture (m) is easily made.

When the mixture (n) consisting of the zinc source and the monocarboxylic acid or consisting of these and the metal (M) compound is added to a medium consisting of at least alcohol, the mixture (n) is a solution. It is preferable. When the mixture (n) is a solution, the zinc source and the monocarboxylic acid, or these and the metal (M) compound are compatible with each other, or are dissolved in a solvent having a high compatibility with them. Is desirable. As a solvent used for that purpose, a zinc source and a monocarboxylic acid, or these and a metal (M) compound can be easily dissolved at a temperature of from room temperature to about 100 ° C., and the solvent also forms a phase with the medium. From the viewpoint of high solubility, water, alcohols, ketones and esters are preferable. The alcohols here include all the alcohols described above.

During the process in which the zinc source is converted into zinc oxide which is X-ray diffraction crystalline, one or more zinc oxide precursors (the precursors may contain a metal (M)). However, it may not be included). For example, the case where zinc oxide or the like is used as the zinc source can be mentioned. The zinc oxide precursor means an ion or compound state containing at least a zinc atom other than zinc oxide, and includes, for example, zinc (hydrate) ion (Zn ²⁺ ), zinc polynuclear hydroxide ion, and zinc A state in which a part or all of the above ions are chelated by a β-dicarbonyl compound such as acetylacetone or a compound having a chelate-forming ability such as lactic acid, ethylene glycol, ethanolamine, or (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.

In the process of converting the zinc source and the metal (M) compound used as raw materials in the mixture (m) into zinc oxide type fine particles, the monocarboxylic acid present in the mixture (m) changes. If not, or part or all of the monocarboxylic acid causes an esterification reaction with part or all of the alcohol in the mixture (m) to form an ester compound.

The mixture (m) may be any one obtained by mixing four components of the zinc source, the monocarboxylic acid, the alcohol, and the metal (M) compound as essential components, and is necessary. In addition to the above four components, for example, organic solvents such as water, ketones, esters, (cyclo) paraffins, ethers and aromatic compounds, components such as additives described below, or zinc and metal. It may contain a metal component other than (M), for example, an inorganic salt such as a metal acetate, nitrate or chloride, or an organic metal alkoxide such as a metal alkoxide. However, the alkali metal and the alkaline earth metal may reduce the heat ray cutting function and conductivity of the fine particles, and it is preferable that the number is 1/10 or less of the number of atoms of the metal (M) in the mixture (m), 1/100
It is more preferred that: Further, water and an organic solvent are usually contained as solvent components.

The state of existence of the above four components and the form of existence of each component in the mixture (m) are not particularly limited. For example, when the presence state of the zinc source is illustrated, alcohol, and / or the water and the organic solvent are used as solvent components, and the zinc source and / or the metal (M) compound are directly dissolved in the zinc oxide precursor. It may be in a changed and dissolved state or in a colloidal state, an emulsified state or a suspended state.

Therefore, the state of the mixture (m) is not particularly limited, and there is no problem even if it is in the form of liquid, sol, emulsion or suspension. Mixture (m)
Is prepared by mixing the components within the above range. The preparation method is not particularly limited. In particular, in order to obtain a dispersion of zinc oxide-based fine particles in which the average particle size of single particles is controlled in the range of 0.001 to 10 μm, a first mixture (n) containing the zinc source and a monocarboxylic acid is used. Is preferably added to the alcohol-containing solution under heating to prepare the mixture (m) from the viewpoint of obtaining practical productivity.

The preparation method at this time will be described below. Examples of the method for adding the mixture (n) include, for example, a method in which the mixture (n) is added and mixed all at once, a method in which the mixture (n) is mixed by dropping onto or in an alcohol-containing solution, or the mixture (n). ) Can be adopted. Further, the addition and mixing of the mixture (n) may be carried out under any of normal pressure, increased pressure or reduced pressure, but it is preferable to be effected under normal pressure in view of production cost. When adding and mixing under normal pressure, when it is desired to obtain a zinc oxide-based fine particle dispersion that is highly uniform in particle size, shape, etc., and that has a dispersed / aggregated state controlled, an alcohol content is included in the addition and mixing. It is preferable to keep the solution at a temperature of 60 ° C. or higher, particularly 60 ° C. or higher and 300 ° C. or lower. When the temperature of the alcohol-containing solution at the time of addition and mixing is less than 60 ° C., the viscosity of the mixture (m) rapidly increases during or after the addition and mixing,
May form a gel. In such a case, stirring may not be possible and uniform mixing may not be achieved, or heat transfer may be insufficient during the next step, that is, heating may induce a problem such as temperature distribution. It is difficult to obtain zinc oxide-based fine particles having a uniform particle diameter and particle shape, and it is difficult to obtain only aggregates. Such a problem is related to the zinc concentration in the mixture (m), and is more likely to occur as the zinc concentration is higher. Therefore, 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 alcoholic solvent according to the pressure. As described above, when the mixture (n) is added while heating the alcohol-containing solution, a part of the monocarboxylic acid and / or a part of the alcohol in the mixture (m) is distilled out of the system due to evaporation. Although it is sometimes removed, the thus obtained product is also included in the mixture (m).

The raw material composition for preparing the mixture (n) is not particularly limited, but the amount of the zinc source used as the raw material of the mixture (n) is Z based on the total amount of the mixture (n).
It is in the range of 1 to 90% by weight in terms of nO, and the amount of the monocarboxylic acid used as a raw material of the mixture (n) is 0.5 to 5 in terms of molar ratio to Zn atoms in the zinc source.
It is preferably in the range of 0 times the mole.

Mixture (n) prepared as described above
Is added to and mixed with the alcohol-containing solution to obtain a mixture (m). When the mixture (n) is added and mixed,
The mixture (n) may be at room temperature or in a heated state. In addition, when adding and mixing, it is particularly preferable that the alcohol-containing solution is stirred for the purpose of obtaining uniform mixing.

At this time, the content of alcohol contained in the alcohol-containing solution is not particularly limited. The molar ratio to the Zn atom derived from the contained zinc source is 1 to 100
A double molar range is preferred. The concentration of the alcohol in the alcohol-containing solution is usually in the range of 5 to 100% by weight based on the total amount of the solution.

Mixture (m) obtained as described above
By heating, the dispersion containing zinc oxide-based fine particles can be obtained in good yield. The heating temperature is not particularly limited, and it goes without saying that the heating temperature is not lower than the temperature at which crystalline zinc oxide is precipitated, but the particle size, shape, dispersion / aggregation state, etc. of the zinc oxide-based fine particles to be finally obtained. However, the heating temperature and the heating time must be selected from a comprehensive viewpoint including the initial composition of the mixture (m) and the various parameters described above. In particular, the average particle size of single particles is 0.001 to 1
In order to obtain a dispersion of zinc oxide type fine particles controlled in the range of 0 μm with practical productivity, it is preferable to carry out at a heating temperature of 100 ° C. or higher, particularly 100 ° C. or higher and 300 ° C. or lower.

In this case, for example, the mixture (n) is added to 10
When a mixture (m) is obtained by adding and mixing to an alcohol-containing solution maintained at a temperature of 0 ° C. or higher, the temperature may be maintained as it is, or after heating or cooling to a predetermined temperature, heating may be performed. May be processed. When the mixture (n) is added to and mixed with alcohol at a temperature lower than 100 ° C. to obtain the mixture (m), the mixture may be heated to a temperature of 100 ° C. or higher and then heat-treated. Setting the heating temperature of the mixture (m) to 100 ° C. or higher strictly controls the composition of the reaction system including the rate and amount of evaporation and removal of excess or unnecessary components in order to obtain zinc oxide-based fine particles. Therefore, there is an advantage that it is easy to control the particle diameter and the like of the resulting fine particles.

In the heating process for obtaining the dispersion, a part or all of the components other than the above-mentioned components, namely, the alcohol, the ester compound produced by heating, or the solvent component present in the mixture as the case requires. May be removed by evaporation. The heating time is not particularly limited, but is usually 0.1 hours to complete the reaction.
About 30 hours is preferable.

When water is allowed to exist in the mixture (m), it is preferable that the free water concentration in the dispersion is preferable in order to be converted into zinc oxide type fine particles in the heating process. It is preferable to carry out the distillation until the content is 5% by weight or less, more preferably 1% by weight or less. The reason is that if the water concentration exceeds this range, the crystallinity of the zinc oxide-based fine particles becomes low and the above-mentioned function cannot be sufficiently exhibited depending on the type of other components such as alcohol contained in the dispersion. Because there is.

As the (final) composition in the produced zinc oxide type fine particle dispersion, the amount of the above-mentioned monocarboxylic acid is based on the total amount of zinc atoms contained in the produced dispersion. It is preferably 0.5 times or less mol. The reason is that if it exceeds 0.5 times by mole, the crystallinity of the zinc oxide-based fine particles is lowered and the function as zinc oxide may not be sufficiently exhibited. Therefore, when the amount of the monocarboxylic acid present in the mixture (m) exceeds 0.5 times the total amount of zinc atoms contained in the produced dispersion in terms of zinc atoms, heating is performed. In the process
At least the excess needs to be distilled off. Of course, even if the above ratio is 0.5 mol or less, distillation may be performed during the heating process.

When the single particles are used as primary particles and secondary particles formed by aggregating the primary particles are obtained, it is effective to make a lactic acid source coexist when the temperature is maintained at 100 ° C. or higher. Is. The source of lactic acid is lactic acid; ammonium lactate, sodium lactate, lithium lactate, calcium lactate, magnesium lactate, zinc lactate, aluminum lactate, manganese lactate,
Metal lactates such as iron lactate, nickel lactate, and silver lactate; lactic acid ester compounds that can generate lactic acid by hydrolysis such as methyl lactate, ethyl lactate, and n-butyl lactate, and any one of them alone. May be used, or
You may use 2 or more together.

The amount of the lactic acid source used is not particularly limited, but the molar ratio to zinc in the mixture (m) is, for example, in the range of 0.001 to 0.4. Below the range, zinc oxide crystals cannot be obtained because the coexisting effect of lactic acid is insufficient. On the other hand, above the range, the precipitation reaction of zinc oxide crystals is difficult to occur, and it is difficult to obtain the target fine particles. In order to obtain fine particles having a uniform particle shape, the molar ratio of lactic acid to zinc is preferably in the range of 0.001 to 0.2, and in order to obtain fine particles having a uniform particle diameter and good dispersibility, the ratio to zinc is The molar ratio of lactic acid is 0.001
0.1 is preferred.

The addition of the lactic acid source is as follows, for example. When lactic acid (CH ₃ CH (OH) COOH) and / or lactic acid ester is used, the above steps I to II are performed.
I may be added at any time, and a method of directly adding or a method of adding a solution dissolved in a solvent (for example, alcohol) can be adopted. The latter addition method is preferable especially when the lactic acid source is added in step III because lactic acid easily diffuses quickly. If a metal lactate is used, it may be at any time in steps I-III above, preferably dissolved in mixture (n) with or as a zinc source in step I. For example, a zinc source powder and a metal lactate powder are added to and mixed with a solution containing a monocarboxylic acid and stirred to prepare a uniform solution. At this time, stirring with heating in order to increase the dissolution rate and solubility of each powder is preferably adopted because a high-concentration solution can be obtained in a short time.

When lactic acid is dissolved or dispersed in the medium, the zinc oxide crystals grow anisotropically to form flaky zinc oxide crystals, and these flaky zinc oxide crystals have their tips facing outward. A dispersion containing zinc oxide-based fine particles having a crowded surface may be obtained. At this time, when the molar ratio of lactic acid to zinc is in the range of 0.001 to 0.4, the resulting single particles are flaky (anisotropic shape), for example, the length (shortness) of 1.0 to 5.0 ( Major axis /
Minor axis), flatness of 2 to 200 (major axis / thickness), major axis 5
The thickness is 1000 nm, which is preferable because of excellent light diffusion and transmission. The major axis is the longest of the triaxial diameters measured for the particles, and the thickness is the lesser of the width and height of the triaxial diameters (particle diameter at the shortest part). .

The polymer used in the production method of the present invention is the same as that described for the polymer contained in the zinc oxide type fine particles of the present invention. The amount of the polymer used is not particularly limited, but is a weight ratio of the amount of zinc atoms in the zinc source (that is, in the second mixture) to the amount converted to zinc oxide, for example, in the range of 0.01 to 2.0. Done. If the amount is less than the above range, it may be difficult to obtain composite particles, and if the amount is more than the above range, it may be difficult to cause precipitation reaction of zinc oxide crystals. In order to obtain zinc oxide type fine particles having the above-mentioned multi-layered structure among the composite particles and having a uniform particle shape and particle size and good dispersibility, it depends on the type of polymer and other reaction conditions. The amount is preferably a weight ratio of 0.05 to 0.5 with respect to the above zinc oxide equivalent amount.

In the production method of the present invention, the polymer is added in any one of the above steps or in two or more steps. The addition of the polymer is performed at any time before the zinc oxide based fine particles are deposited. For example, a method of adding and mixing to the mixture (n) or adding and mixing to the mixture (m) is exemplified. 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 zinc oxide based fine particles are formed.

The polymer is preferably dissolved in the alcohol used in the above-mentioned medium in advance or dissolved in an arbitrary 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 (the above-mentioned ones),
Organic solvents such as aliphatic and aromatic carboxylic acids, aliphatic and aromatic carboxylic acid esters, ketones, ethers, ether esters, aliphatic and aromatic hydrocarbons, halogenated hydrocarbons; water; minerals Oil; vegetable oil;
At least one selected from the group consisting of wax oil and silicone oil.

The mixture (m) may be any one obtained by mixing four components of zinc, monocarboxylic acid, alcohol and metal (M) as essential components, and is a stage before the formation of zinc oxide type fine particles. The polymer is added at. The mixture (m) containing the polymer is heated at a temperature of 100 ° C. or higher, preferably 100 to 300 ° C., more preferably 150 to 200 ° C. for 0.1 to 30 hours, preferably 0.5 to
By maintaining for 10 hours, the zinc oxide type fine particles of the present invention according to the kind of raw material and composition ratio can be obtained as zinc oxide type crystal-polymer composite particles with practical productivity. 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 and for the time within the above range. . Since the polymer is also dissolved or dispersed in the medium, nuclei of zinc oxide crystals are deposited, and the polymer is complexed in the process of crystallization, so that a dispersion containing zinc oxide-polymer composite particles is obtained. can get. Type of polymer used, type of raw material such as alcohol contained in the medium, composition of raw material, reaction liquid composition and temperature when composite particles are formed based on temperature history until composite particles are formed, etc. It is possible to control the internal structure of the composite particles, the particle shape and particle size, the particle size of the single particles (metal oxide coprecipitate) contained, and the like by controlling the above.

According to the production method of the present invention, zinc oxide containing a metal oxide coprecipitate and a polymer and having a number average particle size of 0.001 to 10 μm and a coefficient of variation of particle size of 30% or less. The system fine particles are dispersed and contained in the range of 1 to 80% by weight, and a dispersion having an alcohol and / or the ester compound and / or an organic solvent as a solvent is obtained. Furthermore, the particle size of the single particle of the finally obtained zinc oxide based fine particles,
For the purpose of controlling the particle shape, dispersed state or higher order structure and / or the polarity or composition of the fine particle surface, it is possible to coexist with a specific additive in the heating process. The timing of adding the additive is not particularly limited, and may be any of the process of preparing the mixture (m) or the mixture (n) or the process of heat treatment, and is appropriately selected depending on the purpose and the type of the additive. For example, when it is added immediately before or immediately after the zinc oxide crystal is precipitated, the effect of the additive is easily exerted sufficiently, which is often preferable.

In particular, in order to obtain zinc oxide type fine particles which are highly uniform in particle diameter and particle shape of a single particle, a carboxyl group, amino group, imino group, amide group,
Amide bond, imide group, imide bond, ureido group, ureylene bond, isocyanato group, sulfonic acid group, sulfuric acid group,
A compound having one or two or more atomic groups selected from the group consisting of a phosphoric acid group, a metal hydroxyl group, a metal alkoxy group, an epoxy group, a urethane group, a urethane bond, and an ester bond, and having a molecular weight of less than 1000, and / Alternatively, it is preferable that a so-called chelating agent (polydentate ligand) that forms a chelate compound by being multidentately coordinated with zinc ions is used as an additive and is allowed to coexist during the heat treatment.

Examples of the additives include long-chain saturated fatty acids such as caprylic acid, lauric acid, myristic acid, palmitic acid and stearic acid, and the above-mentioned carboxyl group-containing compounds and ester compounds thereof; monoethanolamine, Alcohols having primary, secondary, and tertiary amino groups such as diethanolamine and N, N-dimethylethanolamine, tetramethylammonium hydroxide, n
Quaternary ammonium salts such as hexadecyltrimethylammonium hydroxide, 6-aminocaproic acid, N, N
-Amino acids such as bis (octylaminoethyl) glycine, p-aminobenzoic acid, aspartic acid and glutamic acid, amino (di) carboxylic acids and their esters or anhydrides, 2-hydroxypyridine, pyridine-2,6
-Pyridine derivatives such as dicarboxylic acids, amino group-containing compounds such as aliphatic amines such as octadecylamine and stearylamine; amides such as dimethylformamide, dimethylacetamide, benzamide, oxamide and oxamic acid; acid imides such as succinimide and phthalimide, Imino (di) carboxylic acids such as imino (di) acetic acid, imino group-containing compounds such as imino ethers; dicarboxylic acid ureides such as parabanic acid, alloxan, barbituric acid and dialuric acid, ureido acids such as oxalic acid and malonuric acid, uric acid And the like, β-aldehyde acid ureides such as uracil, ureido group-containing compounds and derivatives such as α-oxyacid ureido such as 5-methylhydantoin; urethane compounds such as ethyl carbamate and their N-nitrosides, N- Chlorasse Derivatives such as chilled compounds; tolylene diisocyanate, diisocyanyl diphenylmethane, hexamethylene diisocyanate, isobutyl isocyanate, phenyl isocyanate, and other isocyanato group-containing compounds; 1,2-epoxycyclohexene, 1,8-cineole, ethylene Glycol diglycidyl ether, 1,
Aliphatic diglycidyl ethers such as 6-hexanediol diglycidyl ether, polyglycidyl ethers such as glycerol triglycidyl ether, pentaerythritol tetraglycidyl ether, and aliphatic and aromatic diglycidyl esters such as adipic acid diglycidyl ester In addition to the above, compounds containing an epoxy group such as resorcin diglycidyl ether, bisphenol A diglycidyl ether, oligomers having an epoxy group as a functional group; isopropyl triisostearoyl titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, tetra Octyl bis (ditridecyl phosphite) titanate, isopropyl tri (N-
Aminoethylaminoethyl) titanate, various coupling agents such as titanate coupling agents, and partial hydrolysates thereof; other than the above-mentioned coupling agents, for example, tetraethoxy titanium, tetrabutoxy titanium,
Diethyldiethoxytitanium, tetrabutoxytitanium, tetramethoxyzirconium, tetrabutoxyzirconium, hexaethoxytungsten, di-n-butoxymanganese, diisopropoxycobalt, diethoxynickel, di-n-butoxynickel, triethoxylanthanum, triethoxy. Yttrium, diethoxy copper, di-n
-Butoxy copper, pentaethoxyniobium, penta-n-butoxyniobium, pentaethoxytantalum, penta-n-
Organometallic compounds containing metal hydroxyl groups and / or metal alkoxy groups represented by metal alkoxides such as butoxytantalum, triethoxyiron, tri-n-butoxyiron and the like, derivatives thereof, and specific examples of the derivatives include organic compounds of these. Metal compounds alone or in mixture (partially)
Condensate such as (partial) hydrolyzate obtained by hydrolysis and / or condensation reaction; trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris (2-chloroethyl) phosphate, (polyoxyethylene) bis [bis (2 -Chloroethyl) phosphate] and the like, methyl acid phosphate, propyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, acid phosphates such as bis-2-ethylhexyl phosphate, diisodecyl phosphate, phosphorous acid such as trimethyl phosphite Organophosphorus compounds such as acid esters, thiodiphosphoric acid esters such as dimethyldithiophosphoric acid and diisopropyldithiophosphoric acid; at least primary amino group and secondary amino group in the molecule Organopolysiloxanes having a molecular weight of less than 1000 and containing the above-mentioned atomic groups such as tertiary amino groups, amino groups such as quaternary ammonio groups, carboxyl groups, sulfonic acid groups, phosphoric acid groups, hydroxyl groups and epoxy groups; sodium lauryl sulfate , Sodium dodecylbenzene sulfonate (sodium), sodium polyoxyethylene lauryl ether sulfate, sodium dialkyl sulfosuccinate, anionic surfactants such as calcium stearate, polyoxyethylene lauryl ether, polyoxyethylene alkylamine, polyethylene glycol monolaurate, Nonionic surfactants such as glycerol monostearate; cationic surfactants such as lauryl dimethylamine, stearyl trimethyl ammonium chloride, lauryl betaine, stearyl amine acetate Amphoteric surfactants such as Tate, various surfactants or the like having the above-mentioned atomic group are exemplified.

Examples of so-called chelating agents (polydentate ligands) that form chelate compounds by polydentate coordination with zinc ions include β-diketones such as acetylacetone, ethyl acetoacetate, benzoylacetone, ethylenediamine, Dimethylglyoxime, benzyldioxime, cyclohexane1,2-dionedioxime, dithizone, oxine, glycine, glycolic acid, oxalic acid, catechol, dipyridyl, 1,10-phenanthroline,
α-hydroxypropionic acid, monoethanolamine,
Examples thereof include diethanolamine and ethylene glycol.

As described above, the size and shape of single particles of the obtained zinc oxide type fine particles, the dispersed state and higher order structure of single particles, surface polarity,
The surface composition and so on differ greatly. For example, when a compound having a hydrophilic main chain such as methoxypoly (oxyethylene) monoglycolic acid is used as an additive, the size and shape of the primary particles are uniform, and the primary particles are compatible with polar solvents such as water. Zinc oxide-based fine particles having excellent dispersibility can be obtained. On the other hand, when a compound having a highly hydrophobic or lipophilic main chain such as alkyltrialkoxysilane and octadecylamine is used as an additive, Thus, it is possible to obtain zinc oxide type fine particles having a uniform shape and excellent in dispersibility of primary particles in a low polar solvent such as toluene or a nonpolar solvent.

The amount of the above-mentioned additive added is not particularly limited, but is usually 0.1% or more and 80% or less in terms of the weight ratio of the additive to zinc oxide contained in the zinc oxide type fine particle dispersion. Is preferred. If it is less than 0.1%, the effect of adding the additive is not substantially observed, while if it exceeds 80%, zinc oxide type fine particles may not be obtained in some cases. The above-mentioned additives can be used alone or as a mixture, and the addition method is not particularly limited, and may be appropriately selected depending on the kind of the additive, the addition timing and the like. For example, when the additive is added during heating, a method of adding the additive directly or by dissolving and / or diluting it in an arbitrary solvent such as alcohol is exemplified. The latter method is an additive in the reaction system. Is preferable because it easily diffuses rapidly and the effect of addition is easily exhibited.

Next, in the above-mentioned present invention, the preferred embodiment for obtaining zinc oxide type fine particles in which the average particle size of single particles is controlled in the range of 0.001 to 0.1 μm is described above. Among the conditions, the following (I)
To (IV), preferably (I) to (I).
V) is carried out under two or three conditions, more preferably under conditions that satisfy all of (I) to (IV).

As the zinc source (I), those containing, as a main component, at least one selected from the group consisting of zinc oxide, zinc hydroxide and zinc acetate among the above zinc or its compounds, and particularly preferably oxidized It is mainly composed of zinc and / or zinc hydroxide. The reason for this is that zinc oxide, zinc hydroxide, and zinc acetate do not substantially contain impurities that hinder the reaction of forming zinc oxide-based fine particles in the heating process, so that they are 0.001 to 0.1 μm. This is because it is easy to strictly control the particle size in a fine region. Among them, zinc oxide and zinc hydroxide are not only inexpensively available, but also the type of carboxyl group-containing compound can be arbitrarily selected. This is because it is particularly easy to obtain fine particles having the above-mentioned particle diameter range by using the above raw material.

(II) As the monocarboxylic acid, the monocarboxylic acid is a saturated fatty acid having a boiling point of 200 ° C. or less at normal pressure. Specifically, formic acid, acetic acid, propionic acid, butyric acid, and isobutyric acid are preferable, and acetic acid is particularly preferable. The reason is that it is easy to control the content of the carboxyl group in the reaction system during the heating process from the preparation process of the mixture, and thus it is easy to strictly control the particle size in a fine region. Further, it is preferable to use the saturated fatty acid in a ratio of 80 mol% or more in the total amount of the monocarboxylic acid.

The content of the monocarboxylic acid is not particularly limited as long as it is within the above range, but the content of the monocarboxylic acid in the mixture (n) is equal to that in the zinc oxide. 2.2 to 1 in terms of molar ratio to atoms
The range of 0 times the molar ratio is particularly preferable in that fine particles with suppressed secondary aggregation and excellent dispersibility can be obtained. (III) As a method for preparing the mixture (m), a mixture (n obtained by mixing the zinc source and the monocarboxylic acid, and optionally the zinc source, the monocarboxylic acid and the metal (M) compound ) Is continuously or intermittently added dropwise to the alcohol-containing solution maintained at a temperature of 100 ° C. or higher, preferably 100 ° C. or higher and 300 ° C. or lower.

In this case, the mixture (n) is preferably in a liquid state, and when the zinc source and the monocarboxylic acid also contain a metal (M) compound, the zinc source, the monocarboxylic acid and the metal (M). It is desirable that the compound be dissolved in a solvent that is compatible or highly compatible with these compounds. As a solvent used for that purpose, water and alcohols can be easily dissolved in a zinc source and a monocarboxylic acid described below by heating from room temperature to about 100 ° C., and have high compatibility with an alcoholic solvent. , Ketones and esters are preferred. The alcohols here include all the alcohols described above.

(IV) The heating temperature of the mixture (m) is 10
0 ° C or higher and 300 ° C or lower, particularly preferably 150 ° C or higher and 3
It is to be performed at 00 ° C or lower. When the mixture (m) is heated to precipitate ZnO crystals and the fine particles of the present invention are produced, the ZnO conversion concentration with respect to the mixture (m) is 0.5 wt% or more and 20 wt% or less, further 2.0 wt% or more. 1
When the amount is less than 0 wt%, it is preferable that the average particle size of the primary particles is in the range of 0.001 to 0.1 μm because fine particles in which secondary aggregation is suppressed can be easily obtained.

Further, the average particle size is 0.001 to 0.1.
An effective method for controlling the particle diameter and shape more uniformly, controlling the surface state such as hydrophilicity / hydrophobicity, controlling the dispersion / aggregation state, etc. in zinc oxide type fine particles in the range of μm Will be described below. Average particle size 0.001
Even in a preferable method for producing zinc oxide type fine particles having a range of 0.1 μm, by using the above-mentioned additives in the same manner as described above, it is possible to control the shape of particles, the dispersed state of particles, higher-order structure, surface polarity and the like. The obtained zinc oxide-based fine particles can be obtained. In addition, in the case of obtaining zinc oxide type fine particles in which the particle size distribution of the primary particles is uniform and the average particle size is substantially within the above range and secondary aggregation is suppressed, zinc or its compound used as a raw material Is a basic zinc carbonate and / or a zinc salt of a monocarboxylic acid having a boiling point at atmospheric pressure higher than the heating temperature, at least one selected from the group consisting of zinc oxide, zinc hydroxide and zinc acetate. It is also preferable to use a method of using a resin containing as a subcomponent. The ratio of the subcomponent to the main component is usually 0.01% or more and 20% or less in atomic ratio of zinc in the component.
If the proportion is less than 0.01%, the combined effect of subcomponents is insufficient, while if it exceeds 20%, zinc oxide with high crystallinity may not be obtained.

As an alternative method for obtaining zinc oxide type fine particles having a uniform shape and particle size distribution and excellent dispersibility, a method of coexisting carbonate ions and / or CO ₂ in the heat treatment process is also effective. For example, carbon dioxide gas is intermittently or continuously supplied into the mixture (m) before and / or during the zinc oxide formation reaction in the heat treatment process, urea, ammonium (hydrogen) carbonate, basic Examples thereof include a method of adding a compound such as zinc carbonate which produces carbon dioxide or carbonate ions under heating conditions.

Among the production methods of the present invention, particularly according to the above-mentioned production conditions, the particle shape, the surface state, the dispersed / aggregated state and the like are controlled in the range of the average particle diameter of 0.001 to 0.1 μm. When the zinc oxide concentration is in the range of 1 to 80% by weight, a dispersion of zinc oxide based fine particles using an alcohol and / or the ester compound and / or an organic solvent as a solvent can be obtained. The zinc oxide-based fine particle dispersion obtained in the present invention may be used as it is, but if necessary, it may be used in a zinc oxide-based fine particle powder, a coating containing zinc oxide-based fine particles, or another solvent by solvent substitution. It can be easily converted into a dispersion in which zinc oxide-based fine particles are dispersed.

As a method for obtaining the powder of zinc oxide type fine particles obtained in the present invention, the fine particles are separated by subjecting the dispersion to a commonly used method such as filtration, centrifugation and solvent evaporation, and then dried. Alternatively, a firing method may be employed. Among them, the powderization method by the solvent evaporation method using the vacuum flash evaporation device after performing the concentration operation of the dispersion as needed is a method in which the secondary aggregation of fine particles, which tends to occur in the drying process, is suppressed. Therefore, it is preferable as a method for pulverizing zinc oxide based fine particles having excellent dispersibility.

As a method for obtaining a dispersion in which the zinc oxide type fine particles are dispersed in a solvent different from the dispersion containing the zinc oxide type fine particles obtained in the present invention, it is obtained by pulverizing according to the above-mentioned method. After mixing the powder with a solvent, such as water, that you want to replace, a known method of dispersing by mechanical energy such as a ball mill, sand mill, ultrasonic homogenizer or heating the dispersion to evaporate part or all of the solvent in the dispersion -A so-called heating solvent replacement method in which a solvent to be replaced is mixed while being distilled off can be adopted. The solvent component constituting the dispersion is not particularly limited, alcohols,
Organic solvents such as aliphatic and aromatic carboxylic acid esters, ketones, ethers, ether esters, aliphatic and aromatic hydrocarbons, halogenated hydrocarbons, water, mineral oil, vegetable oil, wax oil, Silicone oil or the like is exemplified, and may be appropriately selected according to the purpose of use.

The combined use of the zinc oxide type fine particles and the heat ray absorbing agent is a great feature of the present invention, and zinc oxide type fine particles and the heat ray absorbing agent are used in the process of producing a composition such as a coating composition and a resin composition. When and coexist, the combined effect described later can be better obtained. A composite composition powder or a composite composition powder dispersion of zinc oxide-based fine particles and a heat-ray absorbent is also prepared, such as a powder in which zinc oxide-based particles are surface-treated (adsorbed on the surface) with a heat-ray absorbent such as a phthalocyanine compound in advance. It is within the scope of the invention.

The surface treatment of the zinc oxide type fine particles with a heat ray absorbing agent such as a phthalocyanine compound is carried out, for example, by mixing the zinc oxide type fine particles and the heat ray absorbing agent in a solvent capable of dissolving the heat ray absorbing agent and heating at room temperature or heating. The method of stirring below is mentioned. In order to perform the surface treatment uniformly,
The solvent is preferably a solvent in which the zinc oxide type fine particles are easily dispersed. Examples thereof include alcohols such as ethylene glycol monoalkyl ether such as ethylene glycol monobutyl ether and n-butanol; ketones such as methyl ethyl ketone; esters such as butyl acetate; water and the like.

Preferred embodiments of the composition of the present invention are as follows. (1) A composition for shielding ultraviolet rays and heat rays, which contains fine particles of a metal oxide coprecipitate consisting of 80 to 99.9 atomic% of zinc and the remainder of a Group IIIB metal element, and a heat ray absorber. (2) The composition for shielding ultraviolet rays and heat rays according to (1) above, wherein the heat ray absorbent is a phthalocyanine compound. (3) The composition for shielding ultraviolet rays and heat rays according to (1) or (2) above, further comprising a dispersion medium, wherein the dispersion medium disperses the fine particles and the heat ray absorbent. (4) The composition for shielding ultraviolet rays and heat rays according to any one of (1) to (3), wherein the Group IIIB metal element is indium and / or aluminum. (5) The average crystallite size of the fine particles is 0.001 to 0.0
The composition for shielding ultraviolet rays and heat rays according to any one of (1) to (4) above, which has a thickness of 5 μm. (6) The average dispersed particle size of the fine particles is 0.001 to 0.
The composition for shielding ultraviolet rays and heat rays according to any one of (1) to (5) above, which has a thickness of 1 μm. (7) The fine particles contain a zinc source and a monocarboxylic acid in a medium containing at least an alcohol, and at least 1
100 ° C in the presence of a compound containing a group IIIB metal element
The composition for shielding ultraviolet rays and heat rays according to any one of (1) to (6) above, which is fine particles generated by a method of holding at the above temperature. (8) The composition for shielding ultraviolet rays and heat rays according to the above (7), wherein the Group IIIB metal element is indium and / or aluminum. (9) In the above method, a mixture of a zinc source and a monocarboxylic acid is mixed with water, and the mixture is added to a medium heated to 100 ° C. or higher and composed of at least an alcohol.
The composition for shielding ultraviolet rays and heat rays according to (7) or (8) above, further comprising a step of removing at least a part of the water and / or monocarboxylic acid by evaporation. (10) The ultraviolet and heat ray shielding composition according to any of (7) to (9), wherein the zinc source is at least one selected from the group consisting of zinc oxide, zinc hydroxide and zinc acetate. (11) The ultraviolet and heat ray shielding composition according to any of (7) to (10), wherein the monocarboxylic acid is a saturated fatty acid having a boiling point of 200 ° C. or less under normal pressure. (12) The composition for shielding ultraviolet rays and heat rays according to any one of (7) to (11) above, wherein the temperature is maintained at 100 ° C. or higher in the presence of carbon dioxide or a carbonic acid source. (13) Maintaining the temperature of 100 ° C. or higher is carried out in the molecule by carboxyl group, amino group, quaternary ammonio group, amide group, imide bond, (alcoholic or phenolic) hydroxyl group, 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, one or more at least one kind of atomic group selected from the group consisting of sulfonic acid groups, the molecular weight is less than 1000 The composition for shielding ultraviolet rays and heat rays according to any one of the above (7) to (11), which is carried out in the coexistence of the additive compound of (1). (14) The dispersion medium is a binder component, and the amount of the fine particles, the heat ray absorbent, and the binder component is 0.1 to 99% by weight of the fine particles with respect to the total solid weight of these three members. The heat ray absorbent 0.0005-2
0% by weight, the binder component 0.1 to 99.9% by weight
The composition for shielding ultraviolet rays and heat rays according to any one of (3) to (13) above, which is a coating composition having the following ratio. (15) The composition for shielding ultraviolet rays and heat rays according to the above (14), wherein the total weight of the solid content of the fine particles, the heat ray absorber and the binder component is 1 to 80% by weight, and the balance is a solvent. (16) The composition for shielding ultraviolet rays and heat rays according to the above (15), wherein the amount of the heat ray absorbent is 0.05 to 30% by weight based on the total weight ratio of the solid content to the fine particles. (17) The dispersion medium is a resin, and the amount of the fine particles, the heat ray absorbent, and the resin is 0.01 to 99% by weight of the fine particles based on the total solid weight of these three members.
The heat ray absorbent is 0.0005 to 20% by weight, and the resin is 0.1 to 99.9% by weight, the above (3) to
A composition for shielding ultraviolet rays and heat rays according to any one of (13). (18) The composition for shielding ultraviolet rays and heat rays according to the above (17), wherein the amount of the heat ray absorbent is 0.05 to 30% by weight based on the total weight ratio of the solid content to the fine particles. [Coated Product] The coated product of the present invention includes a base material and a coating film formed on the surface of the base material. The base material is at least one selected from the group consisting of a resin molded body, glass and paper. The coating film comprises the ultraviolet and heat ray shielding composition of the present invention when the dispersion medium is a binder component.
This coating film is formed by applying the ultraviolet and heat ray shielding composition of the present invention, which is a coating composition, to the surface of a substrate.

When the composition of the present invention is a coating composition, it has been already described in the description of the composition of the present invention, and therefore its explanation is omitted here. The coating composition of the present invention may also be obtained by directly adding a heat ray absorbent and a binder component or a solvent containing a heat ray absorbent and a binder component to the fine particle dispersion obtained by the method for producing zinc oxide based fine particles, and mixing them. can get.

The coating composition may be any substrate, for example, a plastic film or sheet such as polyester film; fibers such as natural fibers and synthetic fibers; transparent such as vinyl chloride resin, polycarbonate resin, acrylic resin, polyethylene terephthalate resin, or the like. A film containing a zinc oxide type fine particle and a heat ray absorbent can be formed by applying to a semitransparent synthetic resin plate; glass; paper or the like and drying.

To form a film, heating may be performed at a temperature not higher than the deformation temperature of the substrate, if necessary. Heating is performed, for example, by using an inorganic binder such as a silicon alkoxide as the binder component and sufficiently promoting the condensation reaction between the molecules of the binder component to form a tough film, or the binder component as a thermosetting resin. To form a cured film by sufficiently advancing the curing reaction of the thermosetting resin, or a resin and isocyanate having two or more active hydrogen atoms such as polyether and / or polyester in at least part of the binder component. This is because the crosslinking reaction can be efficiently performed when the crosslinking reaction is performed, such as when a polyurethane film is finally formed using a crosslinking agent such as.

The binder component in the coated article of the present invention is a coating film formed by drying or dry curing (dry crosslinking) the above organic and / or inorganic binder. The method for applying the coating composition of the present invention is not particularly limited, and a conventionally known method such as a dipping method, a spray method, a screen printing method, a roll coater method or a flow coating method is adopted.

The coated article of the present invention may be coated paper. The coated paper is a paper on which a coating containing zinc oxide-based fine particles and a heat ray absorbing agent is applied on a paper base material and dried to form a film containing the fine particles and the heat ray absorbing agent. The manufacturing method of the coated paper is not particularly limited, except that the zinc oxide-based fine particles and the heat ray absorbent are used, the paper obtained by the conventionally known general manufacturing method is used as a base material, and the conventionally known coating method is used as it is. Applicable.

Examples of the coating composition used for making the coated paper include the coating composition of the present invention containing a solvent. 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.

In the case of producing coated paper, the composition of the coating composition containing the zinc oxide type fine particles and the heat ray absorbent to be used, the solvent to be used, the kind of the binder and the preparation method thereof are the same as the conventionally known raw materials. It can be used and may be prepared according to a conventionally known preparation method. The film-laminated paper means a paper laminated with a polymer film containing zinc oxide type fine particles and a heat ray absorbent dispersed therein. As the polymer film, the resin molded product of the present invention described below can be used.

The coated paper obtained according to the above production method is useful as a paper excellent in appearance. The use of the obtained paper is arbitrary, and it can be used in various uses such as art paper and wallpaper. The coating film in the coated article of the present invention contains zinc oxide-based fine particles, a binder component that binds the zinc oxide-based fine particles, and a heat ray absorber. The amounts of the zinc oxide-based fine particles, the heat ray absorbent, and the binder component (dispersion medium) are, for example, 0.1 to 99 of the zinc oxide-based fine particles based on the total solid weight of these three.
%, Heat ray absorber 0.0005 to 20% by weight, binder component 0.1 to 99.9% by weight, preferably,
The proportions are 10 to 79.9% by weight of zinc oxide type fine particles, 0.1 to 10% by weight of a heat ray absorbent, and 20 to 89.9% by weight of a binder component. If the proportion of zinc oxide-based fine particles is less than the above range, the thickness of the coating film must be increased in order to obtain sufficient ultraviolet shielding properties, and if it exceeds the above range, the dispersibility of the fine particles is reduced and the coating film against visible light. Transparency may decrease. If the proportion of the heat ray absorbent is less than the above range, it may be difficult to obtain sufficient heat ray shielding property, and if it exceeds the above range, the transparency of the coating film to visible light may be lowered or the cost may be increased. When the proportion of the binder component as the dispersion medium is less than the above range, the dispersibility of the fine particles is lowered and the transparency of the coating film to visible light is lowered, and the physical properties of the coating film such as mechanical properties and chemical resistance are In some cases, the thickness of the coating film must be increased in order to obtain sufficient ultraviolet light shielding properties.

The amount of each of the zinc oxide type fine particles and the heat ray absorbent contained in the coating film varies depending on the required ultraviolet and heat ray shielding ability, the transparency in the visible range, the thickness of the coating film and the shape of the coating film. When expressed as the content per unit area of the coating film or the weight in the projected area from the normal direction (above), the range of 1 to 10 g / m ² is preferable for the zinc oxide based fine particles, and 1.5 to 6 g / m ² is preferable. The range of m ² is more preferable; in the heat ray absorbent, the range of 0.005 to 2.4 g / m ² is preferable, and the range of 0.01 to 1.2 g / m ² is more preferable.

The resin molding used as the base material is, for example, at least one selected from the group consisting of plates, sheets, films and fibers. The base material may be a transparent base material or a semitransparent base material. The preferred embodiments of the coated article of the present invention are as follows. (1) At least one base material selected from the group consisting of a resin molded body, glass and paper, and fine particles of an oxide coprecipitate of a metal consisting of 80 to 99.9 atomic% zinc and the balance of the Group IIIB metal element, A heat ray absorbent, and a dispersion medium, wherein the dispersion medium is a binder component comprising a composition that disperses the fine particles and the heat ray absorbent,
A coated product comprising a coating film formed on the surface of the base material. (2) The heat ray absorbent is a phthalocyanine compound,
The coated product of (1) above. (3) The coated article according to (1) or (2) above, wherein the Group IIIB metal element is indium and / or aluminum. (4) The average crystallite size of the fine particles is 0.001 to 0.0
The coated article according to any one of (1) to (3) above, which has a thickness of 5 μm. (5) The average dispersed particle diameter of the fine particles is 0.001 to 0.
The coated product according to (4) above, which has a thickness of 1 μm. (6) The fine particles contain a zinc source and a monocarboxylic acid in a medium containing at least alcohol, and at least 1
100 ° C in the presence of a compound containing a group IIIB metal element
The coated article according to any one of (1) to (5) above, which is fine particles produced by a method of holding at the above temperature. (7) In the above method, a mixture obtained by mixing a zinc source and a monocarboxylic acid with water is added to and mixed with a medium which is heated to 100 ° C. or higher and is composed of at least alcohol.
The coated article according to (6) above, further including a step of removing at least a part of the water and / or the monocarboxylic acid by evaporation. (8) The coated article according to the above (6) or (7), wherein the zinc source is at least one selected from the group consisting of zinc oxide, zinc hydroxide and zinc acetate. (9) The coated product according to any one of (6) to (8), wherein the monocarboxylic acid is a saturated fatty acid having a boiling point of 200 ° C. or less under normal pressure. (10) The coated product according to any one of (6) to (9), wherein the temperature of 100 ° C. or higher is maintained in the presence of carbon dioxide or a carbonic acid source. (11) Maintaining the temperature of 100 ° C. or higher is carried out in the molecule by carboxyl group, amino group, quaternary ammonio group, amide group, imide bond, (alcoholic or phenolic) hydroxyl group, 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, containing at least one atomic group selected from the group consisting of sulfonic acid groups, the molecular weight is less than 1000 The coated article according to any one of (6) to (9) above, which is carried out in the coexistence of the additive compound according to (4). (12) The amounts of the fine particles, the heat ray absorbent, and the binder component are 0.1 to 99% by weight of the fine particles and 0.0005 to 20% of the heat ray absorbent with respect to the total solid weight of the three. % By weight, the binder component 0.1
The coated article according to any one of (1) to (11) above, which is a proportion of 99.9% by weight. (13) The coated product according to the above (12), wherein the amount of the heat ray absorbent is 0.05 to 30% by weight based on the total solid content weight ratio to the fine particles. (14) The coated article according to any one of (1) to (13) above, wherein the base material is one selected from the group consisting of a resin molded body, glass and paper. (15) The coating film contains the zinc oxide-based fine particles in an amount of 1 to 10 g / m ² in terms of the content per unit area or the weight in the projected area from the normal direction (above), and the heat ray absorbent. In the range of 0.005 to 2.4 g / m ² , the coated article according to any one of the above (1) to (14). [Resin Molded Article] The resin molded article of the present invention is obtained by molding the ultraviolet and heat ray shielding composition of the present invention, which is a resin composition, into at least one shape selected from the group consisting of plates, sheets, films and fibers. It was done.

When the composition of the present invention is a resin molded article, it is already explained in the explanation of the composition of the present invention, and therefore the explanation is omitted here. The amount of each of the zinc oxide-based fine particles and the phthalocyanine compound compounded in the molded product varies depending on the required ultraviolet / heat ray shielding ability, the transparency in the visible range, the thickness of the molded product, and the shape of the molded product.
For example, when expressed as the content per unit area of the molded product or the weight in the projected area from the normal direction (from above), the range of 1 to 10 g / m ² is preferable for the zinc oxide based fine particles, and 1.5 to 6 g. / M ² is more preferable; in the phthalocyanine compound, the range of 0.005 to 2.4 g / m ² is preferable, and the range of 0.01 to 1.2 g / m ² is more preferable.

When the composition of the present invention is a resin composition and a resin molded product, a resin molded product can be obtained by molding the resin composition into a plate, sheet, film, fiber or the like. it can. A 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 adopted as it is. An example will be described below.

When it is desired to obtain a polycarbonate resin plate containing zinc oxide type fine particles and a heat ray absorbent dispersed therein, for example, a polycarbonate resin pellet or powder, a predetermined amount of fine particle powder and a heat ray absorbent are melt-kneaded to form a resin in the resin. To obtain a composition in which the zinc oxide-based fine particles and the heat ray absorbent are uniformly mixed, and then continuously or once pelletized, and then subjected to injection molding, extrusion molding, compression molding, or the like to obtain a flat or curved surface. A method of processing into a plate shape 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.

When it is desired to obtain fibers such as nylon fiber or polyester fiber containing a dispersion of zinc oxide type fine particles and a heat ray absorbent, or a film such as a polyolefin film, a polyamide film or a polyester film, for example, zinc oxide type fine particle powder And a heat ray absorbent and resin pellets or powder are melt-kneaded to obtain a composition in which the fine particles and the heat ray absorbent are uniformly mixed in the resin, and then continuously or once pelletized, and then melt spinning, etc. The conventionally known fiberizing method, or a conventionally known (stretched) film manufacturing method in which it is formed into a sheet by extrusion molding and, if necessary, uniaxially or biaxially stretching is performed.

In order to obtain a polyester fiber or a polyester film in which zinc oxide type fine particles and a heat ray absorbent are dispersed and contained, the following other conventionally known methods can be adopted.
That is, as a method for obtaining a polyester fiber, zinc oxide fine particles and a heat ray absorbent are added in an amount of, for example, 0.1 to 50 weight% during a polyester production process, that is, at any time in a series of steps in a transesterification reaction to a polymerization reaction. % To obtain a polyester polymer in which the zinc oxide fine particles and the heat ray absorbent are dispersedly contained in the polyester by adding and mixing a dispersion obtained by dispersing in glycol in a ratio of 100% to complete the polymerization reaction of the polyester. 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 zinc oxide type fine particles and a heat ray absorbent are dispersed and contained in polyester is similarly obtained, and then extruded into a sheet by extrusion molding, A method of performing stretching treatment in uniaxial or biaxial directions can be adopted as necessary. Preferred embodiments of the resin molded product of the present invention are as follows. (1) Fine particles of a metal oxide co-precipitate consisting of 80 to 99.9 atomic% zinc and the remainder of a Group IIIB metal element, a heat ray absorbent, and a dispersion medium, wherein the dispersion medium is a resin. And a resin molded article obtained by molding the composition for shielding ultraviolet rays and heat rays, in which the heat ray absorbent is dispersed, into a shape selected from the group consisting of a plate, a sheet, a film and a fiber. (2) The heat ray absorbent is a phthalocyanine compound,
The resin molded product of (1) above. (3) The resin molded product according to (1) or (2) above, wherein the Group IIIB metal element is indium and / or aluminum. (4) The average crystallite size of the fine particles is 0.001 to 0.0
The resin molded product according to any one of (1) to (3), which has a thickness of 5 μm. (5) The average dispersed particle diameter of the fine particles is 0.001 to 0.
The resin molded product according to (4) above, which has a thickness of 1 μm. (6) The fine particles contain a zinc source and a monocarboxylic acid in a medium containing at least alcohol, and at least 1
100 ° C in the presence of a compound containing a group IIIB metal element
The resin molded product according to any one of (1) to (5) above, which is fine particles produced by a method of holding at the above temperature. (7) In the above method, a mixture obtained by mixing a zinc source and a monocarboxylic acid with water is added to and mixed with a medium which is heated to 100 ° C. or higher and is composed of at least alcohol.
The resin molded product according to (6), further including a step of removing at least a part of the water and / or the monocarboxylic acid by evaporation. (8) The resin molded product according to (6) or (7) above, wherein the zinc source is at least one selected from the group consisting of zinc oxide, zinc hydroxide and zinc acetate. (9) The resin molded product according to any one of (6) to (8), wherein the monocarboxylic acid is a saturated fatty acid having a boiling point of 200 ° C. or less under normal pressure. (10) The resin molded product according to any one of (6) to (9), wherein the temperature is maintained at 100 ° C. or higher in the presence of carbon dioxide or a carbonic acid source. (11) Maintaining a temperature of 100 ° C. or higher in a molecule, a carboxyl group, amino group, quaternary ammonio group, amide group, imide bond, (alcoholic or phenolic) hydroxyl group, 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, one or more at least one kind of atomic group selected from the group consisting of sulfonic acid groups, the molecular weight is less than 1000 The resin molded product according to any one of (6) to (9) above, which is carried out in the coexistence of the additive compound according to (4). (12) The amount of the fine particles, the heat ray absorbent, and the resin is 0.01 to 99% by weight of the fine particles, 0.0005 of the heat ray absorbent, based on the total solid weight of the three.
The resin molded product according to any one of (1) to (11) above, wherein the resin molded product is in a proportion of ˜20% by weight and 0.1 to 99.9% by weight of the resin. (13) The resin molded article according to (12), wherein the amount of the heat ray absorbent is 0.05 to 30% by weight based on the total weight ratio of the solid content to the fine particles. (14) Content per unit area or normal direction (upward)
1 to 10 g / by weight in the projected area from
0.005 to 2.4 g of the heat ray absorbent in the range of m ^2.
/ M ² The resin molded product according to any one of (1) to (13) above, which is included in the range.

[0120]

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. The physical properties of the zinc oxide-based fine particles used in Examples and Comparative Examples were measured and evaluated by the following methods. (Physical Properties of Zinc Oxide Fine Particles) (Crystallinity) It was evaluated by powder X-ray diffraction measurement.

(Average crystallite diameter) Powder X-ray diffraction measurement of a powder sample was performed, and the Scherrer (Sc
It was calculated using the formula of (Herrer). Scherrer
The formula is as follows. D = Kλ / β cos θ (where D [nm]: crystallite diameter, K: Scherrer constant (equipment constant), λ [nm]: wavelength of X-ray, β [radian]: based on crystallite size only Diffraction line width, θ: Diffraction angle.) (Average dispersed particle diameter) 1 part of fine particle powder in n-butanol
After adding and mixing to n-butanol so as to be wt% and stirring for 2 hours, a particle size analyzer by a dynamic light scattering method (NICOMP commercially available from Nozaki Sangyo Co., Ltd.
Model 370 was used) to determine the number-based average particle diameter, and this was used as the average dispersed particle diameter.

When the fine particles are produced by the method of the present invention,
The fine particle dispersion obtained by the reaction and concentration operations was diluted with n-butanol so that the fine particle concentration became 1% by weight, and this was used as a measurement sample. In addition, the concentration adjusting solvent at the time of measurement is n-
Butanol was used. (Fine particle composition) A powder sample was obtained by fluorescent X-ray analysis, atomic absorption analysis, gravimetric analysis, elemental analysis and the like.

(Concentration of Fine Particles in Dispersion) Part of the dispersion was vacuum dried at 100 ° C. until the volatile components such as the solvent could be completely removed (until no weight loss was observed), to obtain a dry powder. Obtained, in air at 500 ℃ 1
The residue after heating for a period of time was used as the metal oxide, and the weight fraction of the metal oxide content with respect to the dispersion was determined, and this value was defined as the concentration of fine particles in the dispersion (concentration in terms of metal oxide).

(Presence or absence of fine particle heat ray cutting function: Evaluation P) A dispersion containing 10% by weight of fine particles was coated on a glass plate having a thickness of 2 mm by using a bar coater and dried (80 ° C. under nitrogen atmosphere). A) to obtain a dry film.
The coating amount is variously changed in the range of 1 to 10 g / m ^{2 in} terms of fine particles, and the spectral characteristics of each dry film (wavelength 2200 to 200 nm)
Is measured by a self-recording spectrophotometer (UV-3100, Shimadzu Corporation). From the obtained spectroscopic curve, the film having a coating amount of 3 g / m ^{2 in} terms of fine particles was evaluated in comparison with the following criteria.

Evaluation Criteria: Cut amount at wavelength 2 μm ≧ 10%, and T ₇₀₀
> T ₂₀₀₀ : Heat ray cutting ability ・ If the above conditions are not satisfied: No heat ray cutting ability However, the heat ray cutting amount is: Wavelength 2 μm
It is T _700, T _{20 00} Each wavelength 700 nm, the light transmittance to 2 [mu] m (%); light transmittance to (%)).

The above dispersion is obtained by adding and mixing fine particle powder to n-butanol so as to be 10% by weight and stirring, and when fine particles are produced by the method of the present invention,
It was obtained by concentrating the fine particle dispersion obtained by the reaction to a fine particle concentration of 10% by weight. Reference) The transmittance of the glass substrate used is as follows.

Wavelength 350 nm 700 nm 2 μm Transmittance (%) 86 91 91 (Reference Example 1) In a 10 L glass reactor equipped with a stirrer, a dropping port, a thermometer, and a reflux condenser, 2.2 kg of acetic acid and ion exchange were carried out. 0.3 kg of zinc oxide powder and indium hydroxide (In ₂ O ₃ · nH) in a mixed solvent of 1.6 kg of water
12.80 g of ₂ O: In ₂ O ₃ content of 80% by weight) was added and mixed, and then the mixture was heated to 100 ° C. with stirring to obtain a uniform zinc-containing solution (A1).

Next, 10.7 kg of 2-butoxyethanol was charged into a 20 L glass reactor equipped with a stirrer, a dropping port, a thermometer and a distillate gas outlet and capable of heating a heat medium from the outside, and the internal temperature was 159 ° C. The temperature was raised to and maintained at that temperature. To this, a zinc-containing solution (A
1) The whole amount was dropped by a metering pump over 33 minutes.
After the dropwise addition was completed, when the internal temperature was raised to 168 ° C., 800 g of 2-butoxyethanol solution in which 36.9 g of lauric acid was dissolved was added for 10 seconds, and the mixture was heated and maintained at that temperature for 5 hours to obtain a blue-gray color. Dispersion of (D1) 5.64k
g was obtained. Dispersion (D1) has a fine particle concentration of 5.5% by weight
It was dispersed and contained in.

Next, the dispersion D1 was concentrated in an evaporator under reduced pressure at a bath temperature of 130 ° C. to a fine particle concentration of 26% by weight, and butyl cellosolve was added so that the fine particle concentration became 20% by weight. D1
C) was obtained. Table 2 shows the physical properties of the resulting fine particle dispersion (D1C) and the fine particles dispersed therein.

Reference Examples 2 to 3 The same as Reference Example 1 except that the type and amount of the raw material or the type and amount of the bottom solvent and the type of additive solution in the zinc-containing solution (A1) in Reference Example 1 were changed. Then, the reaction is performed, and each dispersion (D2 to D3)
And a concentration operation and a concentration adjustment are performed to obtain a fine particle dispersion (D2C to D) having a fine particle concentration of 20% by weight.
3C) respectively.

Table 2 shows the physical properties of the resulting fine particle dispersions and the fine particles dispersed therein. (Reference Example 4) The fine particle dispersion (D1C) obtained in the same manner as in Reference Example 1 was heated in a evaporator under reduced pressure at a bath temperature of 130 ° C to remove the heating solvent, and further at 100 ° C.
Vacuum drying treatment was carried out to obtain a fine particle powder (P1).

Table 2 shows the physical properties of the resulting fine particle powder (P1).
Shown in Reference Example 5 Table 3 shows the results of evaluation of physical properties such as crystallite diameter and dispersed particle diameter of the ZnO fine particle powder (P2) obtained by the French method.

[0133]

[Table 1]

[0134]

[Table 2]

[0135]

[Table 3]

Reference Example 6 Isopropyl alcohol 24 in a four-necked flask equipped with a reflux condenser, a stirrer and a thermometer.
1 part by weight, 16 parts by weight of water, and 0.005 parts by weight of 35% hydrochloric acid were sequentially charged, and methyltrimethoxysilane 1 was added while stirring.
After adding 0 part by weight and 30 parts by weight of tetraethoxysilane, the temperature was raised to 80 ° C, the reaction was performed at 80 ° C for 2 hours, and then the mixture was cooled. The resulting mixture (x) has a nonvolatile content of 1
It was a 7.0% by weight homogeneous solution. Hereinafter, the obtained mixture (x) is referred to as a silicate polymer solution (A).

Reference Example 1 100 parts by weight of the fine particle dispersion (D1C) obtained in the same manner as in Reference Example 1 (fine particles 2
0 part by weight), phthalocyanine compound (ph-1) 0.
After adding 5 parts by weight and stirring for 3 hours, the obtained dispersion liquid was evaporated under reduced pressure in a bath at a temperature of 130 ° C.
Then, the heating solvent was removed, and further vacuum drying treatment was carried out at 100 ° C. to obtain a fine particle powder (Zph1).

[0138]

[Table 4]

[0139]

[Table 5]

Hereinafter, the above-mentioned fine particle dispersion and fine particle powder as fine particle raw materials, and the coating composition, coated article, and resin using the phthalocyanine compounds (ph-1) to (ph-5) shown in Table 4 are used. Examples of the composition and the resin molded product will be shown, and the evaluation method will be described below. (Spectral characteristics) For spectral characteristics, refer to the self-recording spectrophotometer (U
V-3100, Shimadzu Corporation, irradiation wavelength 2
The transmittance for each wavelength of light at 200 to 200 nm was measured and evaluated.

(Heat Ray Cut Performance) From the measured spectral characteristics, the heat ray cut performance was evaluated based on the following criteria. The heat ray cut performance is obtained according to the following equation with respect to the heat ray cut amount at a wavelength of 2 μm obtained according to the following formula, the presence or absence of absorption due to the presence of a dye at a wavelength of 0.8 to 1.2 μm, and the case where the absorption is “present”. The amount of heat ray cut was used as a reference and judged as follows.

Heat ray cut amount S2 = 2 μm wavelength
Light transmittance (%) of the base material itself for the wavelength of 2 μm-Light transmittance of the coated product for the wavelength of 2 μm (%)-Amount of heat ray cut S1 = 0.8 to 1.2 μm
-(Light transmittance (%) at the maximum absorption wavelength (λX) of the sample in the same wavelength region-Light transmittance (%) at the wavelength λX of the base material itself) <Judgment criteria> Cut performance for 2 μm light S2 ≧ 30% ◎ 10% ≤ S2 <30% ○ S2 <10% × 0.8 to 1.2 µm Cut performance against light With selective absorption by dye S1 ≥ 30% ◎ 10% ≤ S1 <20% ○ S1 <10% △ Selection by dye No absorption x (UV blocking performance) From the measured spectral characteristics, the UV blocking performance and the like were evaluated based on the following criteria.

The light transmittance at a wavelength of 365 nm was measured by Tuv
(%) (Transparency in visible range: total light transmittance and haze) Measurement and evaluation were performed using a turbidimeter (NDH-1001 DP Nippon Denshoku Industries Co., Ltd.). Regarding the haze, Example 11,
For 12 and Comparative Examples 10 to 12, the actual measured values of the obtained films are shown, but in other cases, the haze UP (increase) with respect to the substrate was displayed.

(Comparative Example 1) Fine particle dispersion (D1C) 60 parts by weight Acrylic binder resin solution 20 parts by weight (Arosette 5858 (solid content 60% by weight), manufactured by Nippon Shokubai Co., Ltd.) n-butanol 40 parts by weight A paint consisting of That is, 60 parts by weight of the fine particle dispersion (D1C) was added to 40 parts by weight of n-butanol, and an acrylic binder resin solution (Alloset 5858 (solid content 60% by weight, Nippon Shokubai Co., Ltd.) 2
A coating material (R1) was prepared by adding and mixing 0 parts by weight, stirring for 3 hours, and then performing a dispersion treatment with an ultrasonic homogenizer for 30 minutes.

Next, the obtained coating material (R1) was applied to glass with a bar coater and dried to obtain a coated product (R1). The coated product (R1) had a property of shielding ultraviolet rays and heat rays and had excellent transparency in the visible region. The evaluation results of the coated product (R1) are shown in Table 7, and the spectral transmittance curve is shown in FIG.

Comparative Example 2 Phthalocyanine compound (ph-1) 0.127 parts by weight Acrylic binder resin solution 20 parts by weight (Alloset 5858 (solid content 60% by weight), manufactured by Nippon Shokubai Co., Ltd.) n-butanol 40 parts by weight Part A coating material comprising the above components was produced. That is, 40 parts by weight of n-butanol was added to phthalocyanine compound (ph-1) 0.
127 parts by weight were added and mixed to form a uniform solution, and the acrylic binder resin solution (Aroset 585
A coating material (R2) was prepared by adding and mixing 20 parts by weight of 8 (60% by weight of solid content, Nippon Shokubai Co., Ltd.), stirring for 3 hours, and then performing a dispersion treatment for 30 minutes with an ultrasonic homogenizer.

Next, the obtained coating material (R2) was applied to glass with a bar coater and dried to obtain a coated product (R2). The coated product (R2) has a wavelength of 0.8-1.
Although it had a shielding property against a heat ray of 2 μm, it did not have an ultraviolet ray cutting performance. Table 7 shows the evaluation results of the coated product (R2), and FIG. 1 shows the spectral transmittance curve.

(Example 1) Fine particle dispersion (D1C) 60 parts by weight Phthalocyanine compound (ph-1) 0.127 parts by weight Acrylic binder resin solution 20 parts by weight (Aroset 5858 (solid content 60% by weight), Ltd. Nippon Shokubai) n-Butanol 40 parts by weight A coating material comprising the above components was produced. That is, 0.127 parts by weight of the phthalocyanine compound (ph-1) was dissolved in 40 parts by weight of n-butanol, and the fine particle dispersion (D1) was added thereto.
C) 60 parts by weight was added and the resulting mixed dispersion was stirred for 1 hour. Next, 20 parts by weight of an acrylic binder resin solution (Aloset 5858 (solid content 60% by weight, Nippon Shokubai Co., Ltd.)) is added to the mixed dispersion, mixed and stirred for 3 hours, and then dispersed with an ultrasonic homogenizer for 30 minutes. A paint (1) was prepared according to.

Next, the obtained coating material (1) was applied to glass by a bar coater and dried to obtain a coated product (1). The coated product (1) was excellent in shielding ultraviolet rays and heat rays, and was also excellent in transparency in the visible region. The coated product (1) is based on the phthalocyanine compound (ph-1) which is not found in the coated product (R1).
Absorption with a peak of 0 nm and coated products (R
It was found that the transmittance in the entire heat ray wavelength range was lower than that in 1), so that the heat ray shielding rate was higher than that of the coated product (R1) and the haze value for visible light was low. Further, it was found that the coated product (1) was superior to the coated product (R2) in UV blocking performance. The evaluation results are shown in Table 7, and the spectral transmittance curve is shown in FIG.

(Examples 2 to 6, Comparative Example 3) As shown in Table 6,
Coating materials (2) to (6) and (R3) composed of a fine particle raw material, a phthalocyanine compound, and a binder component were produced in the same manner as in Example 1, coated on various base materials shown in Table 7 under the conditions shown in Table 7, and dried. By doing, coated products (2) to (6)
And a coated product (R3) was obtained.

The coated products (2) to (6) were excellent in the ability to shield ultraviolet rays and heat rays, and also excellent in transparency in the visible range. Coated products (2) to (6) and coated products (R
Table 7 shows the evaluation results of 3). The coated product (3) obtained in Example 3 was excellent in solvent resistance because the film was crosslinked.

The film of the coated article (4) obtained in Example 4 had a pencil hardness of 9H or higher and was excellent in scratch resistance.

[0153]

[Table 6]

[0154]

[Table 7]

(Examples 7, 8 and Comparative Examples 4 to 6) 100 parts by weight of a molten polycarbonate resin (manufactured by Teijin Kasei Co., Ltd., trade name: Panlite 1285) were mixed with the phthalocyanine compound and fine particles shown in Table 8 in Table 8. A 2 mm thick sheet was molded at 280 ° C. by a T-die extruder. Table 8 shows the evaluation results of the obtained sheets.

[0156]

[Table 8]

(Examples 9 and 10, Comparative Examples 7 to 9) Methyl methacrylate 10 was used between two pieces of hard glass according to a conventional method.
0 parts by weight, 0.2 parts by weight of azobisisobutyronitrile,
0.1 parts by weight of a release agent (ZELEC UN, manufactured by DuPont), the phthalocyanine compound shown in Table 9 and the fine particles added in the amounts shown in Table 9 were injected, and the mixture was immersed in a water bath at 65 ° C. for 14 hours. Then, the mixture was heated in an oven at 90 ° C. for 1 hour to complete the polymerization. After completion of the polymerization, the transparent resin plate having a thickness of 3 mm was peeled off from the glass. The evaluation results of the obtained plate are shown in Table 9.

[0158]

[Table 9]

(Examples 11 and 12, Comparative Examples 10 to 12)
The amounts of the phthalocyanine compound and the fine particles shown in Table 10 are shown in Table 10, respectively.
PP pellets (A) were obtained by melt-kneading with 100 parts by weight. Next, a two-layer PP film was obtained using an extruder equipped with a multilayer feed block die. That is, PP pellets (B) containing no phthalocyanine compound and no fine particle component are fed to the main extruder and melted at 220 ° C, and PP pellets (A) are fed to the auxiliary extruder and melted at 180 ° C. By adjusting the discharge rate, PP
A laminated sheet consisting of the (A) layer and the PP (B) layer is obtained, and the obtained sheet is stretched to obtain a thickness of 8
An OPP film in which a μmPP (A) layer and a PP (B) layer having a thickness of 20 μm were laminated was obtained.

Table 10 shows the evaluation results of the obtained film.

[0161]

[Table 10]

(Example 13) Fine particle powder (Zph-1)
5 parts by weight and 95 parts by weight of polyester resin pellets are mixed and melt-kneaded to obtain a polyester composition in which 5% by weight of fine particles are uniformly dispersed. The polyester composition is extruded into a sheet, and then stretched to obtain a thickness. A 40 μm polyester film was obtained. The film was a film in which fine particles were uniformly and highly dispersed, and was excellent in visible light transmittance, ultraviolet ray shielding property, and heat ray shielding property.

(Example 14) In the same manner as in Example 13,
After obtaining a polyester composition containing 5% by weight of fine particles (Zph-1), melt spinning was performed to obtain a polyester fiber. The fiber was a fiber in which fine particles were uniformly and highly dispersed, had a transparent feeling, and was excellent in ultraviolet ray shielding property and heat ray shielding property.

(Examples 15 to 17) The fine particle raw material, heat ray absorbent, binder resin solution and additional solvent shown in Table 11 were mixed and stirred for 3 hours, and then mixed with an ultrasonic homogenizer.
By performing a dispersion treatment for 0 minutes, paints (15) to (1
7) was prepared. Next, the obtained coating material was applied to a PET film with a bar coater and dried at 80 ° C. for 10 minutes to obtain coated products (15) to (17).

Table 12 shows the evaluation results of the coated products.

[0166]

[Table 11]

[0167]

[Table 12]

[0168]

The composition for shielding ultraviolet rays and heat rays of the present invention comprises fine particles of an oxide coprecipitate of a metal consisting of 80 to 99.9 atomic% zinc and 0.1 to 20 atomic% IIIB metal element ( Zinc oxide-based fine particles) and a heat ray absorbent,
A transparent material that simultaneously blocks ultraviolet rays and heat rays can be constructed. Furthermore, in the composition of the present invention, zinc oxide fine particles having an infrared ray cutting ability over a wide wavelength range of heat rays and a heat ray absorbent having a selective infrared ray cutting ability at a specific wavelength range of heat rays are combined, so that the conventional It is possible to construct a transparent material that achieves an unprecedented heat ray cutting ability and can arbitrarily control the cutting performance (cut wavelength, cut amount, etc.) according to needs.

The resin molded product of the present invention comprises zinc 80-99.
Fine particles of a metal oxide coprecipitate containing 9 atomic% and a Group IIIB metal element of 0.1 to 20 atomic% (zinc oxide fine particles)
And a heat ray absorbent, and a dispersion medium, the dispersion medium is a resin for dispersing the zinc oxide-based fine particles and the heat ray absorbent, ultraviolet and heat ray shielding composition, plate, sheet, film and fiber Since it is formed into at least one shape selected from the group consisting of, it is a transparent material that simultaneously cuts ultraviolet rays and heat rays. In the resin molded article of the present invention, zinc oxide fine particles having an infrared ray cutting ability over a wide wavelength range of heat rays, and by appropriately changing the combination of a heat ray absorbent having a selective infrared ray cutting ability in a specific wavelength range of heat rays, Achieves unprecedented heat ray cutting ability, and can arbitrarily control cutting performance (cut wavelength, cut amount, etc.) according to needs.

The coated article of the present invention comprises a resin molding, glass,
And at least one base material selected from the group consisting of paper and a coating film formed on the surface of the base material, wherein the coating film comprises 80 to 99.9 atomic% zinc and 0.1 to 2 Group IIIB metal element.
A fine particle of an oxide coprecipitate of 0 atom% (zinc oxide type fine particles), a heat ray absorbent, and a dispersion medium are contained, and the dispersion medium is a binder component and the zinc oxide type fine particles and the heat ray absorbent are dispersed. The coating film is a transparent material that simultaneously cuts ultraviolet rays and heat rays, since it contains the composition for shielding ultraviolet rays and heat rays. In the coated product of the present invention, zinc oxide fine particles having an infrared ray cutting ability over a wide wavelength range of heat rays, and by appropriately changing the combination of a heat ray absorbent having a selective infrared ray cutting ability in a specific wavelength range of heat rays, Achieves unprecedented heat ray cutting ability, and can arbitrarily control cutting performance (cut wavelength, cut amount, etc.) according to needs.

[Brief description of drawings]

FIG. 1 is a spectral transmittance curve of a coated product obtained in Example 1 and Comparative Examples 1 and 2 and a glass plate used as a substrate.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor, Koji Yoshito, 1-25-25 Kannondai, Tsukuba-shi, Ibaraki 12 Incorporated company Nippon Shokubai (72) Inventor Osamu Kaieda 1-25-25 Kannondai, Tsukuba-shi, Ibaraki Stock company Nippon Shokubai

Claims (5)

[Claims] 1. An ultraviolet and heat ray shield containing fine particles of an oxide coprecipitate of a metal, which comprises 80 to 99.9 atomic% zinc and 0.1 to 20 atomic% Group IIIB metal element, and a heat ray absorbent. Composition. 2. The composition according to claim 1, wherein the heat ray absorber is a phthalocyanine compound. 3. The composition according to claim 1, further comprising a dispersion medium, wherein the dispersion medium disperses the fine particles and the heat ray absorbent. 4. A resin molded product obtained by molding the composition according to claim 3, wherein the dispersion medium is a resin, into at least one shape selected from the group consisting of plates, sheets, films and fibers. 5. A surface of the base material comprising at least one base material selected from the group consisting of a resin molded body, glass and paper, and the composition according to claim 3, wherein the dispersion medium is a binder component. A coated product having a coating film formed on.