JP2957924B2 - Ultraviolet and heat ray shielding composition and use thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention 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 to the titanium oxide fine particles, the ultraviolet cut wavelength region is wider up to the longer wavelength side, and the ultraviolet cut effect is maintained for a long time. For this reason, zinc oxide fine particles are contained in a resin to be used as a resin molded product such as a film, a fiber and a resin plate, or zinc oxide fine particles are contained in an organic or inorganic binder to form a film, a fiber, a resin plate, glass and A transparent product having an ultraviolet shielding effect is produced by using it as a paint applied to a base material such as paper.

[0003]

A 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. It is an object of the present invention to provide a composition that can transmit visible light and simultaneously block ultraviolet light and heat rays.

Another object of the present invention is to transmit visible light,
An object of the present invention is 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 shielding ultraviolet rays and heat rays.

[0005]

The ultraviolet and heat ray shielding composition of the present invention contains 80 to 99.9 atomic% of zinc and
It contains fine particles of a metal oxide coprecipitate comprising a Group IIIB metal element of 0.1 to 20 atomic% and a heat ray absorber. The composition of the present invention may further include a dispersion medium regardless of whether the heat ray absorbent is a phthalocyanine compound. The dispersion medium is for dispersing the fine particles and the heat ray absorbent.

[0006] The resin molded product of the present invention has a zinc content of 80-99.
A composition comprising 9 atomic% and a metal oxide coprecipitate composed of 9 atomic% and 0.1-20 atomic% of a group IIIB metal element, a heat ray absorbent, and the dispersion medium, is prepared from a plate, a sheet, a film, or a fiber. It is formed 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 substrate and a coating film formed on the surface of the substrate. The substrate is at least one selected from the group consisting of a resin molded product, glass and paper. The coating film contains a composition containing 80 to 99.9 atomic% of zinc and 0.1 to 20 atomic% of a Group IIIB metal element as fine particles of a metal oxide coprecipitate, a heat ray absorbent, and the dispersion medium. Comprising. Here, the dispersion medium is a binder component.

In the composition of the present invention, the resin molded article of the present invention, and the coated article 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

[Ultraviolet ray and heat ray shielding composition] The ultraviolet ray and heat ray shielding composition according to the present invention comprises a metal oxide consisting of 80 to 99.9 atomic% of zinc and 0.1 to 20 atomic% of a group IIIB metal element. It contains body particles and a heat ray absorber.

Fine particles of a metal oxide coprecipitate comprising 80 to 99.9 atomic% of zinc and 0.1 to 20 atomic% of a Group IIIB metal element (hereinafter, may be referred to as "zinc oxide-based fine particles") Is capable of transmitting visible light, has a wider cut-off wavelength range for ultraviolet light than titanium oxide fine particles, extends the long-wavelength side, has a long-lasting UV cut effect, and has a wide infrared range including heat rays. Has cutting ability. The heat ray absorbent has a selective ability in a near infrared specific wavelength range. Therefore, by combining the zinc oxide-based fine particles and the heat ray absorbent, an unprecedented heat ray cut ability can be achieved, and the cut performance (cut wavelength, cut amount, etc.) can be arbitrarily controlled according to needs.

[0010] 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, squarium dyes, dithiol nickel complex dyes, azo dyes,
Examples include naphthoquinone, anthraquinone dye, triphenylmethane dye, aminium dye, diimonium dye, phthalocyanine dye (the above phthalocyanine compound), and naphthalocyanine dye.

Since the dye used in the present invention preferably needs to have solubility in a dispersion medium and weather resistance, it is preferable to use a soluble phthalocyanine dye among the above-mentioned dyes (ie, a soluble phthalocyanine compound among the above phthalocyanine compounds). )
Is preferred. Such soluble phthalocyanine dyes,
JP-A-6-107766, JP-A-6-25548
JP, JP-A-5-345861, JP-A-5-5-2
No. 22301, JP-A-5-22047, JP-A-4-39361, JP-A-4-23868, JP-A-2-175763, JP-A-64-45
No. 474 (above, Nippon Shokubai Co., Ltd.)
Japanese Patent Application Laid-Open No. 152767/1987, Japanese Patent Application Laid-Open No. 61-152689 and Japanese Patent Application Laid-Open No.
K), JP-A-7-70129, JP-A-4-273
879, JP-A-60-209583, JP-A-63-308073 (above, ICI and / or Zeneca), JP-A-5-25177, JP-A-5-25177
These are described in, for example, JP-A-1272, JP-A-3-62878, JP-A-3-31247, and JP-A-63-270765 (all mentioned above, Mitsui Toatsu). Specifically, for example, 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-ethoxycarbonyl cobalt phthalocyanine-Octafluoro-octakis-n- Octylaminodichlorotin phthalocyanine octafluoro-octakisphenylthiozinc phthalocyanine octafluoro-octakis-m-tetrahydrofurfuryloxycarbonylphenoxyoxyvanadium phthalocyanine dodecafluoro-tetrakistordinodichlorotin phthalocyanine (hereinafter referred to as ph-4) )-Dodecafluoro-tetrakis-1-naphthylaminodichlorotin phthalocyanine-dodecafluoro-tetrakisbenzylamino Phthalocyanine • Dodecafluoro-tetrakiscyclohexylaminopalladium phthalocyanine • Dodecafluoro-tetrakisphenylthiodichlorotin phthalocyanine • Octafluoro-tetrakisphenylenedithio zinc phthalocyanine • Octakisanilino-octakisphenylthiooxyvanadium phthalocyanine (hereinafter referred to as ph-2) )-Octakisanilino-octa-o-methoxyphenylthio copper 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-dichlorooxyvanadium phthalocyanine octa-3,6-n-octyloxy-octa-4,
5-bisphenylthiocopper phthalocyanine octa-3,6-isohexyloxy-octa-4,
5-bis-p-tert-butylphenylthio copper phthalocyanine tetrakis-3- (2,4-dimethyl) pentyloxy palladium phthalocyanine tetrabromo-tetrakis-2- (3-methyl) pentyloxy nickel phthalocyanine mono (phenylamino) ) Tetradeca (4-methylphenylthio) copper phthalocyanine penta (4-aminophenylamino) deca (2-methylphenylthio) copper phthalocyanine di (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 ultraviolet and heat ray shielding composition of the present invention is not particularly limited, but may be appropriately determined according to the purpose of use. 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 to be dispersed.
The dispersion medium is a resin, a resin solution, a resin dispersion, or the like.
Examples of the resin include (1) a polyolefin resin such as polyethylene and polypropylene; a polystyrene resin; a vinyl chloride resin; a vinylidene chloride resin; a polyvinyl alcohol; a polyester resin such as polyethylene terephthalate and polyethylene naphthalate; a polyamide resin; (Meth) acrylic resin such as (meth) acrylate, phenolic resin; urea resin; melamine resin; unsaturated polyester resin; polycarbonate resin; thermoplastic or thermosetting resin such as epoxy resin;
(2) Ethylene-propylene copolymer rubber, polybutadiene rubber, styrene butadiene rubber, synthetic rubber or natural rubber such as acrylonitrile butadiene rubber, and the like, one of which may be used alone, or
Two or more may be 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 product, the amounts of the zinc oxide-based fine particles, the heat ray absorbent, and the resin (dispersion medium) in the composition of the present invention are, for example, as follows. 0.01 to 99% by weight of zinc oxide-based fine particles and 0.00% of heat ray absorbent, based on the total weight of the three solids
It is a ratio of 0.5 to 20% by weight and a resin of 0.1 to 99.9% by weight (preferably 5 to 99.9% by weight). If the ratio of the zinc oxide-based fine particles is less than the above range, the thickness of the molded product must be increased in order to obtain sufficient ultraviolet shielding properties, and if it exceeds, the dispersibility of the fine particles is reduced and the visible light of the molded product is reduced. Transparency may decrease. If the ratio of the heat ray absorbent is lower than the above range, it may be difficult to obtain sufficient heat ray shielding properties. If the ratio is higher than that, the transparency of the molded product to visible light may decrease or the price may increase. When the proportion of the resin as the dispersion medium is below the above range, the dispersibility of the fine particles is reduced, the transparency of the molded product to visible light is reduced, or the molded product has poor physical properties such as mechanical properties and chemical resistance. If it exceeds, the thickness of the molded product must be increased in order to obtain a sufficient ultraviolet shielding property. 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 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. 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; organic binder such as synthetic rubber or natural rubber such as ethylene-propylene copolymer rubber, polybutadiene rubber, styrene butadiene rubber, and acrylonitrile butadiene 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 abrasion resistance of a film obtained by applying and drying the coating composition on a substrate, and the purpose of use such as the type of the substrate. One alone, or
Two or more are used in combination.

[0013] The binder component may be dissolved, emulsified or suspended in a solvent. The solvent for the binder component is appropriately selected depending on the purpose of use of the coating composition, the type of the binder, and the like.For example, alcohols, aliphatic and aromatic carboxylic esters, ketones, ethers,
Organic solvents such as ether esters, aliphatic and aromatic hydrocarbons, and halogenated hydrocarbons; water; mineral oils, vegetable oils, wax oils, silicone oils, and the like. Alternatively, two or more may be mixed and used in an optional ratio as needed. As a solvent for the binder component, a solvent for a dispersion of zinc oxide-based fine particles can be used.

When the composition of the present invention is a coating composition,
In the composition of the present invention, zinc oxide-based fine particles, heat ray absorbent,
The amount of the binder component (dispersion medium) is, for example, 0.1 to 99% by weight of zinc oxide-based fine particles and 0.0005 to 0.005% of the heat ray absorbent based on the total weight of the solid contents of these three components.
20% by weight, 0.1 to 99.9% by weight of a binder component, preferably 10 to 79.9% by weight of zinc oxide-based fine particles, 0.1 to 10% by weight of a heat ray absorbent, and 20 to 89. 9% by weight. If the ratio of the zinc oxide-based fine particles is less than the above range, in order to obtain sufficient ultraviolet shielding properties, the thickness of the coating film must be increased, and if it exceeds, the dispersibility of the fine particles is reduced and the visible light of the coating film is reduced. Transparency may decrease. If the ratio of the heat ray absorbent is lower than the above range, it may be difficult to obtain sufficient heat ray shielding properties. If the ratio is higher than that, the transparency of the coating film to visible light may be reduced or the price may be increased. When the proportion of the binder component as the dispersion medium is below the above range, the dispersibility of the fine particles is reduced, the transparency of the coating film to visible light is reduced, and the physical properties of the coating film such as mechanical properties and chemical resistance are reduced. In some cases, the thickness of the coating film must be increased in order to obtain a sufficient ultraviolet shielding property.

When the composition of the present invention is a coating composition,
The total solid content of the zinc oxide-based fine particles, the heat ray absorbent, and the binder component is 1 to 80 with respect to the total weight of the composition.
%, Preferably 5 to 50% by weight. When the thickness is below the above range, a uniform film may be hardly obtained or the control of the film thickness may be difficult. It may be difficult to form a proper film. The remainder is a solvent for dispersing the zinc oxide-based fine particles and dissolving or dispersing the binder component, or an additive such as a pigment used depending on the purpose of use of the solvent and the coating composition.

When the composition of the present invention is a resin composition, a resin molded product, or a paint composition, the mixing ratio of the zinc oxide-based fine particles and the heat ray absorbent is such that the ratio of the heat ray absorbent to the zinc oxide-based fine particles is small. It is a ratio of 0.05 to 30% by weight, preferably 0.3 to 20% by weight in terms of a solid content weight ratio. If the ratio is below the above range, the effect of adding the heat ray absorbent may decrease, and if it exceeds the range, the visible light transmittance may decrease.

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 the zinc oxide-based fine particles and the heat ray absorbent in the resin as the dispersion medium, For example, when melt-kneading a pellet or powder resin, a master batch method in which a zinc oxide-based fine particle powder and a heat ray absorbent are added and mixed, and a zinc oxide-based fine particle and a heat ray absorbent are mixed in a solution in which the resin is dissolved. A conventionally known method such as a method of removing the solvent after the dispersion can be employed. Alternatively, a method of mixing and dispersing zinc oxide-based fine particles and a heat ray absorbent in the process of producing the resin, for example, when the resin is a polyester resin, a series of processes in the polyester production process, i.e., a transesterification reaction to a polymerization reaction. It is also possible to adopt a method of adding and mixing a dispersion obtained by dispersing a powder of zinc oxide-based fine particles and a heat ray absorbent in glycol, which is a polyester raw material, at any time in the process.

According to the above-mentioned method, a resin composition in which zinc oxide-based fine particles and a heat ray absorbent are dispersed and contained in a resin is obtained. The resin composition may be in the form of a usual molding material such as a 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, mixing and dispersing a powder of zinc oxide-based fine particles in a solvent containing a heat ray absorber and a binder component, a dispersion of the zinc oxide-based fine particles dispersed in a solvent and a solvent containing a heat ray absorber and a binder component And a method in which a heat ray absorber and a binder component are added to a dispersion in which zinc oxide-based fine particles are dispersed in a solvent and mixed, and the like. 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 employed.

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-described method for producing zinc oxide-based 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-based fine particles, a heat ray absorber, a binder component, and a solvent can be obtained.

The zinc oxide-based fine particles used in the composition of the present invention contain at least one additive element selected from the group consisting of group IIIB metal elements and zinc as a metal component, and the zinc content is at least 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 exhibiting zinc oxide (ZnO) crystallinity as viewed from X-ray diffraction is mainly used. It is a zinc oxide type fine particle as a constituent. Here, the crystal form of zinc oxide is not particularly limited, and for example, a hexagonal crystal (wurtzite structure), a cubic crystal (salt-type structure), a cubic face-centered structure, and the like are known. What is necessary is just to show those X-ray diffraction patterns. 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 99.9%, expressed as a ratio of the number of zinc atoms to the total number of metal components.
9.5%. When the ratio is below the above range, it is difficult to obtain fine particles having a controlled uniformity in particle shape, particle diameter, higher order structure and the like. When the ratio exceeds the above range, the function as a coprecipitate, that is, the infrared ray shielding properties including heat rays becomes insufficient.

The zinc oxide-based fine particles referred to in the present invention may be, for example, a coupling agent such as a silane coupling agent or an aluminum coupling agent or an organic siloxane such as an organosiloxane or a chelate compound as long as it is as described above. Fine particles formed by bonding a metal compound to the surface of a zinc oxide crystal or forming a coating layer on the surface, inorganic acids such as halogen elements, sulfate groups, and nitrate groups, or organic compounds such as fatty acids, alcohols, and amines are contained inside the fine particles. Particles and / or the like 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 seed additional element and the metal element other than zinc, it is not preferable that the alkali metal and the alkaline earth metal are present in the form of a solid solution in the ZnO crystal, and the group IIIB metal element constituting the coprecipitate is not preferable. Is preferably 1/10 or less, more preferably 1/100 or less, based on the total number of atoms of at least one additional element selected from the group consisting of:

In the zinc oxide-based fine particles of the present invention, the group IIIB metal element as an additive element constituting the metal oxide coprecipitate is, for example, boron, aluminum (Al), gallium (Ga), indium (In) and thallium. At least one selected from (Tl), of which indium and / or aluminum is most preferred.

The zinc oxide fine particles of the present invention include the following
~ 3. 1. Single particles of the metal oxide coprecipitate, ie, when crystallites are dispersed in a single crystal state without secondary aggregation,
When the secondary aggregation is partially or completely loose (above,
The first case). 2. The case where 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 first and second cases, the coprecipitate is a complex with a polymer (third case). In any of the first to third cases, excellent in transparency,
Preferred embodiments of the zinc oxide-based fine particles for obtaining the resin molded product or the coated product of the present invention are described below. That is, the zinc oxide-based fine particles have an average crystallite diameter of 0.001 to 0.05 μm.
m and an average dispersed particle size of 0.001 to 0.2 μm are preferable because the composition, resin molded article and coating film of the present invention containing the fine particles have excellent transparency. More preferably, the average crystallite diameter is 0.005 to 0.5.
03 μm range, average dispersed particle diameter is 0.005 to 0.1
μm, and particularly preferably, the average crystallite diameter is in the range of 0.005 to 0.03 μm, and the average dispersed particle diameter is in the range of 0.005 to 0.03 μm. If the average crystallite diameter is less than 0.005 μm or the average dispersed particle diameter is less than 0.005 μm, the UV absorption edge may be blue-shifted to a shorter wavelength. When the average crystallite diameter is larger than 0.03 μm, visible light is scattered, so that the transparency of a coating film or the like containing the fine particles may be reduced. When the average dispersed particle size is larger than 0.1 μm, the transparency of a coating film or the like containing the fine particles is reduced,
The dispersion stability of the paint may be reduced.

The average crystallite diameter is a value D (μm) obtained from the diffraction angle θ and the diffraction line width β (radian) obtained by X-ray diffraction measurement using the Scherrer equation (the following equation). is there. K is the Scherrer constant and λ is the X used.
The wavelength of the line (μm). D = Kλ / βcosθ The average dispersed particle diameter refers to the weight or the number average 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 diameter of the fine particles in the coating composition refers to the average particle diameter of the fine particles in a dispersed state in the coating composition. Usually, when the medium is a liquid, it is measured by a dynamic light scattering method or a centrifugal sedimentation method, and when the medium is a solid (a resin molded product or the like), it is measured by a transmission electron microscope. However, when the crystallite has a flake shape, the length in the thickness direction is 0.05 μm or less, preferably 0.03 μm or less.
μm or less, and when these flaky crystals are dispersed in a state where 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-based fine particles is arbitrary. For example,
Flakes, flakes such as (hexagonal) plates, etc .; needles, columns, rods, cylinders; grains, such as cubes, pyramids; and spheres. Further, in the second case, the secondary particles of the zinc oxide-based fine particles may be hollow having only the outer shell. When it is hollow, it has excellent light diffusion transmittance. In this case, the relationship between the size of the zinc oxide-based fine particles of the single particles and the secondary particles that are aggregates thereof is such that the ratio of the shortest particle diameter of the single particles to the shortest particle diameter of the fine particles is 1/10 or less. Preferably, there is.

In the third case, the form of compounding is free. For example, first, (A) the surface of a single particle of the polymer and / or the surface of a plurality of the single particles And then (B)
There is a form in which the polymer binds the single particles to each other. Finally, (C) the polymer constitutes a matrix, and the single particles do not aggregate in the matrix and / or There is a form in which a set of individuals is dispersed. Also in this case, the single particle and the polymer may be a hollow one in which only the outer shell part is formed. When the hollow one is used, the light diffusion and transparency 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 composite 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, or a polyimide resin. Polymer, polyurethane resin polymer, polyester resin polymer, phenol resin polymer, organopolysiloxane polymer, acrylic silicone resin polymer, polyalkylene glycol, etc., polyolefin polymer such as polyethylene and polypropylene, polystyrene polymer etc. Thermoplastic or thermosetting resins; synthetic rubbers and natural rubbers such as ethylene-propylene copolymer rubber, polybutadiene rubber and acrylonitrile-butadiene rubber.

Preferred polymers are those having one or more polar atomic groups because zinc oxide-based fine particles are excellent in chemical stability such as solvent resistance and chemical resistance and mechanical properties. Preferred polar atomic groups are a carboxyl group, an amino group (primary amino group, secondary amino group, tertiary amino group, imino group, imino bond), quaternary ammonium 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 at least one sulfonic acid group. 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 the crushing strength is excellent, and the fine (average particle diameter of 0.001 to 0.1 μm)
m) Single particles can be easily obtained, and zinc oxide-based fine particles having a uniform particle size (a variation coefficient of the particle size is 30% or less) and a uniform particle shape are easily obtained.

Among the polymers exemplified above as the polymer used for the composite, selected from the group consisting of (meth) acrylic, styrene, vinyl, copolymers thereof, alkyds, polyesters and polyamides. 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 are particularly excellent in affinity and dispersibility for a transparent resin.

In both the second case and the third case, the average particle size of the zinc oxide-based fine particles is not particularly limited.
Usually, it is in the range of 0.001 to 10 μm. For example,
In the mode (A) of the third case, the thickness is preferably 0.001 to 0.05 μm from the viewpoint of high transparency as described above. ~ 5
μm is preferred.

The zinc oxide fine particles of the present invention may be used as a dispersion dispersed in a solvent. In this case, as a medium, water, alcohols, ketones,
In addition to aliphatic and aromatic carboxylic 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 paint applications. As the organic binder,
(Meth) acrylic, vinyl chloride, silicone, melamine, urethane, styrene, alkyd, phenol, epoxy, polyester and other thermoplastic or thermosetting resins; ethylene-propylene copolymer rubber, There are synthetic rubber or natural rubber such as polybutadiene rubber and acrylonitrile-butadiene rubber. Examples of the inorganic binder include silica sol, alkali silicate, silicon alkoxide, and phosphate.

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

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

In the above-mentioned production method, a mixture obtained by mixing a zinc source and a monocarboxylic acid in water is added to and mixed with a medium comprising at least an alcohol heated to 100 ° C. or higher, whereby the water and / or monocarboxylic acid is mixed. It is preferable to include a step of evaporating and removing at least a part of the acid. It is good to use the zinc source and the monocarboxylic acid after dissolving them in water. However, it prevents the crystallinity of the fine particles from being impaired, and prevents secondary aggregation to improve the uniformity of the size and shape of the fine particles. This is because it is better to remove water and monocarboxylic acid out of the system as much as possible. In addition,
Fine particles may be formed during the addition of the mixture to the heating medium, but usually, the formation is caused 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 under normal pressure of 200 °.
It is preferably a saturated fatty acid of C or less. In the above-mentioned production method, the zinc source and the monocarboxylic acid are mixed at a temperature of 100 ° C. or higher in a medium comprising at least an alcohol and in the presence of a compound containing at least one additional 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 the system, or a carboxyl group, an amino group, a quaternary ammonium group, an amide group, an imide bond, an alcoholic and / or phenolic hydroxyl group,
Carboxylic acid ester bond, urethane group, urethane bond,
It has one or two or more atomic groups 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. , Molecular weight 100
In some cases, less than 0 additive compounds may coexist, carbon dioxide and / or a carbonate source may coexist, and a lactic acid source may coexist.

When the system is kept at a temperature of 100 ° C. or higher, if a polymer is allowed to coexist, zinc oxide-based 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 polymer, alkyd resin-based polymer, amino resin-based polymer, vinyl resin-based polymer, epoxy resin-based polymer, polyamide resin-based polymer, polyimide resin-based polymer, and polyurethane. In addition to resin-based polymers, polyester resin-based polymers, phenolic resin-based polymers, organopolysiloxane-based polymers, acrylic silicone resin-based polymers, polyalkylene glycols, and the like, thermoplastic resins such as polyethylene, polypropylene, and other polyolefin-based polymers, and polystyrene-based polymers, Thermosetting resins; synthetic rubbers such as ethylene-propylene copolymer rubber, polybutadiene rubber, and acrylonitrile-butadiene rubber; and natural rubbers. When the polymer has the specific functional group described above, the surface treatment of the fine particles becomes possible, and the particle diameter can be controlled.

When the system is maintained at a temperature of 100 ° C. or higher, the presence of the above-mentioned compound having a specific functional group enables the surface treatment of the fine particles and the control of the particle size. When the system is kept at a temperature of 100 ° C. or higher, the presence of carbon dioxide and / or a carbonic acid source makes it easy to obtain fine (0.05 μm or less) fine particles having excellent water dispersibility. In this case, the carbon source can be replaced by using (basic) zinc carbonate as a part of the zinc raw material. However, the amount of the carbonic acid source is suitably from 0.1 to 20 mol% with respect to zinc in a molar ratio. If the amount is too large, crystallization of zinc oxide may be hindered, and it is necessary to increase the heat treatment temperature. As the carbonate source, for example, compounds such as ammonium carbonate, ammonium hydrogen carbonate, and urea that 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 and the like are exemplified, and each is used alone or in combination of two or more.

One effective method for obtaining the zinc oxide-based fine particles in the form of single particles composed of a coprecipitate of a metal oxide as primary particles and secondary particles formed by aggregating the primary particles is as follows.
A method in which a lactic acid source coexists when the system is maintained at a temperature of 100 ° C. or higher is exemplified. Lactic acid source used in the present invention,
Lactic acid; metal lactates such as ammonium lactate, sodium lactate, lithium lactate, calcium lactate, magnesium lactate, zinc lactate, aluminum lactate, manganese lactate, iron lactate, nickel lactate, silver lactate; methyl lactate, ethyl lactate;
Lactate ester compounds, such as n-butyl lactate, which can generate lactic acid by hydrolysis or the like. One of these compounds 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 the secondary particles are further hollow, they function as porous fine particles or microcapsules. , Oil absorption, moisture absorption, adsorption of harmful metal ions, absorption and separation of toxic gases and odors, etc. Adsorption separation, removal and collection; heat and sound insulation and other heat and sound shielding functions (insulation filler, Immobilizing function for metal ions, enzymes and bacteria (catalyst carrier, chromatographic packing, etc.); light weight; imparting a sustained release function for liquids and fragrances held inside to the composition of the present invention. it can.

Hereinafter, an example of the method for producing the zinc oxide fine particles used in the present invention will be described in detail. This method, for example,
The mixture (m) obtained by dissolving or dispersing the zinc source and the monocarboxylic acid in at least an alcohol medium is converted into at least one additive element selected from the group consisting of Group IIIB metal elements (hereinafter, referred to as a group IIIB metal element). A compound containing a “metal (M)” (which may be referred to as “metal (M) compound”). 100 under coexistence
By maintaining the temperature at a temperature equal to or higher than ℃, the crystallinity of the metal oxide containing 80 to 99.9% of zinc and 0.1 to 20% of metal (M) in a ratio of the number of atoms to the total number of atoms of the metal element. Zinc oxide-based fine particles consisting of coprecipitates are deposited.

The zinc source is converted into X-ray diffraction crystalline zinc oxide by heating a mixture (m) containing a monocarboxylic acid and an alcohol. ) By the coexistence of the compound, a dispersion containing the zinc oxide-based fine particles of the present invention can be obtained. At this time, if at least one of the three components of the zinc source, the monocarboxylic acid, and the alcohol is lacking as a starting material, a precipitation reaction of zinc oxide crystals does not occur, and if the metal (M) does not exist, the present invention will be described. Cannot 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 powder), zinc oxide (zinc white), zinc hydroxide, basic zinc carbonate, mono- or di-carboxylates which may have a substituent (for example, zinc acetate, zinc octylate, stearin) Zinc acid, zinc oxalate At least one selected from the group consisting of zinc lactate, zinc tartrate and zinc naphthenate) is preferred. When these zinc sources are used, a desalting step is not required, and the number of steps is smaller than when zinc chloride, zinc nitrate, or zinc sulfate that requires a desalting step is used.

Among them, at least one zinc source selected from the group consisting of zinc metal (zinc powder), zinc oxide (zinc white), zinc hydroxide, basic zinc carbonate and zinc acetate is inexpensive and can be handled. 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 inhibit the reaction of forming zinc oxide crystals during the heating process, This is more preferable because the size and shape of the particles and the particles can be easily controlled.

Zinc oxide and / or zinc hydroxide are not only available inexpensively, but also the type of monocarboxylic acid can be arbitrarily selected. In addition, by using these materials, fine particles having a controlled shape or particle diameter can be obtained. It is particularly preferable because it is easily obtained. The amount of the zinc source is, for example, 0.1 to 95% by weight, preferably 0.5% by weight, in terms of ZnO, based on the total amount of the zinc source, the monocarboxylic acid and the medium.
-50% by weight, more preferably 1-30% by weight.
If the ratio is below the above range, the productivity may be low. If the ratio is higher than the above range, secondary agglomeration of fine particles may easily 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; monocarboxylic 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.

Preferred monocarboxylic acids are 20 at 1 atmosphere.
It is a saturated fatty acid having a boiling point of 0 ° C. or less. Specifically, formic acid, acetic acid, propionic acid, butyric acid, and isobutyric acid are preferred. The reason is that the content of the monocarboxylic acid in the reaction system is easily controlled in the process from the preparation of the mixture to the heating, and therefore, the precipitation reaction of zinc oxide crystals is easily controlled strictly. The saturated fatty acid is preferably used in a range of 60 to 100 mol%, more preferably in a range of 80 to 100 mol%, based on the total amount of the monocarboxylic acid. If the ratio 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 monocarboxylate such as zinc acetate. When the zinc salt is used, it is not always necessary to separately add the monocarboxylic acid as a raw material. The amount (or charge) of the monocarboxylic acid used in the production method of the present invention is, for example, 0.5 to 50, preferably 2.2 to 10 in a molar ratio to the amount of Zn atoms in the zinc source. Economical within the above range,
It is preferable in terms of easy generation of the fine particles, easy aggregation of the fine particles which 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-based fine particles having good ZnO crystallinity and fine particles having a high uniformity in shape and particle diameter. May 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, Butyl alcohol, propargyl alcohol, etc.), alicyclic monohydric alcohols (cyclopentanol, cyclohexanol, etc.), aromatic monohydric alcohols (benzyl alcohol, cinnamyl alcohol, methylphenylcarbinol, etc.), heterocyclic monovalent Monohydric alcohols such as alcohols (furfuryl alcohol and the like); 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-
Glycols such as 1,2-diol, cyclohexane-1,4-diol, and 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 and 2,2-bis (4-hydroxyphenyl) propane and their monoethers and monoesters; And polyhydric alcohols and their monoethers, monoesters, diethers and diesters. Any one of these alcohols may be used alone, or two or more of them may be used in combination.

The amount of alcohol in the medium composed of at least alcohol is not particularly limited. However, in order to carry out the reaction for generating zinc oxide-based fine particles in a short time, the molar ratio of alcohol to Zn atom derived from the zinc source is, for example, 1-100, preferably 5-80, more preferably 1
0 to 50. Below this range, it is difficult to obtain zinc oxide-based fine particles having good ZnO crystallinity, or dispersibility,
Fine particles having excellent uniformity in shape and particle diameter may not be easily obtained.

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

The metal (M) compound used in the production method of the present invention includes, for example, metals such as simple metals and alloys of metal (M); oxides; hydroxides; (basic) carbonates, nitrates , Sulfates, chlorides, fluorides, etc., inorganic salts such as halides; acetates, propionates, butyrates, laurates, etc .; metal alkoxides; β-diketones, hydroxycarboxylic acids, ketoesters And all compounds containing a trivalent or tetravalent metal (A), such as metal chelate compounds with keto alcohol, amino alcohol, glycol, quinoline, etc .; 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 be finally changed to trivalent or tetravalent during the process of forming fine particles (this compound Gobutsu is a concept including a metal such as an elemental metal or an alloy) is used.

III When aluminum is used as the Group B metal element, examples of the compound 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, acetoalkoxy aluminum diisopropylate, aluminum laurate, aluminum stearate, diisopropoxy aluminum Stearate, ethyl acetoacetate aluminum diisopropylate and the like are used.

III When boron is used as the Group B metal element, examples of the boron-containing compound include boron trioxide, boric acid, boron oxalate, boron trifluoride diethyl ether complex, boron trifluoride monoethylamine complex, trimethyl Borate,
Triethyl borate, triethoxy borane, tri-n-
Butyl borate and the like are used.

When gallium is used as the IIIB metal element, the compound containing gallium may be, 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.

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

When thallium is used as a Group IIIB metal element, the compound containing thallium includes, for example,
Thallium, thallium oxide (I), thallium (III) oxide,
Basic thallium hydroxide (I), thallium chloride (I), thallium (I) iodide, 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 (II) sulfate
I) and thallium (III) hydrogen sulfate are used.

The metal (M) oxide; hydroxide may be in the form of powder, but a colloidal metal oxide such as alumina sol and / or an aqueous sol of metal hydroxide or an 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 more of steps I, II and III, a metal (M) compound Can be added.

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

In the production method of the present invention, it is preferable that the step I is a step of preparing a mixture (n) further containing water. By this step, a solution-like mixture (n) is easily obtained. The order of addition of the zinc source, monocarboxylic acid and water is arbitrary. For example, a mixture (n) is prepared by dissolving the zinc source in a mixed solvent of monocarboxylic acid and water. In the production method of the present invention, it is preferable that the step II and the step III include a step of adding the mixture (n) to a medium composed of at least an alcohol maintained at a temperature of 100 ° C. or higher and mixing. By this step, the mixture (m) is easily made.

When a mixture (n) consisting of the zinc source and the monocarboxylic acid or a mixture thereof and a metal (M) compound is added to a medium comprising at least an alcohol, the mixture (n) is a solution. Is preferred. When the mixture (n) is a solution, the zinc source and the monocarboxylic acid, or the zinc source and the metal (M) compound are compatible, or the zinc source and the metal (M) compound are dissolved in a highly compatible solvent. Is desirable. As a solvent used for this purpose, a zinc source and a monocarboxylic acid or a metal (M) compound and a zinc source can be easily dissolved at a temperature from room temperature to about 100 ° C. From the viewpoint of high solubility, water, alcohols, ketones, and esters are preferred. The alcohols here include all the alcohols described above.

In the course of the conversion of the zinc source to zinc oxide which is X-ray diffraction crystalline, one or more zinc oxide precursors, which may include a metal (M) And may not be included). For example, there is a case where zinc oxide or the like is used as a zinc source. The zinc oxide precursor means an ion or a compound containing at least a zinc atom other than zinc oxide, such as zinc (hydrate) ion (Zn ²⁺ ), a polynuclear hydroxide ion of zinc, and zinc. A state in which some or all of the above ions are chelated by a β-dicarbonyl compound such as acetylacetone or a compound capable of forming a chelate such as lactic acid, ethylene glycol, ethanolamine, or the like; (basic) zinc acetate; Basic) zinc salicylate, (basic)
Examples thereof include (basic) carboxylate salts such as zinc lactate. The 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 an alcohol is also included.

In the process in which the zinc source and the metal (M) compound used as the raw materials in the mixture (m) are converted into zinc oxide-based fine particles, the monocarboxylic acid present in the mixture (m) changes. Otherwise, a part or all of the monocarboxylic acid causes an esterification reaction with a part or all of the alcohol in the mixture (m) to produce an ester compound.

The mixture (m) may be any mixture obtained by mixing the zinc source, the monocarboxylic acid, the alcohol, and the metal (M) compound as essential components. Depending on the components, components other than the four components, for example, water, ketones, esters, (cyclo) paraffins, ethers, organic solvents such as aromatic compounds, components such as additives described below, or zinc and metal Metal components other than (M), for example, inorganic salts such as metal acetates, nitrates and chlorides, and organic metal alkoxides such as metal alkoxides may be contained. However, the alkali metal and the alkaline earth metal may reduce the heat ray cut function and conductivity of the fine particles, and are preferably 1/10 or less of the number of atoms of the metal (M) in the mixture (m). 1/100
It is more preferred that: Water and organic solvents are usually contained as solvent components.

The state of mutual existence of the four components and the form of each component in the mixture (m) are not particularly limited. For example, when the zinc source is present, for example, the zinc source and / or the metal (M) compound is dissolved as it is using the alcohol and / or the water and the organic solvent as a solvent component. It is in a state of being dissolved after being changed or in a state of being dispersed in a colloidal, emulsified or suspended state.

Accordingly, the state of the mixture (m) is not particularly limited, and there is no problem, for example, whether it is liquid, sol, emulsion, or suspension. Mixture (m)
Is prepared by mixing the respective components within the above-mentioned 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 diameter of single particles is controlled in the range of 0.001 to 10 μm, the first mixture (n) comprising the zinc source and a monocarboxylic acid is used. Is added to the alcohol-containing solution while heating to prepare a mixture (m), from the viewpoint of obtaining practical productivity.

The preparation method at this time will be described below. As a method of adding the mixture (n), for example, a method of adding and mixing the mixture (n) at a time, a method of mixing the mixture (n) by dropping it on or in an alcohol-containing solution, or a method of adding the mixture (n) ) Can be adopted. The addition and mixing of the mixture (n) may be performed at normal pressure, increased pressure or reduced pressure, but is preferably performed at normal pressure in terms of production cost. When the addition and mixing are performed under normal pressure, when it is desired to obtain a zinc oxide-based fine particle dispersion having a high uniformity in particle diameter, shape, and the like, and a controlled dispersion / aggregation state, the alcohol-containing mixture is added during the addition and mixing. It is preferable to maintain 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 lower 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, agitation becomes impossible and uniform mixing is not achieved, or heat transfer becomes insufficient at the next step, that is, heating, and a problem such as a temperature distribution is caused. It is difficult not only to obtain zinc oxide-based fine particles having a uniform particle diameter and particle shape, but also 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 temperatures of these optimum temperatures differ 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) remains outside the system by evaporation. Sometimes obtained, the mixture obtained in this way 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 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 the raw material of the mixture (n) is 0.5 to 5 in terms of a molar ratio to Zn atoms in the zinc source.
It is preferably in the range of 0 moles.

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 the alcohol contained in the alcohol-containing solution is not particularly limited. However, in order to carry out the reaction of forming zinc oxide-based fine particles during heating in a short time, the mixture (m) of the alcohol is used. 1 to 100 in terms of molar ratio to Zn atoms derived from the contained zinc source
A 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.

The mixture (m) obtained as described above
Is heated to obtain a dispersion containing zinc oxide-based fine particles at a high yield. The heating temperature is not particularly limited, and it is needless to say that the heating is performed at a temperature not lower than the temperature at which crystalline zinc oxide is precipitated. The heating temperature and the heating time need to be selected from the comprehensive viewpoint including the initial composition of the mixture (m) and the various parameters described above, not uniquely determined according to the morphology. In particular, the average particle diameter of a single particle is 0.001 to 1
In order to obtain a dispersion of zinc oxide-based fine particles controlled in the range of 0 μm with practical productivity, it is preferable to perform the heating at a heating temperature of 100 ° C. or more, particularly 100 ° C. or more and 300 ° C. or less.

In this case, for example, the mixture (n) is
When the 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 processed. When the mixture (n) is obtained by adding and mixing the mixture (n) with alcohol at a temperature lower than 100 ° C., the mixture may be heated to a temperature of 100 ° C. or higher and then subjected to a heat treatment. By setting the heating temperature of the mixture (m) to 100 ° C. or higher, the composition of the reaction system including the rate and amount of evaporating and removing excess or unnecessary components is strictly controlled 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 obtained fine particles.

In the heating step for obtaining the dispersion, a part or all of the components other than the above-mentioned components, that is, alcohol, the ester compound produced by heating, or the solvent component if necessary in the mixture. 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.

In the case where water is present in the mixture (m), it is preferable that the concentration of free water in the dispersion is preferably in order to be converted into zinc oxide type fine particles in the heating step. Is preferably 5% by weight or less, more preferably 1% by weight or less. The reason is that when the water concentration exceeds this range, depending on the type of other components such as alcohol contained in the dispersion, the crystallinity of the zinc oxide-based fine particles is lowered and the above-mentioned function is not sufficiently exhibited. Because there is.

As the (final) composition in the formed zinc oxide-based fine particle dispersion, the amount of the monocarboxylic acid is based on the total amount in terms of zinc atoms contained in the formed dispersion. It is preferred that the amount be 0.5 mole or less. The reason is that, when the molar ratio exceeds 0.5 times, 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 in terms of zinc atoms contained in the resulting dispersion, heating is performed. In the process,
At least the excess must 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 to obtain secondary particles obtained by assembling the primary particles, it is effective to coexist a lactic acid source when the temperature is maintained at 100 ° C. or higher. It is. Lactic acid source 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; lactate esters such as methyl lactate, ethyl lactate, and n-butyl lactate that can produce lactic acid by hydrolysis, etc .; May be used, or
Two or more may be used in combination.

The amount of the lactic acid source to be 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 above range, zinc oxide crystals cannot be obtained because the coexistence effect of lactic acid is insufficient. On the other hand, above the above range, the precipitation reaction of the zinc oxide crystals hardly occurs, so that the desired fine particles cannot be obtained. 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. The molar ratio of lactic acid is 0.001 to
0.1 is preferred.

The addition of the lactic acid source is, for example, as follows. When lactic acid (CH ₃ CH (OH) COOH) and / or lactic acid ester is used, the above steps I-II
Any method of I may be used, and a direct addition method or a method of adding a solution dissolved in a solvent (for example, alcohol) can be adopted. The latter addition method is preferable particularly when the lactic acid source is added in Step III, because lactic acid is easily diffused quickly. If a metal lactate is used, it can be at any time in steps I-III above, and is preferably dissolved in step (I) with or as a zinc source in mixture (n). For example, a zinc source powder and a metal lactate powder are added to a solution containing a monocarboxylic acid, mixed, and stirred to prepare a uniform solution. At this time, stirring while heating to increase the dissolution rate and solubility of each powder is preferably adopted in that 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 are oriented with their tips outward. In some cases, 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 generated single particles are flaky (anisotropic), for example, having a length of 1.0 to 5.0. Long diameter /
Minor axis), flatness of 2 to 200 (major axis / thickness), major axis 5
It is 1000 nm, which is excellent in light diffusion transmittance and is preferable. The major axis is the longest length of the triaxial diameters measured for the particle, and the thickness is the smaller of the width and height of the triaxial diameter (the particle diameter of 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 fine particles of the present invention. The amount of the polymer to be 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 ratio is less than the above range, composite particles are difficult to be obtained. If the ratio is above the range, the precipitation reaction of zinc oxide crystals may be difficult to occur. Of the composite particles, having the above-mentioned multilayer structure, in order to obtain zinc oxide-based fine particles having good particle shape and particle size and good dispersibility, depending 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 zinc oxide equivalent.

In the process of the present invention, the polymer is added in any one or more of the above steps. The addition of the polymer is performed at any time before the zinc oxide-based fine particles are precipitated. 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 timing of adding the polymer may be any of the above steps as long as it is a stage before the zinc oxide-based fine particles are generated.

The polymer is preferably dissolved in the alcohol used for the medium in advance or dissolved in any solvent and added to the reaction system because it can quickly 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. For example, alcohols (described above),
Organic solvents such as aliphatic and aromatic carboxylic acids, aliphatic and aromatic carboxylic esters, ketones, ethers, ether esters, aliphatic and aromatic hydrocarbons, halogenated hydrocarbons; water; minerals Oil; vegetable oil;
Wax oil; at least one selected from the group consisting of silicone oils.

The mixture (m) may be any mixture obtained by mixing four components of zinc, monocarboxylic acid, alcohol and metal (M) as essential components, and is a step before zinc oxide-based fine particles are formed. The polymer is added at. The mixture (m) containing the polymer is heated at a temperature of 100 ° C. or more, preferably 100 to 300 ° C., more preferably 150 to 200 ° C. for 0.1 to 30 hours, preferably 0.5 to 30 hours.
By maintaining for 10 hours, the zinc oxide-based fine particles of the present invention according to the type and composition ratio of the raw material can be obtained as zinc oxide-based crystal-polymer composite particles with practical productivity. That is, the zinc dissolved or dispersed in the medium is converted into X-ray diffraction crystalline zinc oxide by maintaining the second mixture at a temperature within the above range and for a time within the above range. . Since the polymer is also dissolved or dispersed in the medium, zinc oxide crystal nuclei are precipitated, and the polymer is complexed in the course of crystallization, whereby a dispersion containing zinc oxide-polymer composite particles is formed. can get. The type of polymer to be used, the type of raw material such as the type of alcohol contained in the medium, the composition of the raw material, the composition and temperature of the reaction solution when the composite particles are generated based on the temperature history until the composite particles are generated, etc. By controlling the particle size, it is possible to control the internal structure, particle shape and particle diameter of the composite particles, the particle diameter of the contained single particles (metal oxide coprecipitate), and the like.

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 diameter of 0.001 to 10 μm and a coefficient of variation of the particle diameter of 30% or less is provided. A dispersion is obtained in which the system fine particles are dispersed and contained in the range of 1 to 80% by weight and the alcohol and / or the ester compound and / or the organic solvent are used as a solvent. Furthermore, the particle size of a single zinc oxide-based fine particle finally obtained,
For the purpose of controlling the particle shape, the dispersed state or the higher-order structure and / or the polarity or composition of the fine particle surface, a specific additive can be made to coexist in the heating step. 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-based fine particles which are highly uniform in the particle diameter and particle shape of a single particle, a carboxyl group, an amino group, an imino group, an amide group,
Amide bond, imide group, imide bond, ureido group, ureylene bond, isocyanato group, sulfonic acid group, sulfate group,
A compound having at least one kind of atomic group 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, having a molecular weight of less than 1,000, and / or Alternatively, a so-called chelating agent (polydentate ligand) which forms a chelate compound by polydentate coordination with zinc ions is preferably used as an additive to coexist at the time of heat treatment.

Examples of the additives include the above-mentioned carboxyl group-containing compounds including long-chain saturated fatty acids such as caprylic acid, lauric acid, myristic acid, palmitic acid and stearic acid, 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 acid, 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 iminoethers; dicarboxylic acid ureides such as parabanic acid, alloxan, barbituric acid and dialluric acid; ureido acids such as oxalic acid and malonuric acid; uric acid Ureide group-containing compounds and derivatives such as β-aldehyde acid ureides such as uracil, uracil and the like, α-oxyacid ureides such as 5-methylhydantoin; urethane compounds such as ethyl carbamate and N-nitrosated compounds thereof; Chlorase Derivatives such as chilled products; isocyanato group-containing compounds such as tolylene diisocyanate, diisocyanyl diphenylmethane, hexamethylene diisocyanate, isobutyl isocyanate, and phenyl isocyanate; 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 and pentaerythritol tetraglycidyl ether; aliphatic and aromatic diglycidyl esters such as diglycidyl adipate; And other compounds containing an epoxy group such as resorcinol diglycidyl ether, bisphenol A diglycidyl ether, and 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-
Various coupling agents such as titanate coupling agents such as aminoethylaminoethyl) titanate and partial hydrolysates thereof; other than the above coupling agents, for example, tetraethoxytitanium, tetrabutoxytitanium,
Diethyldiethoxytitanium, tetrabutoxytitanium, tetramethoxyzirconium, tetrabutoxyzirconium, hexaethoxytungsten, di-n-butoxymanganese, diisopropoxycobalt, diethoxynickel, di-n-butoxynickel, triethoxysilanetan, triethoxy Yttrium, diethoxy copper, di-n
-Butoxycopper, pentaethoxyniobium, penta-n-butoxyniobium, pentaethoxytantalum, penta-n-
Organometallic compounds containing a metal hydroxyl group and / or a metal alkoxy group typified by metal alkoxides such as butoxytantalum, triethoxyiron, and tri-n-butoxyiron, derivatives thereof, and specific examples of the derivatives include these organic compounds. Metal compounds alone or in mixture (partly)
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], an acid phosphate such as methyl acid phosphate, propyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, bis-2-ethylhexyl phosphate, diisodecyl phosphate, and a phosphorous acid such as trimethyl phosphite. Organic phosphorus compounds such as thiophosphates such as acid esters, dimethyldithiophosphoric acid and diisopropyldithiophosphoric acid; at least a primary amino group and a secondary amino group in the molecule Organopolysiloxanes having a molecular weight of less than 1,000 containing the above-mentioned atomic groups such as amino groups such as tertiary amino group, quaternary ammonium group, carboxyl group, sulfonic acid group, phosphoric acid group, hydroxyl group and epoxy group; sodium lauryl sulfate , Dodecylbenzenesulfonic acid (sodium), anionic surfactants such as sodium polyoxyethylene lauryl ether sulfate, sodium dialkyl sulfosuccinate, calcium stearate, polyoxyethylene lauryl ether, polyoxyethylene alkylamine, polyethylene glycol monolaurate, Nonionic surfactants such as glycerol monostearate; cationic surfactants such as lauryl dimethylamine and stearyltrimethylammonium chloride; lauryl betaine; 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) which form a chelate compound by polydentate coordination with zinc ions include β-diketones such as acetylacetone, ethyl acetoacetate and benzoylacetone, ethylenediamine, and the like. Dimethylglyoxime, benzyldioxime, cyclohexane 1,2-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, depending on the type and amount of the additive, the size and shape of the obtained single particles of the zinc oxide-based fine particles, the dispersion state and higher order structure of the single particles, the surface polarity,
The surface composition and the like 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 can be used in a polar solvent 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 or octadecylamine is used as an additive, the size of primary particles can be reduced. Thus, zinc oxide-based fine particles having a uniform shape and excellent in dispersibility of primary particles in a low-polar solvent such as toluene or a non-polar solvent can be obtained.

The amount of the above-mentioned additive is not particularly limited, but is usually 0.1% or more and 80% or less as a weight ratio of the additive to zinc oxide contained in the zinc oxide-based 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-based fine particles may not be obtained. The above-mentioned additives can be used alone or as a mixture. The method of adding the additives is not particularly limited, and may be appropriately selected according to the type of the additive, the timing of addition, and the like. For example, in the case of adding during heating, a method of adding the additive directly or dissolved and / or diluted in an arbitrary solvent such as alcohol is exemplified. Is preferred because it is easily diffused quickly and the effect of addition is easily exerted sufficiently.

Next, in the above-mentioned present invention, the preferred embodiment for obtaining zinc oxide-based fine particles in which the average particle diameter 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 performed under two or three conditions, more preferably under conditions that satisfy all of (I) to (IV).

(I) As a zinc source, a source mainly containing at least one selected from the group consisting of zinc oxide, zinc hydroxide and zinc acetate among the above-mentioned zinc or a compound thereof, particularly preferably oxide It is mainly composed of zinc and / or zinc hydroxide. The reason is that zinc oxide, zinc hydroxide, and zinc acetate have a thickness of 0.001 to 0.1 μm because they do not substantially contain impurities that inhibit the reaction of forming zinc oxide-based fine particles in the heating process. 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 available at a low price, but also in addition to being able to arbitrarily select the type of the carboxyl group-containing compound, these This is because the use of the above raw material makes it particularly easy to obtain fine particles having the above-mentioned particle size range.

(II) As the monocarboxylic acid, the monocarboxylic acid is a saturated fatty acid having a boiling point at normal pressure of 200 ° C. or less. Specifically, formic acid, acetic acid, propionic acid, butyric acid, and isobutyric acid are preferred, and acetic acid is particularly preferred. The reason is that the content of the carboxyl group in the reaction system is easily controlled in the process of preparing the mixture and in the process of heating, and therefore the particle diameter is easily controlled strictly in a fine region. Further, it is preferable to use the saturated fatty acid in a range of 80 mol% or more based on 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-mentioned range, but the content of the monocarboxylic acid in the mixture (n) is limited to Zn 2.2 to 1 in terms of molar ratio to atoms
The range of 0 moles is particularly preferred in that fine particles having suppressed secondary aggregation and excellent dispersibility can be obtained. (III) As a method for preparing the mixture (m), a mixture (n ) Is continuously or intermittently dropped into an 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. Further, 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 is compatible with or dissolved in a solvent having high compatibility with these. As a solvent used for this purpose, a zinc source and a monocarboxylic acid described later can be easily dissolved by heating from room temperature to about 100 ° C., and water and alcohols are highly compatible with alcoholic solvents. , 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 to 300 ° C, particularly preferably 150 ° C to 3
This is performed at a temperature of 00 ° C. or less. By heating the mixture (m), ZnO crystals are precipitated, and when the fine particles of the present invention are formed, the concentration in terms of ZnO with respect to the mixture (m) is 0.5 wt% or more and 20 wt% or less, and 2.0 wt% or more. 1
When the amount is less than 0% by weight, it is preferable because the average particle diameter of the primary particles is in the range of 0.001 to 0.1 μm, and fine particles in which secondary aggregation is suppressed are easily obtained.

Further, the average particle size is 0.001 to 0.1.
An effective method for controlling the particle size and shape more uniformly, controlling the surface state such as hydrophilicity / hydrophobicity, and controlling the dispersion / aggregation state of the zinc oxide-based fine particles in the range of μm. Is described below. Average particle size 0.001
In a preferred method for producing a zinc oxide-based fine particle in the range of 0.1 μm, by using the above-described additive in the same manner as described above, control of the shape of the particle, the dispersed state and the higher-order structure of the particle, the surface polarity, and the like. Zinc oxide-based fine particles can be obtained. When the primary particles have a uniform particle diameter distribution, the average particle diameter is substantially in the above range, and zinc oxide-based fine particles with suppressed secondary aggregation are obtained, zinc or a compound thereof used as a raw material Is at least one member selected from the group consisting of zinc oxide, zinc hydroxide and zinc acetate, and is a basic zinc carbonate and / or a zinc salt of a monocarboxylic acid having a boiling point at normal pressure higher than the heating temperature. Is preferably used as well. 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.
When the proportion is less than 0.01%, the effect of using the auxiliary component in combination is insufficient, while when it exceeds 20%, zinc oxide having high crystallinity may not be obtained.

As another method of obtaining zinc oxide-based fine particles having a uniform shape and a uniform 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) prior to 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 that generates carbon dioxide or carbonate ions under heating conditions, such as zinc carbonate.

In the production method of the present invention, in particular, according to the production conditions described above, the particle shape, surface state, dispersion / aggregation state and the like are controlled within 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 is obtained. The dispersion of the zinc oxide-based fine particles obtained in the present invention can be used as it is, but if necessary, a zinc oxide-based fine particle powder, a paint containing the zinc oxide-based fine particles, and another solvent by solvent replacement. It can be easily converted to a dispersion in which zinc oxide-based fine particles are dispersed.

As a method for obtaining the powder of the zinc oxide-based fine particles obtained in the present invention, the fine particles are separated by subjecting the dispersion to a conventional method such as filtration, centrifugation, and solvent evaporation, and then dried. Or firing as needed. Above all, a powdering method by a solvent evaporation method using a vacuum flash evaporator after performing a concentration operation of a dispersion as necessary is a method for suppressing secondary aggregation of fine particles which tends to occur in a drying process. Therefore, it is preferable as a powdering method of zinc oxide type fine particles having excellent dispersibility.

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

A major feature of the present invention is that zinc oxide-based fine particles and a heat ray absorbent are used in combination. In the process of producing a composition such as a coating composition or a resin composition, zinc oxide-based fine particles and a heat ray absorbent are used. When both are present, the combined effect described later can be better obtained. The composite powder or the composite powder dispersion of the zinc oxide-based fine particles and the heat ray absorbent, such as a powder obtained by previously surface-treating (adsorbing to the surface, etc.) the zinc oxide-based fine particles with a heat ray absorbent such as a phthalocyanine compound, is also available. Within the scope of the invention.

The method of surface-treating the zinc oxide-based fine particles with a heat-ray absorbing agent such as a phthalocyanine compound is, for example, mixing the zinc oxide-based 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 under heating. There is a method of stirring under. In order to perform the surface treatment uniformly,
The solvent is preferably a solvent in which the zinc oxide-based fine particles are easily dispersed. For example, alcohols such as ethylene glycol monoalkyl ethers such as ethylene glycol monobutyl ether and n-butanol; ketones such as methyl ethyl ketone; esters such as butyl acetate; water;

Preferred embodiments of the composition of the present invention are as follows. (1) A composition for shielding ultraviolet rays and heat rays, comprising fine particles of a metal oxide coprecipitate comprising 80 to 99.9 atomic% of zinc and the balance of a group IIIB metal element, and a heat ray absorber. (2) The composition for shielding ultraviolet rays and heat rays according to the above (1), wherein the heat ray absorbent is a phthalocyanine compound. (3) The ultraviolet and heat ray shielding composition according to the above (1) or (2), 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 fine particles have an average crystallite diameter of 0.001 to 0.0.
The composition for shielding ultraviolet rays and heat rays according to any one of (1) to (4), which has a thickness of 5 μm. (6) The fine particles have an average dispersed particle diameter of 0.001 to 0.1.
The composition for shielding ultraviolet rays and heat rays according to any one of the above (1) to (5), which is 1 μm. (7) The fine particles are prepared by mixing a zinc source and a monocarboxylic acid in a medium comprising at least an alcohol, and
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 the above (1) to (6), which is fine particles produced by the method of maintaining the above temperature. (8) The ultraviolet and heat ray shielding composition according to (7), wherein the group IIIB metal element is indium and / or aluminum. (9) The method comprises adding a mixture obtained by mixing a zinc source and a monocarboxylic acid in water to a medium comprising at least an alcohol heated to 100 ° C. or higher,
The ultraviolet and heat ray shielding composition according to the above (7) or (8), further comprising a step of evaporating and removing at least a part of the water and / or the monocarboxylic acid. (10) The ultraviolet and heat ray shielding composition according to any one 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 one 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), wherein the temperature is kept at 100 ° C. or higher in the presence of carbon dioxide or a carbonic acid source. (13) The above-mentioned temperature holding of 100 ° C. or more is carried out by adding a carboxyl group, amino group, quaternary ammonium group, amide group, imide bond, (alcoholic, phenolic) hydroxyl group, carboxylic acid ester bond, urethane group, urethane in the molecule. A bond, a ureido group, a ureylene bond, an isocyanate group, an epoxy group, a phosphoric acid group, a metal hydroxyl group, a metal alkoxy group, at least one atomic group selected from the group consisting of a sulfonic acid group, and a molecular weight of 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 co-presence of an additive compound. (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 based on the total weight of solids of the three. The heat ray absorbent 0.0005 to 2
0% by weight, 0.1 to 99.9% by weight of the binder component
The ultraviolet and heat ray shielding composition according to any one of the above (3) to (13), which is a coating composition having a ratio of: (15) The ultraviolet and heat ray shielding composition according to the above (14), wherein the total weight of solids of the fine particles, the heat ray absorbent, and the binder component is 1 to 80% by weight, and the balance is a solvent. (16) The ultraviolet and heat ray shielding composition according to the above (15), wherein the amount of the heat ray absorbent is 0.05 to 30% by weight in terms of the total weight ratio of solids 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 based on the total weight of the solids of the three.
The above-mentioned (3) to (10), wherein the heat ray absorbent has a ratio of 0.0005 to 20% by weight and the resin has a ratio of 0.1 to 99.9% by weight.
The composition for shielding ultraviolet rays and heat rays according to any one of (13). (18) The ultraviolet ray and heat ray shielding composition according to the above (17), wherein the amount of the heat ray absorbent is 0.05 to 30% by weight in terms of the total weight ratio of solids to the fine particles. [Coated Article] The coated article of the present invention comprises a substrate and a coating film formed on the surface of the substrate. The substrate is at least one selected from the group consisting of a resin molded body, glass and paper. The coating 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 in the case of a coating composition to the surface of a substrate.

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

The coating composition may be any substrate, for example, a plastic film or sheet such as a polyester film; a fiber such as a natural fiber or a synthetic fiber; By coating and drying on a translucent synthetic resin plate; glass; paper or the like, a film containing zinc oxide-based fine particles and a heat ray absorbent can be formed.

In order to form a film, the substrate may be heated at a temperature lower than the deformation temperature of the substrate, if necessary. Heating is performed, for example, by using an inorganic binder such as silicon alkoxide as a binder component and sufficiently proceeding a condensation reaction between molecules of the binder component to form a tough film, or a thermosetting resin as a binder component. A resin having two or more active hydrogen atoms such as polyether and / or polyester in at least one part of a binder component and an isocyanate by forming a cured film by sufficiently promoting the curing reaction of the thermosetting resin using When a crosslinking reaction is performed, for example, when it is desired to finally form a polyurethane film using a crosslinking agent such as the above, the crosslinking reaction is efficiently performed.

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

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

Examples of the coating composition used to make coated paper include those containing a solvent among the above-mentioned coating compositions of the present invention. Examples of the dispersion medium of the dispersion used to make the coated paper include the above-mentioned solvents that can be used in the coating composition of the present invention. Depending on the intended use, other additives such as pigments, water-proofing agents, lubricants, defoamers, flow modifiers, and water retention agents may be mixed in the coating composition.

When making coated paper, the composition of the coating composition containing the zinc oxide-based fine particles and the heat ray absorbent, the solvent used, the type of binder, and the method of preparing these, etc., are the same as those of the conventionally known raw materials. It can be used and may be prepared according to a conventionally known preparation method. Film-laminated paper refers to one obtained by attaching a polymer film containing zinc oxide-based fine particles and a heat ray absorbent in a dispersed manner to a paper substrate. As the polymer film, a 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 having excellent appearance. The use of the obtained paper is arbitrary, and can be used for various uses including, for example, art paper and wallpaper. The coating film in the coated product of the present invention contains zinc oxide-based fine particles, a binder component for binding the zinc oxide-based fine particles, and a heat ray absorbent. 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 with respect to the total weight of the solid contents of these three components.
% By weight, 0.0005 to 20% by weight of a heat ray absorbent, and 0.1 to 99.9% by weight of a binder component.
The ratio is 10 to 79.9% by weight of zinc oxide-based 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 ratio of the zinc oxide-based fine particles is less than the above range, in order to obtain sufficient ultraviolet shielding properties, the thickness of the coating film must be increased, and if it exceeds, the dispersibility of the fine particles is reduced and the visible light of the coating film is reduced. Transparency may decrease. If the ratio of the heat ray absorbent is lower than the above range, it may be difficult to obtain sufficient heat ray shielding properties. If the ratio is higher than that, the transparency of the coating film to visible light may be reduced or the price may be increased. When the proportion of the binder component as the dispersion medium is below the above range, the dispersibility of the fine particles is reduced, the transparency of the coating film to visible light is reduced, and the physical properties of the coating film such as mechanical properties and chemical resistance are reduced. In some cases, the thickness of the coating film must be increased in order to obtain a sufficient ultraviolet shielding property.

The blending amounts of the zinc oxide-based fine particles and the heat ray absorbent in the coating film differ depending on the required ability to block ultraviolet rays and heat rays, transparency in the visible region, the thickness of the coating film, and the shape of the coating film. In terms of the content per unit area of the coating film or the weight in the projected area from the normal direction (upward), the zinc oxide fine particles preferably have a range of 1 to 10 g / m ² , and 1.5 to 6 g / m ^2. The range of m ² is more preferable; for the heat ray absorber, 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 molded article used as the substrate is, for example, at least one selected from the group consisting of a plate, a sheet, a film and a fiber. The substrate may be a transparent substrate or a translucent substrate. Preferred embodiments of the coated product of the present invention are as follows. (1) at least one substrate selected from the group consisting of a resin molded body, glass and paper, and fine particles of a metal oxide coprecipitate comprising 80 to 99.9 atomic% of zinc and the balance of a group IIIB metal element; A heat ray absorbent, comprising a dispersion medium, comprising a composition in which the dispersion medium is a binder component and disperses the fine particles and the heat ray absorbent,
And a coating film formed on the surface of the base material. (2) the heat ray absorbent is a phthalocyanine compound,
The coated product of the above (1). (3) The coated product according to the above (1) or (2), wherein the group IIIB metal element is indium and / or aluminum. (4) The fine particles have an average crystallite diameter of 0.001 to 0.0
The coated product according to any one of the above (1) to (3), which is 5 μm. (5) The fine particles have an average dispersed particle diameter of 0.001 to 0.1.
The coated product according to the above (4), which is 1 μm. (6) The fine particles are prepared by mixing a zinc source and a monocarboxylic acid in a medium comprising at least an alcohol, and
100 ° C. in the presence of a compound containing a group IIIB metal element
The coated product according to any one of the above (1) to (5), which is a fine particle generated by the method of maintaining the temperature at the above temperature. (7) The method comprises adding a mixture obtained by mixing a zinc source and a monocarboxylic acid in water to a medium comprising at least an alcohol heated to 100 ° C. or higher,
The coated article according to the above (6), further comprising a step of evaporating and removing at least a part of the water and / or the monocarboxylic acid. (8) The coated product according to (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) above, 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 the above (6) to (9), wherein the holding of the temperature of 100 ° C. or higher is performed in the coexistence of a carbon dioxide or carbon dioxide source. (11) The above-mentioned temperature holding of 100 ° C. or more is carried out by adding a carboxyl group, amino group, quaternary ammonium group, amide group, imide bond, (alcoholic, phenolic) hydroxyl group, carboxylic acid ester bond, urethane group, urethane in the molecule. A bond, ureido group, ureylene bond, isocyanate group, epoxy group, phosphoric acid group, metal hydroxyl group, metal alkoxy group, at least one atomic group selected from the group consisting of sulfonic acid group, and a molecular weight of less than 1000 The coated product according to any one of the above (6) to (9), which is carried out in the coexistence of an additive compound. (12) 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, 0.0005 to 20% of the heat ray absorbent based on the total weight of the solid content of the three. % By weight of the binder component 0.1
The coated product according to any one of the above (1) to (11), which has a ratio of 〜99.9 wt%. (13) The coated product according to the above (12), wherein the amount of the heat ray absorbent is 0.05 to 30% by weight in terms of a total weight ratio of solids to the fine particles. (14) The coated article according to any one of the above (1) to (13), wherein the substrate is one selected from the group consisting of a resin molded body, glass and paper. (15) The heat-ray absorbing agent may be used in a range of 1 to 10 g / m ² in terms of the content of the coating film per unit area or the weight in the projected area from the normal direction (upward). In the range of 0.005 to 2.4 g / m ² . [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.

In the case where the composition of the present invention is a resin molded product, it has already been described in the description of the composition of the present invention, and the description is omitted here. The amount of each of the zinc oxide-based fine particles and the phthalocyanine compound in the molded article depends on the required ultraviolet / heat ray shielding ability, transparency in the visible range, the thickness of the molded article, and the shape of the molded article.
For example, when expressed in terms of the content per unit area of the molded article or the weight in the projected area from the normal direction (upward), the zinc oxide-based fine particles preferably have a range of 1 to 10 g / m ² , and 1.5 to 6 g. / range of m ² is more preferable; a phthalocyanine compound, preferably in the range of 0.005～2.4G / m ^2, the range of 0.01～1.2G / m ² is more preferable.

When the composition of the present invention is a resin composition or 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. The method for obtaining a molded article having a desired shape from the resin composition of the present invention is not particularly limited, and a conventionally known method can be employed as it is. An example will be described below.

When it is desired to obtain a polycarbonate resin plate containing zinc oxide-based 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 obtain a resin. After obtaining a composition in which the zinc oxide-based fine particles and the heat ray absorbent are uniformly mixed, and then continuously or once pelletized, injection molding, extrusion molding, compression molding, etc., to obtain a flat or curved surface A method of processing into a plate shape is employed. Of course, it is also possible to form the sheet into a desired shape such as a corrugated sheet by further processing the flat sheet. Resin plates such as an acrylic resin plate, a vinyl chloride resin plate, and a polyester resin plate can be obtained in the same manner.

When it is desired to obtain a fiber such as a nylon fiber or a polyester fiber or a film such as a polyolefin film, a polyamide film, or a polyester film in which zinc oxide-based fine particles and a heat ray absorbent are dispersed, for example, the zinc oxide-based fine particle powder is used. After melt-kneading a resin pellet or powder with a heat ray absorber to obtain a composition in which the fine particles and the heat ray absorber are uniformly mixed in the resin, continuously or once pelletizing as it is, melt spinning, etc. A conventionally known (stretched) film manufacturing method in which a fiber is formed into a sheet by extrusion and then subjected to uniaxial or biaxial stretching as necessary.

In order to obtain a polyester fiber or a polyester film in which zinc oxide-based fine particles and a heat ray absorbent are dispersed, the following other known methods can be adopted.
That is, as a method for obtaining a polyester fiber, zinc oxide-based fine particles and a heat ray absorbent are added, for example, in an amount of 0.1 to 50 wt. % By adding and mixing a dispersion obtained by dispersing in glycol at a rate of% to complete the polymerization reaction of the polyester, thereby obtaining a polyester polymer in which zinc oxide-based fine particles and a heat ray absorbent are dispersed and contained in 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-based fine particles and a heat ray absorbent are dispersed and contained in a polyester is obtained in the same manner, and extruded into a sheet. If necessary, a method of performing a stretching treatment in a uniaxial or biaxial direction can be adopted. Preferred embodiments of the resin molded product of the present invention are as follows. (1) Fine particles of a metal oxide coprecipitate comprising 80 to 99.9 atomic% of zinc and the balance of a group IIIB metal element, a heat ray absorbent, and a dispersion medium, wherein the dispersion medium is a resin and the fine particles And a resin molded article in which the composition for shielding ultraviolet rays and heat rays, which disperses the heat ray absorbent, is formed into a shape selected from the group consisting of plates, sheets, films and fibers. (2) the heat ray absorbent is a phthalocyanine compound,
The resin molded article of the above (1). (3) The resin molded article according to (1) or (2), wherein the group IIIB metal element is indium and / or aluminum. (4) The fine particles have an average crystallite diameter of 0.001 to 0.0
The resin molded product according to any one of the above (1) to (3), which has a thickness of 5 μm. (5) The fine particles have an average dispersed particle diameter of 0.001 to 0.1.
The resin molded article according to the above (4), which is 1 μm. (6) The fine particles are prepared by mixing a zinc source and a monocarboxylic acid in a medium comprising at least an alcohol, and
100 ° C. in the presence of a compound containing a group IIIB metal element
The resin molded product according to any one of the above (1) to (5), which is fine particles produced by the method of maintaining the temperature at the above. (7) The method comprises adding a mixture obtained by mixing a zinc source and a monocarboxylic acid in water to a medium comprising at least an alcohol heated to 100 ° C. or higher,
The resin molded article according to the above (6), further comprising a step of evaporating and removing at least a part of the water and / or the monocarboxylic acid. (8) The resin molded article according to (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 resin molded article according to any one of (6) to (8) above, 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 article according to any one of (6) to (9), wherein the holding of the temperature of 100 ° C. or higher is performed in the presence of carbon dioxide or a carbonic acid source. (11) The above-mentioned temperature holding of 100 ° C. or more is carried out by adding a carboxyl group, amino group, quaternary ammonium group, amide group, imide bond, (alcoholic, phenolic) hydroxyl group, carboxylic acid ester bond, urethane group, urethane in the molecule. A bond, ureido group, ureylene bond, isocyanate group, epoxy group, phosphoric acid group, metal hydroxyl group, metal alkoxy group, at least one atomic group selected from the group consisting of sulfonic acid group, and a molecular weight of less than 1000 The resin molded product according to any one of the above (6) to (9), which is carried out in the coexistence of the additional compound of (1). (12) The amounts of the fine particles, the heat ray absorbent, and the resin are 0.01 to 99% by weight of the fine particles, 0.0005% of the heat ray absorbent, based on the total weight of the solids of the three.
The resin molded product according to any one of the above (1) to (11), wherein the proportion of the resin is 0.1 to 20% by weight and the resin is 0.1 to 99.9% by weight. (13) The resin molded article according to the above (12), wherein the amount of the heat ray absorbent is 0.05 to 30% by weight in terms of a total weight ratio of solids to the fine particles. (14) Content per unit area or normal direction (upward)
From 1 to 10 g / weight of 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 article according to any one of (1) to (13) above.

[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 the examples and comparative examples were measured and evaluated by the following methods. (Physical Properties of Zinc Oxide-Based Fine Particles) (Crystallinity) Evaluated by powder X-ray diffraction measurement.

(Average Crystallite Diameter) A powder sample was subjected to powder X-ray diffraction measurement, and a Scherrer (Sc) was determined from the diffraction angle θ and the diffraction line width β.
herr). Scherrer
Is as follows. D = Kλ / βcos θ (where D [nm]: crystallite diameter, K: Scherrer constant (apparatus constant), λ [nm]: wavelength of X-ray, β [radian]: based only on crystallite size Diffraction line width, θ: diffraction angle.) (Average dispersed particle diameter)
wt% and added to n-butanol and stirred for 2 hours, and then a particle size analyzer by dynamic light scattering method (NICOMP commercially available from Nozaki Sangyo Co., Ltd.)
(Model 370 was used) to obtain a number-based average particle diameter, which was defined as an average dispersed particle diameter.

When 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 as to have a fine particle concentration of 1% by weight, and this was used as a measurement sample. In addition, the solvent for concentration adjustment at the time of measurement is
Butanol was used. (Fine particle composition) The powder sample was determined by X-ray fluorescence analysis, atomic absorption analysis, gravimetric analysis, elemental analysis and the like.

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

(Presence / absence of heat ray cutting function of fine particles: evaluation P) A dispersion containing 10% by weight of fine particles was applied on a glass plate having a thickness of 2 mm using a bar coater, and dried (at 80 ° C. in a nitrogen atmosphere). ) 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 dried film (wavelength 2200 to 200 nm)
Is measured with a self-recording spectrophotometer (UV-3100, Shimadzu Corporation). From the obtained spectral curve, the film in the case where the coating amount was 3 g / m ^{2 in} terms of fine particles was evaluated by comparing with the following criteria.

Evaluation criteria: Cut amount at a wavelength of 2 μm ≧ 10% and T ₇₀₀
> If satisfies T _2000: If not satisfied heat-ray shielding ability there-above conditions: None ray shielding ability, however, the heat-ray shielding amount (light transmittance versus wavelength 2μm in the substrate (%)) - (in painted Wavelength 2μm
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 the mixture. When fine particles are produced by the method of the present invention,
The fine particle dispersion obtained by the reaction was concentrated to a fine particle concentration of 10% by weight. Reference) The transmittance of the used glass substrate 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 performed. 0.3 kg of zinc oxide powder in a mixed solvent of 1.6 kg of water and indium hydroxide (In ₂ O ₃ .nH
₂ O: In ₂ O ₃ content of 80 wt%) was added and mixed 12.80 g, by mixture heated to 100 ° C. with stirring to obtain a homogeneous zinc-containing solution (A1).

Next, 10.7 kg of 2-butoxyethanol was charged into a 20-liter glass reactor equipped with a stirrer, a dropping port, a thermometer, and a distillate gas outlet and capable of externally heating with a heating medium. 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 dropping, when the internal temperature is raised to 168 ° C., 800 g of a 2-butoxyethanol solution in which 36.9 g of lauric acid is dissolved is added over 10 seconds, and the mixture is heated and maintained at the temperature for 5 hours to obtain a bluish-gray. Dispersion of (D1) 5.64k
g was obtained. The dispersion (D1) has a fine particle concentration of 5.5% by weight.
In a dispersed manner.

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

(Reference Examples 2-3) The same as Reference Example 1 except that the kind and amount of the raw material in the zinc-containing solution (A1) in Reference Example 1, the kind and amount of the bottom solvent, and the kind of the additive liquid 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 D2C) having a fine particle concentration of 20% by weight.
3C) was obtained.

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

Table 2 shows the physical properties of the obtained fine powder (P1).
Shown in (Reference Example 5) Table 3 shows the results of evaluating the physical properties such as the crystallite diameter and the 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 was placed in a four-necked flask equipped with a reflux condenser, a stirrer, and a thermometer.
Parts by weight, 16 parts by weight of water, and 0.005 part by weight of 35% hydrochloric acid were sequentially charged, and while stirring, methyltrimethoxysilane 1 was added.
After adding 0 parts by weight and 30 parts by weight of tetraethoxysilane, the temperature was raised to 80 ° C., the reaction was carried out at 80 ° C. for 2 hours, and then cooled. The resulting mixture (x) has a nonvolatile content of 1
It was a homogeneous solution of 7.0% by weight. The obtained mixture (x) is hereinafter referred to as a silicate polymer solution (A).

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

[0138]

[Table 4]

[0139]

[Table 5]

Hereinafter, the above-mentioned fine particle dispersions and fine particle powders were used as fine particle raw materials, and the coating compositions, coated articles, and resins using the phthalocyanine compounds (ph-1) to (ph-5) shown in Table 4 were used. Examples of compositions, resin molded articles, and the like will be described, and evaluation methods will be described below. (Spectral characteristics) Regarding spectral characteristics, a self-recording spectrophotometer (U
V-3100, Shimadzu Corporation).
The transmittance for each wavelength light in the range of 200 to 200 nm was measured and evaluated.

(Heat ray cutting performance) From the measured spectral characteristics, the heat ray cutting performance was evaluated based on the following criteria. The heat ray cut performance is obtained by the heat ray cut amount at a wavelength of 2 μm obtained according to the following formula, and the presence or absence of absorption based on the presence of a dye at a wavelength of 0.8 to 1.2 μm, and the case where the absorption is “present” according to the following formula. Judgment was made as follows based on the heat ray cut amount.

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

The light transmittance at a wavelength of 365 nm is Tuv
(%) (Transparency in the visible region: total light transmittance and haze) Measurement and evaluation were performed using a turbidity meter (NDH-1001 DP Nippon Denshoku Industries Co., Ltd.). About the haze, Example 11,
12 and Comparative Examples 10 to 12, the measured values of the obtained films were shown. In other cases, the values were indicated by the UP (increase) of the haze relative to the substrate.

(Comparative Example 1) Fine particle dispersion (D1C) 60 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 Was produced. 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
After adding and mixing 0 parts by weight and stirring for 3 hours, a dispersion treatment was carried out for 30 minutes with an ultrasonic homogenizer to prepare a paint (R1).

Next, the coating material (R1) obtained was applied to glass using 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 was excellent in transparency in the visible region. Table 7 shows the evaluation results of the coated product (R1), and FIG. 1 shows the spectral transmittance curve.

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), Nippon Shokubai Co., Ltd.) n-Butanol 40 parts by weight Part A coating consisting of the above components was produced. That is, the phthalocyanine compound (ph-1) was added to 40 parts by weight of n-butanol.
After 127 parts by weight were added and mixed to form a uniform solution, an acrylic binder resin solution (Alloset 585) was added to the uniform solution.
8 (solid content 60% by weight, Nippon Shokubai Co., Ltd.) was added and mixed, and the mixture was stirred for 3 hours, and then subjected to a dispersion treatment with an ultrasonic homogenizer for 30 minutes to prepare a coating material (R2).

Next, the coating material (R2) obtained was applied to glass using a bar coater and dried to obtain a coated product (R2). The coated product (R2) has a wavelength of 0.8 to 1.
Although it had a shielding property against a heat ray of 2 μm, it did not have an ultraviolet cut 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 (Alloset 5858 (solid content 60% by weight); Nippon Shokubai Co., Ltd.) n-butanol 40 parts by weight A paint comprising the above components was produced. That is, after dissolving 0.127 parts by weight of the phthalocyanine compound (ph-1) in 40 parts by weight of n-butanol, a fine particle dispersion (D1
C) The mixed dispersion obtained by adding 60 parts by weight was stirred for 1 hour. Next, 20 parts by weight of an acrylic binder resin solution (Alloset 5858 (solid content: 60% by weight, Nippon Shokubai Co., Ltd.) is added to the mixed dispersion, mixed and stirred for 3 hours, followed by dispersion treatment with an ultrasonic homogenizer for 30 minutes. Thus, paint (1) was prepared.

Next, the coating material (1) obtained was applied to glass with a bar coater and dried to obtain a coated product (1). The coated product (1) was excellent in shielding properties against ultraviolet rays and heat rays, and also excellent in transparency in the visible region. Coated product (1) is based on a phthalocyanine compound (ph-1) that is not found in coated product (R1).
That there is absorption having a peak at 0 nm,
Since the transmittance in the entire heat ray wavelength range was lower than that in 1), it was found that the heat ray shielding rate was higher than that of the coated product (R1) and the haze value for visible light was lower. In addition, it was found that the coated product (1) was superior to the coated product (R2) in ultraviolet cut 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)
Coatings (2) to (6) and (R3) comprising a fine particle raw material, a phthalocyanine compound, and a binder component were produced in the same manner as in Example 1, applied to various substrates shown in Table 7 under the conditions shown in Table 7, and dried. By doing, coated products (2)-(6)
And a coated product (R3).

The coated articles (2) to (6) were excellent in shielding property against ultraviolet rays and heat rays and excellent in transparency in a visible range. Coated products (2) to (6) and coated product (R
Table 7 shows the evaluation results of 3). The coated product (3) obtained in Example 3 had excellent solvent resistance because the film was crosslinked.

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

[0153]

[Table 6]

[0154]

[Table 7]

(Examples 7, 8 and Comparative Examples 4 to 6) A phthalocyanine compound and fine particles described in Table 8 were added to 100 parts by weight of a molten polycarbonate resin (trade name: Panlite 1285, manufactured by Teijin Chemicals Limited). Then, a sheet having a thickness of 2 mm was formed at 280 ° C. using a T-die extruder. Table 8 shows the evaluation results of the obtained sheets.

[0156]

[Table 8]

(Examples 9, 10 and Comparative Examples 7 to 9) Methyl methacrylate 10 was placed between two hard glasses 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), a phthalocyanine compound described in Table 9 and fine particles added thereto in the amounts shown in Table 9 were added, and the resultant was immersed in a 65 ° C water bath for 14 hours. Then, the mixture was heated in an oven at 90 ° C. for 1 hour to complete the polymerization. After the completion of the polymerization, the resultant was peeled from the glass to obtain a transparent resin plate having a thickness of 3 mm. Table 9 shows the evaluation results of the obtained plates.

[0158]

[Table 9]

(Examples 11 and 12, Comparative Examples 10 to 12)
The phthalocyanine compound and the fine particles shown in Table 10 were added in the amounts shown in Table 10 to PP (polypropylene) pellets 1 respectively.
By melt-kneading with 00 parts by weight, a PP pellet (A) was obtained. Next, a two-layer PP film was obtained using an extruder equipped with a feedblock die for multilayer. That is, the PP pellet (B) containing no phthalocyanine compound and fine particle component is supplied to the main extruder and melted at 220 ° C., and the PP pellet (A) is supplied to the sub-extruder and melted at 180 ° C. By adjusting the discharge rate, PP
A laminated sheet composed of the (A) layer and the PP (B) layer is obtained, and the obtained sheet is subjected to a stretching treatment to have a thickness of 8
An OPP film in which a μm PP (A) layer and a 20 μm thick PP (B) layer were laminated was obtained.

Table 10 shows the evaluation results of the obtained films.

[0161]

[Table 10]

Example 13 Fine Particle Powder (Zph-1)
5 parts by weight and 95 parts by weight of polyester resin pellets were mixed and melt-kneaded to obtain a polyester composition in which fine particles were uniformly dispersed at 5% by weight, formed into a sheet by extrusion, and further 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, had excellent visible light transmittance, and had excellent ultraviolet ray shielding properties and heat ray shielding properties.

(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 sense of transparency, and was excellent in ultraviolet ray shielding properties and heat ray shielding properties.

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

Table 12 shows the results of the evaluation of each coated product.

[0166]

[Table 11]

[0167]

[Table 12]

[0168]

The composition for shielding ultraviolet rays and heat rays of the present invention comprises fine particles of a metal oxide coprecipitate comprising 80 to 99.9 atomic% of zinc and 0.1 to 20 atomic% of a group IIIB metal element. Zinc oxide-based fine particles) and a heat ray absorbent,
A transparent material that cuts ultraviolet rays and heat rays simultaneously can be configured. Furthermore, the composition of the present invention combines a zinc oxide-based fine particle having an infrared cut ability over a wide wavelength range of a heat ray and a heat ray absorbent having a selective infrared cut ability in a specific wavelength range of the heat ray. A transparent material capable of arbitrarily controlling the cutting performance (cut wavelength, cut amount, etc.) according to the achievement of unprecedented heat ray cutting performance and needs can be configured.

The resin molded product of the present invention has a zinc content of 80-99.
Fine particles of a metal oxide coprecipitate comprising 9 atomic% and a Group IIIB metal element of 0.1 to 20 atomic% (zinc oxide-based fine particles)
And a heat ray absorber, and a dispersion medium, wherein the dispersion medium is a resin and disperses the zinc oxide-based fine particles and the heat ray absorber. Since it is molded into at least one shape selected from the group consisting of, it is a transparent material that cuts ultraviolet rays and heat rays simultaneously. In the resin molded article of the present invention, by appropriately changing the combination of a zinc oxide-based fine particle having an infrared cut ability over a wide wavelength range of heat rays and a heat ray absorbent having a selective infrared cut ability in a specific wavelength range of the heat rays, Achieving unprecedented heat ray cutting ability and arbitrarily controlling the cutting performance (cut wavelength, cut amount, etc.) according to needs.

The coated article of the present invention comprises a resin molded article, glass,
And at least one substrate selected from the group consisting of paper and a coating film formed on the surface of the substrate, wherein the coating film comprises 80 to 99.9 atomic% of zinc and 0.1 to 2 group IIIB metal element.
Fine particles of a metal oxide coprecipitate comprising 0 atomic% (zinc oxide-based fine particles), a heat ray absorbent, and a dispersion medium, wherein 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 off ultraviolet rays and heat rays, because the composition contains a composition for shielding ultraviolet rays and heat rays. In the coated product of the present invention, by appropriately changing the combination of a zinc oxide-based fine particle having an infrared cut ability over a wide wavelength range of a heat ray and a heat ray absorbent having a selective infrared cut ability in a specific wavelength range of the heat ray, Achieving unprecedented heat ray cutting ability and arbitrarily controlling the cutting performance (cut wavelength, cut amount, etc.) according to needs.

[Brief description of the drawings]

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

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // C09D 5/32 C09D 5/32 (72) Inventor Takashi Yoshinori 1-25-12 Kannondai, Tsukuba-shi, Ibaraki Japan 12 Inside the catalyst (72) Inventor Osamu Kaieda 1-25-12 Kannondai, Tsukuba-shi, Ibaraki Nippon Shokubai Co., Ltd. (56) References JP-A-2-75683 (JP, A) JP-A-4-160037 (JP, A) JP-A-5-42622 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C09K 3/00 104 C09K 3/00 105 C08J 5/18 C08K 3/22 C08L 101 / 00 CA (STN)

Claims (4)

(57) [Claims] 1. Fine particles of an oxide coprecipitate of a metal comprising 80 to 99.9 atomic% of zinc and 0.1 to 20 atomic% of a Group IIIB metal element . Show
An ultraviolet and heat ray shielding composition comprising fine particles and a heat ray absorber comprising a phthalocyanine compound . Wherein further comprising a dispersion medium, wherein it is dispersed medium that disperse the fine particles and the heat-absorbing agent composition of claim 1. 3. A resin molded article obtained by molding the composition according to claim 2 , wherein the dispersion medium is a resin, into at least one shape selected from the group consisting of plates, sheets, films and fibers. 4. The composition according to claim 2 , wherein at least one substrate selected from the group consisting of a resin molded body, glass and paper, and formed on the surface of the substrate.
The dispersion medium forms a coating that binds the fine particles
And a coating comprising a composition that is a binder component that can be used.