JP7518483B2 - Dispersion containing inorganic oxide particles and zinc cyanurate particles, and coating composition - Google Patents

Description

The present invention relates to a coating composition containing a resin and a coating additive comprising a dispersion containing inorganic oxide particles and zinc cyanurate particles, a coating film formed from the coating composition, a method for producing the coating composition, and a coating additive to be added to the coating composition.
The present invention also relates to a dispersion liquid containing an inorganic oxide powder among the above-mentioned inorganic oxide particles and zinc cyanurate particles, and a dispersion liquid containing specific colloidal metal oxide particles among the above-mentioned inorganic oxide particles and zinc cyanurate particles.

Zinc cyanurate is known as a corrosion inhibitor for the surfaces of ferrous metals, and various methods for its production have been disclosed.
For example, Patent Document 1 discloses a method for producing lead and zinc cyanurates, which are known as corrosion inhibitors for metal surfaces, by mixing PbO or ZnO with cyanuric acid in a paste form at 100° C. to 180° C. and applying a shearing action to the obtained paste at 50° C. to 250° C.
Furthermore, Patent Document 2 discloses a corrosion-preventive coating material using zinc salts and/or lead salts of organic compounds such as barbituric acid and cyanuric acid as a corrosion-preventive coating agent for metal surfaces based on zinc salts and/or lead salts of organic compounds.
Furthermore, Patent Document 3 discloses a method for producing needle-shaped or plate-shaped basic zinc cyanurate particles characterized by an average particle diameter _D50 measured by a laser diffraction method of 80 nm to 900 nm, a specific surface area of 20 m ² /g to 100 m ² /g, and a major axis/minor axis length ratio (axial ratio) of 5 to 25, by wet dispersion of a mixed slurry of zinc oxide or basic zinc carbonate, cyanuric acid, and water.
Patent Document 4 discloses a method for producing a basic zinc cyanurate powder by heat treating a mixed powder of zinc oxide, cyanuric acid and water under closed or open conditions, and also discloses an anti-rust pigment composition containing the basic zinc cyanurate powder.

On the other hand, in addition to the purpose of coloring the target object (the surface to be painted), paints are required to have a variety of effects, such as the above-mentioned rust prevention effect and weather resistance. For example, for metal substrates (aluminum, iron, etc.), corrosion prevention is required, while for resin substrates and wood, durability, weather resistance, scratch resistance, corrosion prevention, and color change prevention are required, and for glass substrates and silicon substrates, improved strength and light resistance are required.

Japanese Patent Application Publication No. 59-031779 Japanese Unexamined Patent Publication No. 54-123145 International Publication No. 2011/162353 International Publication No. 2016/006585

Zinc cyanurate has long been known to provide metal surfaces with high corrosion protection. However, the zinc cyanurate obtained by the above manufacturing method has needle-like or plate-like particle shapes and a relatively large particle size, and when dispersed in a medium, it becomes a non-uniform slurry, which makes handling difficult when mixed with a binder resin to form a coating composition.

The present invention has been made in consideration of the above circumstances, and aims to provide a paint composition that can form a coating film that has high adhesion to a substrate, thereby fully exerting the functions of zinc cyanurate, such as corrosion prevention of metal surfaces, and, in the case of PET substrates and wood, improving durability, improving scratch resistance, improving the corrosion resistance of the substrate, and preventing color changes in the substrate (less likely to cause poor appearance).

The inventors of the present invention have conducted extensive research to solve the above problems, and have discovered that by blending a dispersion in which both inorganic oxide particles and zinc cyanurate particles are dispersed as dispersoids in a liquid medium as a paint additive with a resin component such as a resin emulsion, a paint composition can be obtained that is surprisingly good in dispersibility and can maintain a stable dispersion state. The inventors have also discovered that the above paint composition can provide a coating film that not only has excellent adhesion to the substrate (surface to be coated), but also has little cure shrinkage and excellent followability to deformation of the substrate, and that this can be expected to provide various functions of the paint, such as improved durability, scratch resistance, and corrosion resistance of the substrate, and prevention of color change of the substrate, in addition to the corrosion prevention effect on the metal surface, and thus have completed the present invention.

That is, in a first aspect, the present invention relates to a coating composition comprising a coating additive including a dispersion in which dispersoid particles including inorganic oxide particles and zinc cyanurate particles are dispersed in a liquid medium, and a resin.
As a second aspect, the present invention relates to the coating composition according to the first aspect, wherein the surface to be coated is at least one selected from the group consisting of an aluminum substrate, an iron-based substrate, a copper-based substrate, a gold-based substrate, a silver-based substrate, a platinum-based substrate, a mirror material, a glass substrate, a silicon substrate, wood, a resin film, and a resin molding.
As a third aspect, the present invention relates to a coating composition according to the first or second aspect, wherein the resin is in the form of a resin emulsion, the form being an oil-in-water emulsion or a water-in-oil emulsion, and the resin is a resin emulsion containing one or more resin components selected from the group consisting of acrylic resins, acrylic-styrene resins, acrylic-silicone resins, vinyl acetate resins, styrene resins, olefin resins, ethylene-vinyl acetate resins, ester resins, epoxy resins, phenol resins, amide resins, vinyl alcohol resins, fluorine resins, urethane resins, melamine resins, phthalic acid resins, silicone resins, alkyd resins, and vinyl chloride resins.
As a fourth aspect, the present invention relates to a coating composition according to the first or second aspect, wherein the resin is in the form of a water-soluble polymer or a colloidal dispersion, and is a water-soluble resin or a colloidal dispersion containing one or more resin components selected from the group consisting of acrylic resins, acrylic-styrene resins, acrylic-silicone resins, vinyl acetate resins, styrene resins, olefins, ethylene-vinyl acetate resins, ester resins, epoxy resins, phenolic resins, amide resins, vinyl alcohol resins, fluorine-based resins, urethane resins, melamine resins, phthalic acid resins, silicone resins, alkyd resins and vinyl chloride resins.
As a fifth aspect, the present invention relates to a coating composition according to any one of the first to fourth aspects, in which the inorganic oxide particles are an oxide of at least one element selected from the group consisting of Si, Al, Ti, Zr, Fe, Cu, Zn, Li, Na, K, Mg, Ca, Cs, Sr, Ba, B, Ga, Y, Nb, Mo, In, Sn, Sb, Ta, W, Ge, Pb, P, As, Rb, Bi, and Ce.
As a sixth aspect, the present invention relates to a coating composition according to the fifth aspect, in which the inorganic oxide particles are a composite oxide or a mixed oxide of two or more elements selected from the group consisting of Si, Al, Ti, Zr, Fe, Cu, Zn, Li, Na, K, Mg, Ca, Cs, Sr, Ba, B, Ga, Y, Nb, Mo, In, Sn, Sb, Ta, W, Ge, Pb, P, As, Rb, Bi and Ce.
As a seventh aspect, the present invention relates to a coating composition according to any one of the first to fifth aspects, in which the inorganic oxide particles are colloidal oxides of at least one type of atom selected from the group consisting of Si, Al, Ti, Zr, Fe, Cu, Zn, Li, Na, K, Mg, Ca, Cs, Sr, Ba, B, Ga, Y, Nb, Mo, In, Sn, Sb, Ta, W, Ge, Pb, P, As, Rb, Bi, and Ce.
As an eighth aspect, the present invention relates to a coating composition according to the seventh aspect, in which the inorganic oxide particles are colloidal composite oxides or colloidal mixed oxides of two or more types of atoms selected from the group consisting of Si, Al, Ti, Zr, Fe, Cu, Zn, Li, Na, K, Mg, Ca, Cs, Sr, Ba, B, Ga, Y, Nb, Mo, In, Sn, Sb, Ta, W, Ge, Pb, P, As, Rb, Bi, and Ce.
As a ninth aspect, the present invention relates to the coating composition according to any one of the first to eighth aspects, in which the zinc cyanurate particles have a major axis of primary particles of 400 nm to 3,000 nm and a minor axis of primary particles of 10 nm to 300 nm, and a ratio of the major axis to the minor axis of 1.3 to 300, as measured by a transmission electron microscope.
As a tenth aspect, the present invention relates to the coating composition according to any one of the first to ninth aspects, wherein the dispersoid particles in the dispersion have an average particle size of 80 nm to 5,000 nm as measured by a laser diffraction method, and the dispersoid particles in the dispersion have a solid content concentration of 0.1 to 50 mass %.
As an eleventh aspect, the present invention relates to the coating composition according to any one of the first to tenth aspects, in which the dispersoid particles in the dispersion contain inorganic oxide particles:zinc cyanurate particles in a mass ratio of 1:0.01 to 100, and a solid content concentration of the dispersoid particles in the dispersion is 0.1 to 50 mass%.
As a twelfth aspect, the present invention relates to the coating composition according to any one of the first to eleventh aspects, in which the liquid medium is water or an organic solvent.
As a thirteenth aspect, the present invention relates to a coating composition according to any one of the first to twelfth aspects, in which a ratio of solids to resin in the dispersion is 1:0.1 to 20 in terms of a mass ratio of (solids in dispersion):(resin), and a ratio of the total solids in the coating composition is 1 to 70 mass%.
As a fourteenth aspect, the present invention relates to the coating composition according to any one of the first to thirteenth aspects, further comprising a slurry of an inorganic oxide powder, the slurry having a solid content concentration of 0.1 to 50 mass %.
As a fifteenth aspect, the present invention relates to a coating composition according to the fourteenth aspect, in which the ratio of the solid content in the dispersion to the solid content in a slurry of the resin and the inorganic oxide powder is 1:0.1 to 20:0.1 to 1 in terms of a mass ratio of (solid content in the dispersion):(resin):(solid content in the slurry), and the ratio of the total solid content in the coating composition is 1 to 70 mass%.
As a sixteenth aspect, the present invention relates to a coating film of the coating composition according to any one of the first to fifteenth aspects, which is formed on at least one kind of substrate selected from the group consisting of an aluminum substrate, an iron-based substrate, a copper-based substrate, a gold-based substrate, a silver-based substrate, a platinum-based substrate, a mirror material, a glass substrate, a silicon substrate, wood, a resin film, and a resin molding.
As a seventeenth aspect, the present invention relates to a coating film of the coating composition according to any one of the first to fifteenth aspects, the coating film having a thickness of 0.1 μm to 100 μm.
As an eighteenth aspect, the present invention relates to the coating film according to the seventeenth aspect, in which the coating film is a spin-coated film, a bar-coated film, a roll-coated film, or a dip-coated film.
As a nineteenth aspect, the present invention relates to a method for producing a coating composition according to any one of the first to fifteenth aspects, the method including a step of mixing a dispersion in which dispersoid particles including inorganic oxide particles and zinc cyanurate particles are dispersed in a liquid medium, and a resin, using a submerged disperser.
As a twentieth aspect, the present invention relates to a method for producing a coating composition according to the fourteenth or fifteenth aspect, the method including a step of mixing, using a submerged disperser, a dispersion in which dispersoid particles including inorganic oxide particles and zinc cyanurate particles are dispersed in a liquid medium, the resin, and a slurry of the inorganic oxide powder.
As a 21st aspect, the present invention relates to the production method according to the 19th or 20th aspect, in which the submerged disperser is a stirrer, a rotary shear type stirrer, a colloid mill, a roll mill, a high-pressure jet type disperser, an ultrasonic disperser, a container-driven mill, a media stirring mill, or a kneader.
As a twenty-second aspect, the present invention relates to a method for producing a coating composition according to any one of the nineteenth to twenty-first aspects, further comprising, prior to the step of mixing using the submerged disperser, a step of mixing a mixture of inorganic oxide particles and zinc cyanurate particles or a slurry thereof using a grinding device.
As a twenty-third aspect, the present invention relates to the production method according to the twenty-second aspect, in which the pulverizing device is a ball mill, a bead mill, or a sand mill.
As a twenty-fourth aspect, the present invention relates to a method for producing a coating composition according to any one of the nineteenth to twenty-first aspects, further comprising, prior to the step of mixing using the submerged disperser, a step of mixing, using a grinding device, a mixed liquid of an inorganic oxide powder that has been ground in advance and zinc cyanurate particles or a slurry thereof.
As a twenty-fifth aspect, the present invention relates to a dispersion in which dispersoid particles including inorganic oxide particles and zinc cyanurate particles are dispersed in a liquid medium, the inorganic oxide particles being inorganic oxide powder, and the inorganic oxide powder having a specific surface area of 1 to 800 ^m2 /g and a loose bulk density of 0.03 to 3.0 g/ ^cm3 .
As a 26th aspect, the present invention relates to the dispersion liquid according to the 25th aspect, in which the inorganic oxide powder is an oxide of at least one element selected from the group consisting of Si, Al, Ti, Zr, Fe, Cu, Zn, Li, Na, K, Mg, Ca, Cs, Sr, Ba, B, Ga, Y, Nb, Mo, In, Sn, Sb, Ta, W, Ge, Pb, P, As, Rb, Bi, and Ce.
As a twenty-seventh aspect, the present invention relates to the dispersion liquid according to the twenty-fifth aspect or the twenty-sixth aspect, in which the dispersoid particles are particles having an average particle size of 200 nm to 5,000 nm as measured by a laser diffraction method, and the dispersoid particles in the dispersion liquid have a solid content concentration of 0.1 to 50 mass %.
As a twenty-eighth aspect, the present invention relates to a dispersion liquid in which dispersoid particles including inorganic oxide particles and zinc cyanurate particles are dispersed in a liquid medium, wherein the inorganic oxide particles are colloidal metal oxide particles excluding particles mainly composed of colloidal silica.
As a 29th aspect, the present invention relates to the dispersion liquid according to the 28th aspect, in which the colloidal metal oxide particles contain an oxide of at least one element selected from the group consisting of Al, Ti, Zr, Fe, Cu, Zn, Li, Na, K, Mg, Ca, Cs, Sr, Ba, B, Ga, Y, Nb, Mo, In, Sn, Sb, Ta, W, Ge, Pb, P, As, Rb, Bi, and Ce.
As a thirtieth aspect, the present invention relates to the dispersion liquid according to the twenty-eighth aspect or the twenty-ninth aspect, in which the dispersoid particles are particles having an average particle size of 80 nm to 2,000 nm as measured by a laser diffraction method, and the dispersoid particles in the dispersion liquid have a solid content concentration of 0.1 to 50 mass %.

The present invention also relates to a dispersion liquid containing an inorganic oxide powder and zinc cyanurate particles. That is, the present invention includes the following aspects [1] to [21].
[1]
A dispersion in which dispersoid particles containing an inorganic oxide powder and zinc cyanurate particles are dispersed in a liquid medium, the inorganic oxide powder having a specific surface area of 1 to 800 m ² /g and a loose bulk density of 0.03 to 3.0 g/cm ³ .
[2]
The dispersion liquid according to [1], wherein the inorganic oxide powder is an oxide of at least one element selected from the group consisting of Si, Al, Ti, Zr, Fe, Cu, Zn, Li, Na, K, Mg, Ca, Cs, Sr, Ba, B, Ga, Y, Nb, Mo, In, Sn, Sb, Ta, W, Ge, Pb, P, As, Rb, Bi, and Ce.
[3]
The dispersion liquid according to [2], wherein the inorganic oxide powder is a composite oxide or a mixed oxide of two or more elements selected from the group consisting of Si, Al, Ti, Zr, Fe, Cu, Zn, Li, Na, K, Mg, Ca, Cs, Sr, Ba, B, Ga, Y, Nb, Mo, In, Sn, Sb, Ta, W, Ge, Pb, P, As, Rb, Bi and Ce.
[4]
The dispersion liquid according to any one of [1] to [3], wherein the zinc cyanurate particles have a major axis of 400 nm to 3,000 nm, a minor axis of 10 nm to 300 nm, and a ratio of the major axis to the minor axis of 1.3 to 300, as measured by a transmission electron microscope.
[5]
The dispersion liquid according to any one of items [1] to [4], wherein the dispersoid particles have an average particle diameter of 200 nm to 5,000 nm as measured by a laser diffraction method, and the dispersoid particles in the dispersion liquid have a solid content concentration of 0.1 to 50 mass %.
[6]
The dispersion liquid according to any one of items [1] to [5], wherein the dispersoid particles contain inorganic oxide powder:zinc cyanurate particles in a mass ratio of 1:0.01 to 100, and the dispersoid particles in the dispersion liquid have a solid content concentration of 0.1 to 50 mass%.
[7]
The dispersion liquid according to any one of [1] to [6], wherein the liquid medium is water or an organic solvent.
[8]
A coating composition comprising the dispersion according to any one of [1] to [7] and a resin.
[9]
The coating composition according to [8], wherein the resin is in the form of a resin emulsion, the form being an oil-in-water emulsion or a water-in-oil emulsion, and the resin is a resin emulsion containing one or more resin components selected from the group consisting of acrylic resins, styrene-acrylic resins, acrylic-silicone resins, vinyl acetate resins, styrene resins, ethylene resins, ethylene-vinyl acetate resins, propylene resins, ester resins, epoxy resins, olefin resins, phenol resins, amide resins, vinyl alcohol resins, fluorine resins, urethane resins, melamine resins, phthalic acid resins, silicone resins, alkyd resins, and vinyl chloride resins.
[10]
The coating composition according to [8], wherein the resin is in the form of a water-soluble polymer or a colloidal dispersion, and is a water-soluble resin or a colloidal dispersion containing one or more resin components selected from the group consisting of acrylic resins, acrylic-styrene resins, acrylic-silicone resins, vinyl acetate resins, styrene resins, olefins, ethylene-vinyl acetate resins, ester resins, epoxy resins, phenol resins, amide resins, vinyl alcohol resins, fluorine resins, urethane resins, melamine resins, phthalic acid resins, silicone resins, alkyd resins, and vinyl chloride resins.
[11]
The coating composition according to any one of [8] to [10], wherein a ratio of solid content to resin in the dispersion is 1:0.1 to 20 in terms of a mass ratio of (solid content in dispersion):(resin), and a ratio of a total solid content in the coating composition is 1 to 70 mass%.
[12]
The coating composition according to any one of [8] to [11], further comprising a slurry of an inorganic oxide powder having a solid content concentration of 0.1 to 50 mass %.
[13]
The coating composition according to [12], wherein the ratio of the solid content in the dispersion to the solid content in a slurry of the resin and inorganic oxide powder is 1:0.1-20:0.1-1 in terms of a mass ratio of (solid content in the dispersion):(resin):(solid content in the slurry), and the ratio of the total solid content in the coating composition is 1-70 mass%.
[14]
A coating film of the coating composition according to any one of [8] to [13], having a thickness of 0.1 μm to 100 μm.
[15]
The coating film according to [14], which is a spin-coated film, a bar-coated film, a roll-coated film, or a dip-coated film.
[16]
A method for producing the dispersion liquid according to any one of [1] to [7], comprising a step of mixing inorganic oxide powder and zinc cyanurate particles or a slurry thereof in a liquid medium using a grinding device.
[17]
The method according to [16], wherein the grinding apparatus is a ball mill, a bead mill, or a sand mill.
[18]
The method for producing the dispersion liquid according to any one of [1] to [7], further comprising a step of mixing a pre-pulverized inorganic oxide powder and zinc cyanurate particles or a slurry thereof in a liquid medium using a grinding device.
[19]
A method for producing the coating composition according to any one of [8] to [13], comprising a step of mixing the dispersion according to any one of [1] to [7] and the resin using a submerged disperser.
[20]
A method for producing the coating composition according to [12] or [13], comprising a step of mixing the dispersion according to any one of [1] to [7], the resin, and a slurry of the inorganic oxide powder using a submerged disperser.
[21]
The method for producing a coating composition according to [19] or [20], wherein the submerged dispersing machine is a stirrer, a rotary shear type stirrer, a colloid mill, a roll mill, a high-pressure jet type dispersing machine, an ultrasonic dispersing machine, a container-driven type mill, a media stirring mill, or a kneader.

The present invention further relates to a dispersion liquid containing specific colloidal metal oxide particles and zinc cyanurate particles. That is, the present invention includes the following aspects <1> to <17>.
＜1＞
A dispersion in which dispersoid particles including colloidal metal oxide particles, excluding particles mainly composed of colloidal silica, and zinc cyanurate particles are dispersed in a liquid medium.
＜2＞
The dispersion liquid according to <1>, wherein the colloidal metal oxide particles contain an oxide of at least one element selected from the group consisting of Al, Ti, Zr, Fe, Cu, Zn, Li, Na, K, Mg, Ca, Cs, Sr, Ba, B, Ga, Y, Nb, Mo, In, Sn, Sb, Ta, W, Ge, Pb, P, As, Rb, Bi, and Ce.
＜3＞
The dispersion liquid according to <2>, wherein the colloidal metal oxide particles contain a composite oxide or a mixed oxide of two or more elements selected from the group consisting of Al, Ti, Zr, Fe, Cu, Zn, Li, Na, K, Mg, Ca, Cs, Sr, Ba, B, Ga, Y, Nb, Mo, In, Sn, Sb, Ta, W, Ge, Pb, P, As, Rb, Bi, and Ce.
＜4＞
The dispersion liquid according to any one of <1> to <3>, wherein the zinc cyanurate particles have a major axis of 400 nm to 3,000 nm, a minor axis of 10 nm to 300 nm, and a ratio of the major axis to the minor axis of 1.3 to 300, as measured by a transmission electron microscope.
＜5＞
The dispersion liquid according to any one of <1> to <4>, wherein the dispersoid particles have an average particle diameter of 80 nm to 2,000 nm as measured by a laser diffraction method, and the dispersoid particles in the dispersion liquid have a solid content concentration of 0.1 to 50 mass %.
＜6＞
The dispersion liquid according to any one of <1> to <5>, wherein the dispersoid particles contain metal oxide particles:zinc cyanurate particles in a mass ratio of 1:0.01 to 100, and the dispersoid particles in the dispersion liquid have a solid content concentration of 0.1 to 50 mass%.
＜７＞
The dispersion liquid according to any one of <1> to <6>, wherein the liquid medium is water or an organic solvent.
＜8＞
A coating composition comprising the dispersion according to any one of <1> to <7> and a resin.
＜9＞
The coating composition according to <8>, wherein the resin is in the form of a resin emulsion, the form being an oil-in-water emulsion or a water-in-oil emulsion, and the resin is a resin emulsion containing one or more resin components selected from the group consisting of acrylic resins, styrene-acrylic resins, acrylic-silicone resins, vinyl acetate resins, styrene resins, ethylene resins, ethylene-vinyl acetate resins, propylene resins, ester resins, epoxy resins, olefin resins, phenol resins, amide resins, vinyl alcohol resins, fluorine resins, urethane resins, melamine resins, phthalic acid resins, silicone resins, alkyd resins, and vinyl chloride resins.
＜10＞
The coating composition according to <8>, wherein the resin is in the form of a water-soluble polymer or a colloidal dispersion, and is a water-soluble resin or a colloidal dispersion containing one or more resin components selected from the group consisting of acrylic resins, acrylic-styrene resins, acrylic-silicone resins, vinyl acetate resins, styrene resins, olefins, ethylene-vinyl acetate resins, ester resins, epoxy resins, phenol resins, amide resins, vinyl alcohol resins, fluorine resins, urethane resins, melamine resins, phthalic acid resins, silicone resins, alkyd resins, and vinyl chloride resins.
<11>
The coating composition according to any one of <8> to <10>, wherein a ratio of the solid content and the resin in the dispersion is 1:0.1 to 20 in terms of a mass ratio of (solid content in the dispersion):(resin), and a ratio of the total solid content in the coating composition is 1 to 70 mass%.
＜12＞
A coating film of the coating composition according to any one of <8> to <11>, having a thickness of 0.1 μm to 100 μm.
＜13＞
The coating film according to <12>, wherein the coating film is a spin-coated film, a bar-coated film, a roll-coated film, or a dip-coated film.
＜14＞
The method for producing the dispersion liquid according to any one of <1> to <7>, further comprising a step of mixing colloidal metal oxide particles and zinc cyanurate particles or a slurry thereof in a liquid medium using a grinding device.
＜15＞
The method according to <14>, wherein the grinding apparatus is a ball mill, a bead mill, or a sand mill.
＜16＞
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＜１７＞
The method for producing a coating composition according to <16>, wherein the submerged dispersing machine is a stirrer, a rotary shear type stirrer, a colloid mill, a roll mill, a high-pressure jet type dispersing machine, an ultrasonic dispersing machine, a container-driven type mill, a media stirring mill, or a kneader.

The coating composition of the present invention can be applied to a surface to obtain a coating film in which zinc cyanurate particles and inorganic oxide particles are uniformly present, and a coating film having excellent adhesion and hardness can be obtained.
The coating additive used in the coating composition of the present invention is in the form of a dispersion liquid in which both inorganic oxide particles and zinc cyanurate particles as dispersoid particles have high dispersion stability, and has high dispersibility with no sediment even when left at room temperature for several days. The coating additive (dispersion liquid) in which inorganic oxide particles and zinc cyanurate particles are dispersed in a liquid medium maintains good stability even when mixed with a resin component such as a resin emulsion, and has the effect of high handleability when producing a coating composition. The zinc cyanurate particles and inorganic oxide particles also maintain a stable dispersion state in the resulting coating composition, and the zinc cyanurate particles and inorganic oxide particles can be uniformly present in the coating film obtained by applying this to the surface to be coated, and the above-mentioned coating film with excellent adhesion can be obtained. Furthermore, when a highly transparent substrate such as a resin film such as a PET film or glass is used, a coating film with excellent adhesion can be obtained while maintaining the transparency of the substrate.
The coating film of the coating composition of the present invention is expected to exhibit the inherent functions of zinc cyanurate, such as anticorrosion, the functions of inorganic oxide particles, such as hydrophilicity, slipperiness, insulation, thermal conductivity, photocatalysis, and the like, as well as the coating composition's functions of weather resistance, light resistance, waterproofing, scratch resistance, corrosion resistance of substrates, and prevention of color change in substrates, thereby contributing to the prevention of deterioration of substrates.

FIG. 1 is a graph showing an approximation curve calculated from the measured values of the data potential (mV) of inorganic oxide particles versus the pH value (pH 2 to 10 (horizontal axis)) of an aqueous dispersion slurry of inorganic oxide powder: silica powder (fumed silica A, fumed silica B, silica powder C) or titania powder (titania powder).

The present invention relates to a paint composition comprising a paint additive including a dispersion in which dispersoid particles including inorganic oxide particles and zinc cyanurate particles are dispersed in a liquid medium, and a resin emulsion.

[Paint additives]
The paint additive used in the paint composition of the present invention comprises a dispersion in which dispersoid particles, which include inorganic oxide particles and zinc cyanurate particles, are dispersed in a liquid medium.
When the paint additive according to the present invention consists only of a dispersion in which dispersoid particles containing inorganic oxide particles and zinc cyanurate particles are dispersed in a liquid medium, the dispersion can be treated as a paint additive. In such a case, the paint additive may be read as the dispersion in the following description.

<Inorganic oxide particles>
Examples of the inorganic oxide particles constituting the dispersoid particles include particles of an oxide of at least one element selected from the group consisting of Si, Al, Ti, Zr, Fe, Cu, Zn, Li, Na, K, Mg, Ca, Cs, Sr, Ba, B, Ga, Y, Nb, Mo, In, Sn, Sb, Ta, W, Ge, Pb, P, As, Rb, Bi, and Ce. The inorganic oxide particles are particles of oxides of atoms with a valence of 2 to 6, and examples of the form of oxides of these atoms include SiO ₂ , TiO ₂ , Fe ₂ O ₃ , CuO, ZnO, Y ₂ O ₃ , ZrO ₂ , Nb ₂ O ₅ , MoO ₃ , In ₂ O ₃ , SnO ₂ , Sb ₂ O ₅ , Ta ₂ O ₅ , WO ₃ , PbO, Bi ₂ O ₃ , CeO ₂ , etc. These inorganic oxides can be used alone or in combination of two or more kinds.
Examples of the combination method include a method of mixing several kinds of the inorganic oxides, a method of compounding two or more kinds of the inorganic oxides, or a method of forming a solid solution of two or more kinds of the inorganic oxides at the atomic level. That is, the inorganic oxide particles can be particles of a single oxide of one kind of atom selected from the above atomic group, particles of a composite oxide of two or more kinds of atoms selected from the same group, and any mixture of these particles (mixtures of single oxide particles, mixtures of composite oxide particles, mixtures of single oxide particles and composite oxide particles, etc., collectively referred to as mixed oxides).
Examples of the composite oxide particles include TiO ₂ -SnO ₂ composite oxide particles in which TiO ₂ particles and SnO ₂ particles are composited by chemical bonding at their interfaces, SnO ₂ -WO 3 composite oxide particles in which SnO ₂ particles and WO ₃ particles are composited by chemical bonding at their interfaces, SnO ₂ -SiO ₂ composite oxide particles in which SnO ₂ particles and SiO ₂ particles are composited by chemical bonding at their interfaces, SnO 2 -WO 3 -SiO ₂ composite oxide particles in which SnO ₂ particles, WO ₃ particles, and SiO ₂ particles are composited by chemical bonding at their interfaces, SnO ₂ -MoO ₃ -SiO ₂ composite oxide particles in which SnO ₂ particles, MoO ₃ particles, and _{SiO 2} particles _are composited by chemical bonding at their interfaces, _and Sb ₂ O ₅ particles and SiO Examples of the oxide include, but are not limited to, Sb ₂ O ₅ —SiO ₂ composite oxide particles in which _two particles are chemically bonded at their interface to form a composite, and TiO ₂ —SnO ₂ —ZrO ₂ composite oxide particles obtained by forming a solid solution at the atomic level between TiO ₂ , SnO ₂ , and ZrO ₂ .

The inorganic oxide particles can be used regardless of their form, such as inorganic oxide powder, colloidal inorganic oxide particles (also called inorganic oxide colloidal particles), and the like.
The inorganic oxide powder referred to here may, for example, have a specific surface area of 1 to 800 m ² /g and a loose bulk density of 0.03 to 3.0 g/cm ^3. For example, the specific surface area may be 10 to 700 m ² /g, 30 to 500 m ² /g, or 40 to 300 m ² /g, and the loose bulk density may be, for example, 0.03 to 1.0 g/cm ³ , 0.05 to 0.8 m ² /g, 0.05 to 0.5 m ² /g, or 0.05 to 0.2 m ² /g. The loose bulk density is defined as the ratio of the mass of a powder sample in an untapped (loose) state to the volume of the powder including the factor of the interparticle void volume.
Colloidal inorganic oxide particles can be used in the form of an inorganic oxide sol in which the inorganic oxide particles are dispersed in a liquid medium.

The inorganic oxide particles can be produced by a method appropriately selected depending on the type of the inorganic oxide particles, and can be produced by known methods, broadly classified as liquid phase methods (hydrolysis method, sol-gel method, hydrothermal method, coprecipitation method, freeze-drying method, etc.), gas phase methods (melting method, spray drying method, gas phase reaction method (combustion hydrolysis, etc.), etc.), etc.
When the inorganic oxide particles are in the form of colloidal inorganic oxide particles, the particles can be produced by a known method (e.g., ion exchange method, peptization method, hydrolysis method, reaction method (oxidation method), etc.) Furthermore, the obtained colloidal particles can be used after drying.

Examples of the ion exchange method include a method of treating an acid salt of the above atom with a hydrogen-type ion exchange resin, or a method of treating a basic salt of the above atom with a hydroxide-type anion exchange resin. Examples of the peptization method include a method of neutralizing an acid salt of the above atom with a base, or a method of neutralizing a basic salt of the above atom with an acid, and then washing the gel obtained by peptization with an acid or base. Examples of the hydrolysis method include a method of hydrolyzing an alkoxide of the above atom, or a method of hydrolyzing a basic salt of the above atom under heating and then removing unnecessary acid. Examples of the reaction method (oxidation method) include a method of reacting a powder of the above atom or inorganic oxide with an acid (e.g., hydrogen peroxide).

The inorganic oxide particles may be in the form of modified inorganic oxide particles in which the inorganic oxide particles serve as nuclei and at least a portion of the surface thereof is covered with a coating made of another inorganic oxide particle (surface-treated).
In this case, the inorganic oxide particles to be coated may be any of the above-mentioned inorganic oxides (single oxides, composite oxides, mixed oxides), and the production method thereof may be appropriately selected from the above-mentioned known production methods.
The modified inorganic oxide particles can be produced by a conventional method, for example, a method of mixing inorganic oxide particles A as nuclei with another inorganic oxide particle B as a coating, followed by heating. In this case, for example, mixing of inorganic oxide particles A as nuclei with another inorganic oxide particle B as a coating can be carried out at a temperature of 0 to 100°C, for example, room temperature to 60°C, and heating after mixing can be carried out at, for example, 70 to 300°C.

Among these inorganic oxide particles (in the case of modified inorganic oxide particles, the inorganic oxide particles that serve as the core), there can be mentioned particles of an oxide of at least one atom selected from the group consisting of Si, Al, Ti, Zr, Fe, Cu, Zn, Li, Na, K, Mg, Ca, Cs, Sr, Ba, B, Ga, Y, Nb, Mo, In, Sn, Sb, Ta, W, Ge, Pb, P, As, Rb, Bi and Ce, preferably particles of a composite oxide of two or more atoms selected from the same group, or particles of a mixed oxide.

The shape of the inorganic oxide particles is not particularly limited and may be, for example, spherical, polyhedral, angular, hollow, core-shell, porous, rod-like, plate-like, or amorphous, and preferably spherical, hollow, core-shell, or porous.

The average particle size of the inorganic oxide particles (in the case of particles of a modified inorganic oxide, this refers to the entire particle consisting of the core and the coating) can be measured by a laser diffraction method or a dynamic light scattering method.
For example, when the inorganic oxide particles are in the form of the inorganic oxide powder described above, the powder can be dispersed in a suitable medium and the average particle size measured by the laser diffraction method can be in the range of, for example, 500 nm to 100 μm, 1.0 μm to 80 μm, or 1.0 μm to 50 μm.
For example, when the inorganic oxide particles are in the form of colloidal inorganic oxide particles, they can be measured by dynamic light scattering (DLS). The average particle diameter of the colloidal inorganic oxide particles measured by dynamic light scattering is, for example, in the range of 5 nm to 500 nm, or 5 nm to 200 nm, or 5 nm to 100 nm, or 5 nm to 50 nm, or 3 nm to 300 nm, 3 nm to 200 nm, or 3 nm to 100 nm.

As described above, the inorganic oxide particles can be used in the form of colloidal inorganic oxide particles, or in the form of an inorganic oxide sol in which the colloidal inorganic oxide particles are dispersed in a liquid medium. The inorganic oxide concentration in this inorganic oxide sol can be in the range of 0.1% by mass to 40% by mass, or 0.1% by mass to 20% by mass, or 0.1% by mass to 10% by mass.
As the liquid medium, those used for the dispersion liquid described below can be used, that is, aqueous media such as water, organic solvents such as alcohols, glycols, esters, ketones, nitrogen-containing solvents, and aromatic solvents, and mixed solvents of organic solvents and water can be used.

Commercially available inorganic oxide particles can be used, and examples thereof include, but are not limited to, the following:
For example, commercially available inorganic oxide powders include the AEROSIL (registered trademark) series (silicon oxide), AEROXIDE (registered trademark) Alu series (aluminum oxide), AEROXIDE (registered trademark) TiO2 series (titanium oxide), and AEROXIDE (registered trademark) STX series (titanium oxide (core)-silica (shell) composites) manufactured by Nippon Aerosil Co., Ltd.; the Cab-O-SIL (registered trademark) series (silicon oxide) and SpectrAl (registered trademark) series (aluminum oxide) manufactured by Cabot Corporation; NanoTek (registered trademark) manufactured by CIK Nanotec Co., Ltd. (alumina, titanium oxide, tin oxide, zirconium oxide, zinc oxide, copper oxide); and Sylysia (registered trademark) manufactured by Fuji Silysia Chemical Co., Ltd. ) series (silicon oxide); Tokuyama Corporation's Reoloseal (registered trademark) series and Excelica (registered trademark) series (silicon oxide); Asahi Kasei Wacker Silicone Corporation's HDK (registered trademark) series (silicon oxide); Sumitomo Chemical Co., Ltd.'s AKP (registered trademark) series (aluminum oxide); Taimicron series (aluminum oxide) manufactured by Taimei Chemical Industry Co., Ltd.; Sasol's DISPERAL (registered trademark) series and DISPAL (registered trademark) series (aluminum oxide); Sakai Chemical Industry Co., Ltd.'s titanium oxide and zinc oxide; Ishihara Sangyo Kaisha, Ltd.'s titanium oxide, zinc oxide and tin oxide; Daiichi Kigenso Kagaku Kogyo Co., Ltd.'s zirconium oxide; and Shin-Nippon Denko Co., Ltd.'s zirconium oxide.

In addition, examples of commercially available colloidal inorganic oxide particles include SNOWTEX (registered trademark) (silica sol) ST-N-40, ST-XS, ST-OXS, ST-S, T-OS, ST-30, ST-O, ST-N, ST-C, ST-30L, ST-OL, ST-OYL, ST-ZL, etc., manufactured by Nissan Chemical Co., Ltd., Alumina Sol 100 (AS-100), Alumina Sol 200 (AS-200), Alumina Sol 520-A (AS-520A0) (aqueous dispersion of alumina), Nanouse (registered trademark) (zirconia sol) ZR-30BS, ZR- 30AH, ZR-40BL, ZR-30AL, etc.; NanoTek (registered trademark) (alumina, titanium oxide, tin oxide, zirconium oxide, zinc oxide, copper oxide: solvent dispersion product) manufactured by CIK Nanotech Co., Ltd.; Titaniasol, SN-100D (water-dispersed sol of antimony-doped tin oxide) manufactured by Ishihara Sangyo Kaisha, Ltd.; Silicadol (registered trademark) manufactured by Nippon Chemical Industry Co., Ltd.; Adelite (registered trademark) AT series manufactured by ADEKA Corporation; Cataloid (registered trademark) S series manufactured by JGC Catalysts and Chemicals Co., Ltd.; Fuso Chemical Co., Ltd. Examples of suitable materials include Quartron (registered trademark), titanium oxide manufactured by Teika Co., Ltd., alumina sol manufactured by Kawaken Fine Chemical Co., Ltd., Needral (aqueous cerium oxide dispersion liquid) manufactured by Taki Chemical Co., Ltd., Cataloid (registered trademark) A series (alumina aqueous dispersion sol) and Neo Sunveil (registered trademark) PW (aqueous titanium oxide dispersion sol) manufactured by JGC Catalysts and Chemicals Co., Ltd.

In addition, when the inorganic oxide particles are in the form of an inorganic oxide powder or a mixture of an inorganic oxide powder and an inorganic oxide colloidal particle, the inorganic powder may be replaced with an inorganic nitride, an inorganic oxynitride, an inorganic sulfide, an inorganic hydride, an inorganic carbide, an inorganic chloride, a (slightly soluble) inorganic hydroxide, a sparingly soluble organic polymer particle, an organic polymer-coated inorganic powder, an inorganic fiber (glass fiber), or an inorganic clay mineral powder, and these powders and inorganic oxide powders may be used in combination.
The inorganic powder may contain at least one atom selected from the group consisting of the various atoms listed in the inorganic oxide powder (inorganic oxide particle) described above, i.e., Si, Al, Ti, Zr, Fe, Cu, Zn, Li, Na, K, Mg, Ca, Cs, Sr, Ba, B, Ga, Y, Nb, Mo, In, Sn, Sb, Ta, W, Ge, Pb, P, As, Rb, Bi, and Ce.
The specific surface area, loose bulk density, shape and average particle size of these powders may be those listed for the inorganic oxide powders described above.

<Zinc cyanurate particles>
Cyanuric acid is a tribasic acid, and can produce acidic, neutral, and basic salts by reacting with divalent zinc. For example, when the molar ratio of (zinc oxide)/(cyanuric acid) is 1.0, an acidic salt equivalent to Zn(C ₃ N ₃ O ₃ H) is formed. When the molar ratio of (zinc oxide)/(cyanuric acid) is 1.5, _a neutral salt equivalent to Zn ₃ (C ₃ N 3 O ₃ ) ₂ is formed. When the molar ratio of (zinc oxide)/(cyanuric acid) is 2.5, a basic salt equivalent to Zn ₃ (C ₃ N ₃ O ₃ ) _2.2ZnO is formed. These salts can contain water of crystallization, and can form, for example, monohydrate, dihydrate, and trihydrate salts.
In the present invention, the zinc cyanurate particles may have a molar ratio of (zinc oxide)/(cyanuric acid) of 1.0 to 5.0.
The zinc source may be zinc oxide or basic zinc carbonate, and may be used in the above molar ratio calculated as zinc oxide. For example, zinc oxide type 2 manufactured by Sakai Chemical Industry Co., Ltd. may be used as the zinc oxide.
In the present invention, it is particularly preferable to use a basic salt, for example Zn ₃ (C ₃ N ₃ O ₃ ) _{2.2ZnO.3H 2} O.

The zinc cyanurate particles have an elongated particle shape such as a needle or plate, and in the present invention, zinc cyanurate particles can be suitably used, in which the length of the major axis of the primary particle is 400 nm to 3,000 nm, the length of the minor axis of the primary particle is 10 nm to 300 nm, and the ratio of the length of the major axis to the minor axis (major axis/minor axis) is 1.3 to 300, as measured by observation with a transmission electron microscope. Furthermore, the zinc cyanurate particles that can be used have a specific surface area of, for example, 10 m ² /g to 100 m ² /g.
For example, zinc cyanurate particles can be preferably used in which the length of the major axis of the primary particles is 400 nm to 1,000 nm, or 400 nm to 800 nm, or 400 nm to 600 nm, the length of the minor axis of the primary particle diameter is 10 to 300 nm, or 10 nm to 90 nm, or 30 nm to 90 nm, and the ratio of the lengths of the major axis to the minor axis (major axis/minor axis) is 1.3 to 100. The ratio of the lengths of the major axis to the minor axis can be any combination of a lower limit of 1.3 or 4.4 and an upper limit of 12, 20, 80, or 100.
Also, for example, zinc cyanurate particles can be preferably used in which the length of the major axis of the primary particle is 1,000 nm to 3,000 nm, or 2,000 nm to 3,000 nm, the length of the minor axis of the primary particle diameter is 80 to 300 nm, or 100 nm to 300 nm, and the ratio of the length of the major axis to the minor axis (major axis/minor axis) is 3.3 to 37.5. The ratio of the length of the major axis to the minor axis can be any combination of a lower limit of 3.3 and an upper limit of 20 or 37.5.

In addition, the average particle size of zinc cyanurate particles in an aqueous dispersion can be measured by dispersing the particles or a dispersion containing the particles in pure water and using a laser diffraction particle size distribution measuring device (for example, Shimadzu Corporation, product name SALD-7500 nano).
The average particle size of the zinc cyanurate particles in the aqueous dispersion, as measured by a laser diffraction method, is, for example, 80 nm to 20,000 nm.

There are two methods for producing zinc cyanurate particles: one is to carry out a liquid-phase reaction in a slurry state where the raw materials are dispersed in water, and the other is to carry out a solid-phase reaction in a powder state where the raw materials are carried out.

A production method in which raw materials are dispersed in water to cause a liquid-phase reaction in a slurry state is, for example, a method in which zinc oxide or basic zinc carbonate, cyanuric acid, and water are mixed so that the cyanuric acid concentration is 0.1% by mass to 10.0% by mass, and the mixed slurry is wet-dispersed at a temperature of 5° C. to 55° C. using a submerged disperser, thereby causing the reaction and dispersing the product, and a slurry (dispersion liquid) of zinc cyanurate particles is obtained.
In addition, since cyanuric acid dissolved in water reacts quickly with zinc oxide or basic zinc carbonate to promote particle growth, the product zinc cyanurate tends to become large particles. Therefore, it is preferable to carry out the reaction at 55° C. or less, or 45° C. or less.

Wet dispersion is performed using a dispersion medium. By performing wet dispersion using a dispersion medium, it is possible to cause a mechanochemical reaction between at least one selected from zinc oxide and basic zinc carbonate and cyanuric acid by mechanical energy generated by collision of the dispersion media. The mechanochemical reaction refers to a chemical reaction caused by applying mechanical energy from multiple directions to zinc oxide, basic zinc carbonate, and cyanuric acid by collision of the dispersion media.
Examples of the dispersion media include stabilized zirconia beads, quartz glass beads, soda-lime glass beads, alumina beads, and mixtures thereof. Considering the contamination caused by the collision of the dispersion media with each other and the crushing of the dispersion media, it is preferable to use glass beads or stabilized zirconia beads as the dispersion media. The size of the dispersion media can be, for example, 0.1 mm to 10 mm in diameter, preferably 0.5 mm to 2.0 mm in diameter. If the diameter of the dispersion media is less than 0.1 mm, the collision energy between the crushing media is small, and the mechanochemical reactivity tends to be weak. In addition, if the diameter of the dispersion media is more than 10 mm, the collision energy between the dispersion media is too large, causing the dispersion media to be crushed and causing a lot of contamination, which is not preferable.

The apparatus (grinding apparatus) for wet dispersion using dispersion media is not particularly limited as long as it is capable of adding the mixed slurry to a container containing dispersion media, stirring the mixture to cause the dispersion media to collide with zinc oxide, basic zinc carbonate, or cyanuric acid, thereby causing a mechanochemical reaction between zinc oxide or basic zinc carbonate and cyanuric acid. Examples of such apparatus include ball mills, bead mills, and sand mills such as Sand Grinder (manufactured by Imex Co., Ltd.), Apex Mill (manufactured by Hiroshima Metal & Machinery Co., Ltd. (formerly Kotobuki Kogyo Co., Ltd.)), Attritor (manufactured by Nippon Coke & Co., Ltd.), and Pearl Mill (manufactured by Ashizawa Finetech Co., Ltd.). The rotation speed and reaction time of the apparatus for stirring the dispersion media can be appropriately adjusted according to the desired particle size, etc.

In the obtained zinc cyanurate particle dispersion, the zinc cyanurate particles are contained in the dispersion (slurry) in a range of 0.10% by weight to 50% by weight, or 0.1% by weight to 20% by weight, or 0.1% by weight to 10% by weight, or 0.1% by weight to 5% by weight as solids.

Furthermore, in order to reduce the particle size of the resulting zinc cyanurate particles, the zinc cyanurate particles can be subjected to a pulverization process using the pulverization processing device. The rotation speed and reaction time of the device for stirring the dispersion medium can be appropriately adjusted according to the desired particle size, etc.
The zinc cyanurate particles obtained by this production method have, for example, a primary particle having a major axis length of 100 nm to 800 nm, a minor axis length of 10 nm to 60 nm, and a ratio of the major axis length to the minor axis length (major axis/minor axis) of 5 to 25, as measured by transmission electron microscope observation, and an average particle diameter of 80 nm to 900 nm as measured by laser diffraction method. The zinc cyanurate particles obtained by drying the aqueous dispersion slurry of this zinc cyanurate particle at 110° C. have a specific surface area of 10 m ² /g to 100 m ² /g.

Also, a production method in which raw materials are subjected to a solid-phase reaction in a powder state is, for example, a method in which a mixed powder consisting of zinc oxide, cyanuric acid, and water, in which the sieve residue on a 1,000 μm mesh is less than 1% by mass, the molar ratio of zinc oxide to cyanuric acid being 2 to 3, and the water content of the mixed powder being 9 to 18% by mass, is heat-treated at 30° C. to 300° C. in a closed or open state.
The obtained zinc cyanurate particles contain about 10% by mass of moisture, so they are subjected to heat treatment in an open state to remove moisture, and the zinc cyanurate particles with a moisture content of less than 1.0% by mass (for example, a commercially available product manufactured by Nissan Chemical Industries, Ltd., product name Starfine) can be used in a dispersion liquid (paint additive) described below. In the case of industrial mass production, the heat treatment here is preferably performed using a powder mixer having a mixing means and a heating means. Specific examples include a vibration dryer, a Henschel mixer, a Loedige mixer, a Nauta mixer, a rotary kiln, and other heated reaction tanks capable of stirring and mixing in an open or closed type.
Furthermore, in order to reduce the particle size of the resulting zinc cyanurate particles, the zinc cyanurate particles can be subjected to a pulverization process using the pulverization processing device. The rotation speed and reaction time of the device for stirring the dispersion medium can be appropriately adjusted according to the desired particle size, etc.
The zinc cyanurate particles obtained by this production method have, for example, less than 10% by mass of residue on a sieve with an opening of 400 μm, and when measured by a transmission electron microscope, the length of the major axis of the primary particles is 400 nm to 3,000 nm, the length of the minor axis of the primary particles is 10 nm to 300 nm, and the ratio of the lengths of the major axis to the minor axis (major axis/minor axis) is 1.3 to 300, and the average particle diameter when measured by a laser diffraction method is 0.5 μm to 20 μm. The specific surface area of the obtained zinc cyanurate particles is, for example, 10 m ² /g to 100 m ² /g.
The surface charge of the obtained zinc cyanurate particles is negative in an aqueous system in the pH range of 3 to 10. Therefore, not only does it have good dispersibility in water in the acidic to alkaline range, but it also has good compatibility with synthetic resins, emulsions, etc. when preparing an aqueous rust-preventive paint (such as a paint composition), and a stable aqueous rust-preventive paint can be obtained.

<Method of producing dispersion (paint additive)>
The method for producing the dispersion is not particularly limited, but for example, the dispersion can be obtained by a step of mixing inorganic oxide particles and zinc cyanurate particles or a slurry thereof in a liquid medium using a grinding device. When inorganic oxide powder is used as the inorganic oxide particles, it may be ground in advance and mixed with zinc cyanurate or a slurry thereof in a liquid medium using a grinding device to obtain a dispersion.

As an apparatus for mixing inorganic oxide particles and zinc cyanurate particles to obtain a dispersion, i.e., a paint additive, the same apparatus (grinding apparatus, dispersion media) as the apparatus for wet dispersion of zinc cyanurate using the above-mentioned dispersion media can be used, specifically, a ball mill, bead mill, or sand mill such as Sand Grinder (manufactured by Imex Co., Ltd.), Apex Mill (manufactured by Hiroshima Metal & Machinery Co., Ltd. (formerly Kotobuki Kogyo Co., Ltd.)), Attritor (manufactured by Nippon Coke & Engineering Co., Ltd.), or Pearl Mill (manufactured by Ashizawa Finetech Co., Ltd.). The rotation speed and reaction time of the apparatus for stirring the dispersion media may be appropriately adjusted according to the desired particle size, etc.
In the resulting dispersion (paint additive) in which dispersoid particles containing inorganic oxide particles and zinc cyanurate particles are dispersed in a liquid medium, the average particle size of the dispersoid particles as measured by a laser diffraction method can be, for example, 80 nm to 5,000 nm, or 80 nm to 2,000 nm, or 200 nm to 5,000 nm, or 80 nm to 1,000 nm, or 10 nm to 500 nm.
Furthermore, when the inorganic oxide particles are in the form of an inorganic oxide powder, in a dispersion in which dispersoid particles containing the obtained inorganic oxide powder and zinc cyanurate particles are dispersed in a liquid medium, the average particle size of the dispersoid particles as measured by a laser diffraction method can be, for example, 200 nm to 5,000 nm, or 300 nm to 5,000 nm, or 1,000 nm to 5,000 nm, or 1,000 nm to 3,0000, or 1,000 nm to 2,000 nm.

In the dispersion (paint additive), the inorganic oxide particles and the zinc cyanurate particles can have a mass ratio of inorganic oxide:zinc cyanurate of, for example, 1:0.01 to 100, or 1:0.1 to 10, or 1:1 to 10. In addition, in the dispersion (paint additive), the concentration of the total solid content (solid content of dispersoid particles) of the inorganic oxide particles and the zinc cyanurate particles can be, for example, 0.1% to 50% by mass, or 0.1% to 30% by mass, or 0.1% to 20% by mass, or 0.1% to 10% by mass.
The Brookfield viscosity of the dispersion (paint additive) can be, for example, 1 mPa·s to 500 mPa·s, 5 mPa·s to 500 mPa·s, 10 mPa·s to 300 mPa·s, or 50 mPa·s to 300 mPa·s.

Since zinc cyanurate dissolves in an acidic solution, it is desirable to adjust the pH of the solution to alkaline or neutral when mixing zinc cyanurate particles with inorganic oxide particles, and then perform a mixing operation (wet grinding process) of these particles. Furthermore, zinc cyanurate particles have a zeta potential of -10 mV to -1 mV at an alkaline or neutral pH.
Furthermore, when obtaining the above-mentioned dispersion liquid, for example, in the case of using inorganic oxide particles having an isoelectric point at pH 5 to pH 12 and a zeta potential of -80 mV to +80 mV in this pH range, a dispersion liquid with excellent dispersibility can be obtained by adjusting the pH to a pH range of -5 mV to -80 mV.
Alternatively, when obtaining the above-mentioned dispersion, by using inorganic oxide particles that do not have an isoelectric point at pH 5 to pH 12 and have a zeta potential of −5 mV to −50 mV in this pH range, a dispersion with excellent dispersibility can be obtained.
Furthermore, when obtaining the above-mentioned dispersion, when inorganic oxide particles that do not have an isoelectric point at pH 5 to 12 and have a zeta potential of +5 mV to +80 mV in this pH range are mixed with zinc cyanurate particles, a dispersion with excellent dispersibility can be obtained by adjusting the concentration of dispersoid particles containing inorganic oxide particles and zinc cyanurate particles to 0.1% by mass to 20% by mass, or 0.1% by mass to 10% by mass.
For example, in the case where the inorganic oxide particles to be mixed with zinc cyanurate particles are silica powders in the form of inorganic oxide powders, the mixing operation may be carried out by adjusting the concentration of dispersed particles containing silica powder and zinc cyanurate particles to 0.1% by mass to 20% by mass and the mass ratio of silica to zinc cyanurate (silica:zinc cyanurate) to 1:0.1 to 10. In the case of titanium oxide powder, when mixed with zinc cyanurate particles in an alkaline region from the isoelectric point, the concentration of dispersed particles containing titanium oxide powder and zinc cyanurate particles is adjusted to 0.1% by mass to 20% by mass and the mass ratio of titanium oxide to zinc cyanurate (titanium oxide:zinc cyanurate) to 1:0.1 to 10. In the case of aluminum oxide powder, when mixed with zinc cyanurate particles in an acidic region from the isoelectric point, the concentration of dispersed particles containing aluminum oxide powder and zinc cyanurate particles is adjusted to 0.1% by mass to 10% by mass. In the case of zirconium oxide powder, when it is mixed with zinc cyanurate particles in an alkaline region below the isoelectric point, it is preferable to adjust the concentration of dispersoid particles containing zirconium oxide powder and zinc cyanurate particles to 0.1% by mass to 20% by mass and the mass ratio of zirconium oxide to zinc cyanurate (zirconium oxide:zinc cyanurate) to 1:0.1 to 10, and then perform the mixing operation.
Furthermore, for example, in the case where the inorganic oxide particles to be mixed with zinc cyanurate particles are alumina sol in the form of colloidal oxide particles [metal oxide particles (metal oxide sol)], when they are mixed with zinc cyanurate particles in an acidic region from the isoelectric point, it is preferable to adjust the concentration of dispersoid particles containing alumina particles and zinc cyanurate particles to 0.1% by mass to 20% by mass and the mass ratio of alumina to zinc cyanurate (alumina:zinc cyanurate) to 1:1 to 10, and then perform the mixing operation. In the case of zirconia sol, when it is mixed with zinc cyanurate particles in an alkaline region from the isoelectric point, the dispersed particles containing zirconia particles and zinc cyanurate particles are adjusted to a concentration of 0.1 mass % to 30 mass %, and the mass ratio of zirconia to zinc cyanurate (zirconia:zinc cyanurate) is adjusted to 1:0.1 to 10. In the case of titania sol, when it is mixed with zinc cyanurate particles in an alkaline region from the isoelectric point, the dispersed particles containing titania particles and zinc cyanurate particles are adjusted to a concentration of 0.1 mass % to 30 mass %, and the mass ratio of zirconia to zinc cyanurate (zirconia:zinc cyanurate) is adjusted to 1:0.1 to 10. In the case of a tin oxide sol, when it is mixed with zinc cyanurate particles in an alkaline region below the isoelectric point, it is advisable to adjust the concentration of dispersoid particles containing tin oxide particles and zinc cyanurate particles to 0.1% by mass to 30% by mass and the mass ratio of tin oxide to zinc cyanurate (tin oxide:zinc cyanurate) to 1:0.1 to 10, and then perform the mixing operation in each case.

In the dispersion (paint additive) in which the obtained dispersoid particles containing inorganic oxide particles and zinc cyanurate particles are dispersed in a liquid medium, the liquid medium can be selected from an aqueous medium or an organic solvent, and the aqueous medium can be replaced with an organic solvent by an evaporation method using a rotary evaporator or the like.

The aqueous medium includes water.
Examples of the organic solvent that can be used include alcohols, glycols, esters, ketones, nitrogen-containing solvents, and aromatic solvents. Examples of these solvents include organic solvents such as methanol, ethanol, propanol, ethylene glycol, propylene glycol, glycerin, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, acetone, methyl ethyl ketone, dimethylformamide, N-methyl-2-pyrrolidone, toluene, xylene, and dimethylethane. In addition, polyethylene glycol, silicone oil, and reactive diluent solvents containing radically polymerizable vinyl groups or epoxy groups can also be used.

Furthermore, the surface of the inorganic oxide particles is treated with tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethoxydiphenylsilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, octyltriethoxysilane, trimethylmonoethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropyl It can be treated with a silane coupling agent such as methyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-isocyanatepropyltriethoxysilane, and hexamethyldisilazane.

The present invention also covers an embodiment in which dispersoid particles containing inorganic oxide particles and zinc cyanurate particles are dispersed in a liquid medium, the inorganic oxide particles being the inorganic oxide powder described above. That is, the present invention covers a dispersion in which dispersoid particles containing inorganic oxide powder and zinc cyanurate particles are dispersed in a liquid medium, the inorganic oxide powder having a specific surface area of 1 to 800 m2/g and a loose bulk density of 0.03 to 3.0 g/ ^cm3 .
As described above, the inorganic oxide powder is a powder of an oxide of at least one element selected from the group consisting of Si, Al, Ti, Zr, Fe, Cu, Zn, Li, Na, K, Mg, Ca, Cs, Sr, Ba, B, Ga, Y, Nb, Mo, In, Sn, Sb, Ta, W, Ge, Pb, P, As, Rb, Bi and Ce.
The inorganic oxide powder and zinc cyanurate particles contained in the present dispersion, their types, average particle sizes, production methods (apparatus, procedures, etc.), blending ratios in the dispersion, types of liquid media, etc. are as described above in the description of inorganic oxide particles and cyanuric acid particles, etc.
The average particle size and solid content concentration of the dispersoid particles in the dispersion, the manufacturing method of the dispersion, etc. are also as described above. Preferably, the dispersoid particles have an average particle size of 200 nm to 5,000 nm as measured by a laser diffraction method, and the dispersoid particles in the dispersion have a solid content concentration of 0.1 to 50 mass %.
Furthermore, the dispersion can be mixed with a resin emulsion described below to produce a coating composition.

Furthermore, the present invention also covers an embodiment in which, in the dispersion in which dispersoid particles containing inorganic oxide particles and zinc cyanurate particles are dispersed in a liquid medium, the inorganic oxide particles are colloidal metal oxide particles excluding particles mainly composed of colloidal silica.
That is, the present invention is directed to a dispersion in which colloidal metal oxide particles, excluding particles mainly composed of colloidal silica, and zinc cyanurate particles are dispersed as dispersoid particles in a liquid medium.
The colloidal metal oxide particles are the above-mentioned colloidal inorganic oxide particles excluding particles mainly composed of colloidal silica, that is, the colloidal metal oxide particles are particles containing an oxide of at least one element selected from the group consisting of Al, Ti, Zr, Fe, Cu, Zn, Li, Na, K, Mg, Ca, Cs, Sr, Ba, B, Ga, Y, Nb, Mo, In, Sn, Sb, Ta, W, Ge, Pb, P, As, Rb, Bi and Ce.
The colloidal metal oxide particles contained in this dispersion are the same as those described above in terms of type, average particle size, production method, proportion in the dispersion, etc., as those of the aforementioned colloidal inorganic oxide particles, except for the particles mainly composed of colloidal silica. The type, average particle size, production method (apparatus, procedure, etc.), blending ratio in the dispersion, and type of liquid medium of the zinc cyanurate particles are also the same as those described above.
The average particle size and solid content concentration of the dispersoid particles in the dispersion, the manufacturing method of the dispersion, etc. are also as described above. Preferably, the dispersoid particles have an average particle size of 80 nm to 2,000 nm as measured by a laser diffraction method, and the dispersoid particles in the dispersion have a solid content concentration of 0.1 to 50 mass %.
In addition, the particles mainly composed of colloidal silica, which are not included in the colloidal metal oxide particles, refer to colloidal particles composed only of silica (SiO ₂ ) or colloidal particles whose main component (for example, 50% by mass) is silica, and these particles are excluded in this embodiment. However, it is possible to contain silica as one component of the composite oxide particles or as one component of the coating material listed in the modified inorganic oxide particles, and in this case, the silica content can be more than 0% by mass and 30% by mass or less with respect to the total mass of the composite oxide particles and the modified inorganic oxide particles.
Furthermore, the dispersion can be mixed with a resin emulsion described below to produce a coating composition.

[resin]
Examples of the resin used in the coating composition of the present invention include one or more resins selected from the group consisting of acrylic resins, acrylic-styrene resins, acrylic-silicone resins, vinyl acetate resins, styrene resins, olefin resins (ethylene resins, propylene resins, etc.), ethylene-vinyl acetate resins, ester resins, epoxy resins, phenol resins, amide resins, vinyl alcohol resins, fluorine resins, urethane resins, melamine resins, phthalic acid resins, silicone resins, alkyd resins and vinyl chloride resins.
For example, "acrylic resin" refers to a resin having a structure derived from an acrylic acid ester (and a methacrylic acid ester) in the resin, and may also have a structure derived from another polymerizable compound in the resin. As an example, an acrylic resin complexed with polysiloxane (referred to as "acrylic (polysiloxane complex)") and an acrylic resin having a structure derived from vinyl acetate (referred to as "acetic acid-acrylic") can be classified as an acrylic resin. In addition, there is a resin having an epoxy-derived and ester-derived structure (referred to as "epoxy-ester"), and this resin can be classified as either an epoxy-based resin or an ester-based resin, but is classified as an epoxy-based resin in this specification.
For example, "acrylic-styrene resin" can be written as "styrene-acrylic resin", and even when the resin names are interchanged in this way, they can be treated as synonyms.

[Resin morphology]
Generally, the form (classification) of the resin component used in the paint can be, for example, a water-soluble polymer (also simply referred to as a water-soluble polymer or a water-soluble resin) or a water-dispersed polymer. The form of the water-dispersed polymer can be, for example, a colloidal dispersion or a resin emulsion, and the resin emulsion can be, for example, an oil-in-water emulsion or a water-in-oil emulsion. The resin composition of the present invention can also use the above various forms, and the above various resins can be used as the resin component.
In general, water-soluble polymers have, for example, a particle size of 0.01 μm or less and a molecular weight of 10 ³ to 10 ⁴ , and when used in a coating composition, a coating with high gloss is obtained, and are used in applications requiring baking at high temperatures. Colloidal dispersions have, for example, a particle size of 0.01 to 0.1 μm and a molecular weight of 10 ⁴ to 10 ⁶ , and when used in a coating composition, a coating with high gloss is obtained, and are used in applications requiring baking at high temperatures or applications requiring drying at room temperature. Resin emulsions have, for example, a particle size of 0.05 μm or more and a molecular weight of 10 ³ or more, and the coating composition dries quickly, and a coating with high water resistance is obtained, and are used in applications requiring baking or applications requiring drying at room temperature.
The form of the resin can be appropriately selected depending on the application of the coating composition, but from the viewpoints of stability and handling of the coating composition, it is preferable to use it in the form of a resin emulsion, and an oil-in-water resin emulsion (also called an aqueous resin emulsion) is more preferable.
Among these, preferred resin emulsions are aqueous resin emulsions having a pH of 7 to 10 or 3 to 6.5, a solid content (proportion of resin components) in the resin emulsion of 30% by mass to 65% by mass, and a viscosity in the range of approximately 20 mPa·s to 20,000 mPa·s.

Examples of acrylic resin emulsions include products manufactured by Japan Coating Resins Co., Ltd. under the trade names Mowinyl DM772, Mowinyl 6520, and Mowinyl 6530 (all of which are anionic resin emulsions), and products manufactured by DIC Corporation under the trade name Boncoat 40-418EF; examples of acrylic (polysiloxane composite) resin emulsions that can be classified as acrylic resin emulsions include products manufactured by DIC Corporation under the trade name Ceranate WHW-822; and examples of acetic acid-acrylic resin emulsions that can also be classified as acrylic resin emulsions include products manufactured by DIC Corporation under the trade name Boncoat CF-2800.
Examples of the acrylic-styrene-based resin emulsion include products manufactured by Japan Coating Resins Co., Ltd. under the trade names Mowinyl DM60, Mowinyl 749E, and LDM6740 (all of which are anionic resin emulsions), and products manufactured by DIC Corporation under the trade name Boncoat CG-8680.
Examples of the acrylic-silicone resin emulsion include trade name LDM7523 (anionic resin emulsion) manufactured by Japan Coating Resins Co., Ltd., and trade name Boncoat SA-6360 manufactured by DIC Corporation.
Examples of vinyl acetate resin emulsions include Movinyl 206 (a nonionic resin emulsion) manufactured by Japan Coating Resins Co., Ltd. and Polysol S-65 (a nonionic resin emulsion) manufactured by Showa Denko KK.
An example of the ethylene-vinyl acetate resin emulsion is Movinyl 109E (nonionic resin emulsion) manufactured by Japan Coating Resins Co., Ltd.
An example of the ester resin emulsion is Eliteru KA-3556 manufactured by Unitika Ltd.
An example of an epoxy resin emulsion is EPICLON H-502-42W (trade name) manufactured by DIC Corporation; an example of an epoxy-ester resin emulsion that can be classified as an epoxy resin emulsion is Watersol EFD-5530 (trade name) manufactured by DIC Corporation.
Examples of olefin-based (ethylene-based) resin emulsions include PE-381 manufactured by Naruse Chemical Co., Ltd.
An example of the fluorine-based resin emulsion is SIFCLEARF-104 manufactured by E-Tech Co., Ltd.
Examples of urethane resin emulsions include Hydran HW-171 (trade name) manufactured by DIC Corporation, and NeoRez R-967 (trade name) manufactured by DSM Coating Resins.
An example of the alkyd resin emulsion is Watersol S-118 manufactured by DIC Corporation.
An example of the vinyl chloride resin emulsion is Vinyblan VE-701 manufactured by Nissin Chemical Industry Co., Ltd.

Among the above resin emulsions, acrylic resin emulsions, acrylic-styrene resin emulsions, acrylic-silicone resin emulsions, vinyl acetate resin emulsions, epoxy resin emulsions, and urethane resin emulsions are preferred.

The coating composition of the present invention may further contain a slurry of an inorganic oxide powder.
The inorganic oxide powder used in the slurry may be any of the inorganic oxide particles used in the paint additive described above in powder form. The atomic species of the inorganic oxide particles used in the paint additive (dispersion liquid) and the atomic species of the inorganic oxide powder used in the slurry may be the same or different, and the inorganic oxide powder used in the slurry may be one type or multiple types. The medium used in the slurry may also be the same as the liquid medium used in the paint additive described above.
The slurry can be prepared by mixing the inorganic oxide powder in a liquid medium using a submerged disperser described below. Alternatively, the powder may be mixed using a grinding device similar to the device used for wet dispersion of zinc cyanurate using the above-mentioned dispersion medium, or these may be used in combination.
The inorganic oxide powder slurry has a solid content of 0.1% by mass to 50% by mass, for example, 0.1% by mass to 30% by mass, or 0.1% by mass to 20% by mass.

The coating composition can be prepared so that the ratio of the solids in the dispersion (coating additive) to the resin (in the case of a resin emulsion, the resin in the emulsion) and the solids in the inorganic oxide powder slurry is 1:0.1 to 20:0 to 1, for example 1:0.1 to 15:0 to 1, or 1:0.1 to 10:0 to 0.5, in terms of mass ratio of (solids in the dispersion):(resin (in the case of a resin emulsion, the resin in the emulsion)):(solids in the slurry), and the proportion of the total solids in the coating composition is 1% by mass to 70% by mass, or 1% by mass to 50% by mass, or 1% by mass to 30% by mass. In addition, when an inorganic oxide powder slurry is included, the lower limit of the proportion of solids in the slurry can be 0.1 relative to the solids (mass ratio) in the dispersion (coating additive) of 1.

The paint composition of the present invention can be obtained by mixing a dispersion of the above-mentioned inorganic oxide particles and zinc cyanurate particles (paint additive), the above-mentioned resin (e.g., a resin emulsion), and, if used, a slurry of inorganic oxide powder, using a submerged disperser.

Submerged dispersers used in the production of the coating composition include stirrers, rotary shear stirrers, colloid mills, roll mills, high-pressure jet dispersers, ultrasonic dispersers, vessel-driven mills, media stirring mills, and kneaders.
An agitator is the simplest dispersing device, and can disperse the target material by speed fluctuations near the agitating blades or by collisions with the agitating blades.
A rotary shear type agitator is a device that disperses materials by passing them through a narrow gap between a high-speed rotating blade and an outer cylinder, and can disperse the target material by using the shear flow and speed fluctuations in the gap.
Colloid mills can disperse the target substance by using shear flow in the narrow gap between a high-speed rotating disk and a fixed disk.
A roll mill can disperse a target substance by using shearing force and compressive force that utilize the gap between two or three rotating rolls.
A high-pressure jet disperser can disperse the target material by jetting a treatment liquid at high pressure and causing it to collide with a fixed plate or with other treatment liquids.
An ultrasonic disperser can disperse a target substance by using ultrasonic vibration.
A vessel-driven mill is a device that disperses a target substance by collision and friction of media (balls) inserted in a fixed vessel, and examples of such mills include rotary mills, vibration mills, and planetary mills.
A media agitation mill is a device that uses balls or beads as a medium to disperse the target material by the impact force and shear force of the medium, and examples of such a mill include an attritor and a bead mill.

A paint composition obtained by mixing the above-mentioned inorganic oxide particles and zinc cyanurate particle dispersion (paint additive) with a resin (and further with a slurry of inorganic oxide powder, if used) can be produced at a pH range of, for example, 7 to 10. The pH can be adjusted to a range of 10 to 11 by adding 100 ppm to 10,000 ppm of ammonia water as an alkaline component. Furthermore, a paint composition mixed with a resin (e.g., a resin emulsion) having a pH of 3 to 6.5 can be produced at a pH range of 3 to 6.5. When mixing inorganic oxide particles and zinc cyanurate particles (when preparing the dispersion), it is preferable to adjust the pH to alkaline or neutral, but the paint composition can be produced and used at an alkaline or acidic pH.

[Other additives]
In addition to the dispersion of inorganic oxide particles and zinc cyanurate particles, and resin (and further a slurry of inorganic oxide powder, if used), the coating composition of the present invention may also contain a mixture of conventional additives used in conventional coatings (compositions), such as curing-accelerating catalysts, pigments, leveling agents, antioxidants, ultraviolet absorbers, light stabilizers, plasticizers, surfactants, and other various additives used in the relevant technical field, within the scope of the invention.
Furthermore, when it is desired to further increase the hardness of the coating film of the coating composition of the present invention, the composition and blending components can be appropriately adjusted according to the purpose by adding a curing agent, a thickener, a dispersant, or an antifoaming agent as an optional component, appropriately adjusting (increasing) the content of inorganic oxide particles, or selecting a resin type of the resin emulsion from a fluorine-based, epoxy-based, or the like (or using or mixing these resin types in combination).

The B-type viscosity of the coating composition can be, for example, 10 mPa·s to 100 mPa·s. Furthermore, depending on the application and substrate of the coating composition, for example, if a thick film is desired, the viscosity can be increased by selecting a resin type with a high viscosity (for example, the resin type of the resin emulsion) or by adding a thickener.

[Applicable Locations]
The object to which the coating composition of the present invention is applied, i.e., the surface to be coated, is not particularly limited, but examples thereof include aluminum substrates, iron-based substrates, copper-based substrates, gold-based substrates, silver-based substrates, platinum-based substrates, mirror materials, glass substrates, silicon substrates, wood, resin films, and resin moldings.
The coating composition is applied to these substrates, dried, and then appropriately cured (thermal curing/photocuring) to form a coating film. The thickness of the coating film of the coating composition varies depending on the viscosity of the coating composition, but can be set in the range of 0.1 μm to 100 μm, for example. The coating film is not particularly limited as long as it has a hardness that does not cause problems in the processing step of the substrate, and the hardness can be appropriately set depending on the type of substrate.
Examples of the coating method include spin coating, bar coating, roll coating, and dip coating. By these methods, a spin-coated film, a bar-coated film, a roll-coated film, or a dip-coated film can be obtained.
Hereinafter, for each substrate, an example of the application, a suitable resin type in the coating composition, and drying conditions after coating on the substrate will be exemplified, but the invention is not limited to these.

Aluminum substrates are used for applications such as building materials, home appliances, and interior panels.
Suitable types of resins in coating compositions for aluminum substrates include acrylic resins (including acrylic (polysiloxane composite) resins, acetate-acrylic resins, etc.), acrylic-styrene resins, acrylic-silicone resins, vinyl acetate resins, olefin resins (including ethylene resins, etc.), ester resins, epoxy resins (including epoxy-ester resins, etc.), fluorine resins, urethane resins, alkyd resins, vinyl chloride resins, etc.
The drying conditions can be 200° C. to 300° C. (heat drying).

The iron-based substrate includes not only substrates consisting of only iron (Fe), but also substrates containing iron (Fe) and other elements (carbon (C), silicon (Si), manganese (Mn), chromium (Cr), molybdenum (Mo), phosphorus (P), sulfur (S), tungsten (W), vanadium (V), nickel (Ni), aluminum (Al), niobium (Nb), nitrogen (N), etc.).
The iron-based substrates are used for applications such as building materials, structures, home appliances, and machinery (steel sheet types: stainless steel sheets, mild steel sheets, galvanized steel sheets, electromagnetic steel sheets, etc.).
Suitable types of resins in coating compositions for iron-based substrates include acrylic resins (including acrylic (polysiloxane composite) resins, acetate-acrylic resins, etc.), acrylic-styrene resins, acrylic-silicone resins, vinyl acetate resins, styrene resins, olefin resins (ethylene resins, etc.), ester resins, epoxy resins, fluorine resins, urethane resins, alkyd resins, etc.
The drying conditions can be from 20° C. to 400° C. (room temperature drying, heated drying).

Copper-based and silver-based substrates also include substrates with metal surface treatments.
Copper-based and silver-based substrates are used for applications such as electronic materials (substrates, wiring, bonding wires), electromagnetic shields, and electric wires.
Examples of the types of resins suitable for use in coating compositions for copper- and silver-based substrates include acrylic resins (including acrylic (polysiloxane composite) resins, acetate-acrylic resins, etc.), acrylic-styrene resins, vinyl acetate resins, styrene resins, olefin resins (ethylene resins, propylene resins, etc.), phenol resins, epoxy resins, fluorine resins, and urethane resins.
Drying and curing conditions include curing by ultraviolet irradiation, electron beam irradiation, and curing by thermal polymerization (40 to 230° C.).

Metal-based substrates also include substrates that have been subjected to a metal surface treatment.
Metal-based substrates are used for applications such as electronic materials (bonding wires for ICs, LSIs, and transistors).
Suitable types of resins in coating compositions for metal substrates include acrylic resins, styrene resins, olefin resins (ethylene resins, propylene resins, etc.), epoxy resins, and fluorine resins.
Drying and curing conditions include curing by ultraviolet irradiation, electron beam irradiation, and curing by thermal polymerization (40 to 80° C.).

Platinum-based substrates also include substrates that have been subjected to a metal surface treatment.
Platinum-based substrates are used for applications such as sensors, electrodes, and catalysts.
Suitable types of resins in coating compositions for platinum-based substrates include fluororesins and urethane resins.
The drying conditions can be 100° C. to 400° C. (heat drying).

Mirror materials are used for purposes such as mirrors.
Suitable types of resins in coating compositions for mirror materials include acrylic resins, phenolic resins, alkyd resins, ester resins, epoxy resins, and urethane resins.
The drying conditions can be 150° C. to 200° C. (heat drying).

Glass substrates are used in applications such as smartphones, solar cells, semiconductors, building materials, and car windows.
Suitable types of resins in coating compositions for glass substrates include acrylic resins, phenolic resins, fluorine resins, epoxy resins, silicone resins, and the like.
The drying conditions can be 80° C. to 400° C. (heat drying).

Silicon substrates are used in applications such as solar cells and semiconductors.
Suitable types of resins in coating compositions for silicon substrates include acrylic resins, ester resins, urethane resins, styrene resins, amide resins, vinyl alcohol resins, vinyl acetate resins, and the like.
Drying and curing conditions include curing by ultraviolet irradiation, electron beam irradiation, and curing by thermal polymerization (100° C. to 300° C.).

Wood is used for building materials, furniture, and other purposes.
Suitable types of resins in paint compositions for wood include acrylic resins (including acetate-acrylic resins, etc.), acrylic-styrene resins, vinyl acetate resins, olefin resins (ethylene resins, etc.), phenol resins, ester resins, epoxy resins, fluorine resins, urethane resins, silicone resins, alkyd resins, and the like.
The drying conditions can be 20° C. to 50° C., or 20° C. to 100° C. (heat drying).

Examples of resin types in resin films and resin moldings include epoxy, melamine, polyurethane, polyimide, polyamideimide, polyethylene, polypropylene, Teflon (registered trademark) (polytetrafluoroethylene), acrylic, acrylonitrile styrene (AS), acrylonitrile butadiene styrene (ABS), polyvinyl chloride, polycarbonate, polyester, PET, and cycloolefin.
Resin films and resin moldings are used for applications such as smartphones, agricultural films, and electronic materials (substrates and sealing materials).
Suitable types of resins in coating compositions intended for resin films and resin molded products include acrylic resins (including acrylic (polysiloxane composite) resins, acetate-acrylic resins, etc.), acrylic-styrene resins, vinyl acetate resins, styrene resins, olefin resins (ethylene resins, propylene resins, etc.), phenol resins, epoxy resins, urethane resins, fluorine resins, alkyd resins, etc.
The drying and curing conditions include curing by ultraviolet irradiation, electron beam irradiation, and curing by thermal polymerization (40 to 80°C). Heat drying at 40 to 60°C is also possible.

In addition, in a coating composition containing a resin (e.g., a resin emulsion) and a dispersion in which dispersoid particles including the inorganic oxide powder and zinc cyanurate particles described above are dispersed in a liquid medium, and in a coating composition containing a dispersion in which dispersoid particles including colloidal metal oxide particles (excluding particles mainly composed of colloidal silica) and zinc cyanurate particles are dispersed in a liquid medium, the resins that can be used (type of resin, form of resin), the ratio of each component in the composition, the method for producing the composition (equipment, procedure, etc.), other components and additives that can be added, and application sites are the same as those listed for the paint composition described above.

The present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples.

The components used in the dispersion and coating composition were prepared according to the following procedure, and the average particle size of the inorganic oxide particles and dispersoid particles, the specific surface area, loose bulk density and zeta potential of the inorganic oxide powder, and the viscosity of the coating composition were measured.

(1) The following inorganic oxide particles were prepared.
Colloidal silica: aqueous silica sol (manufactured by Nissan Chemical Industries, Ltd., product name Snowtex ST-N-40, specific surface area by BET method 122.5 m ² /g, pH 9.4, solid content 40.4 mass%, average particle size by dynamic light scattering method 34.5 nm)
Silica powder: fumed silica A (manufactured by Nippon Aerosil Co., Ltd., product name AEROSIL (registered trademark) 300, specific surface area by BET method 253.2 m ² /g)
Silica powder: fumed silica B (manufactured by Nippon Aerosil Co., Ltd., product name AEROSIL (registered trademark) 50, specific surface area by BET method 45.8 m ² /g)
Silica powder: Silica powder C (Fuji Silysia Co., Ltd., product name Sylysia 380, specific surface area by BET method: 229.7 m ² /g)
Titania powder: Titania powder (Sakai Chemical Industry Co., Ltd., product name R-25, specific surface area by BET method 44.2 m ² /g, surface treated with Al ₂ O ₃ )
- Aqueous alumina sol (colloidal alumina) (manufactured by Nissan Chemical Industries, Ltd., product name AS-200, pH 4.6, solid content 10.3 mass%, average particle size measured by dynamic light scattering method 244 nm)
Aqueous zirconia sol (colloidal zirconia) (Nissan Chemical Industries, Ltd., product name Nanouse (registered trademark) ZR-30BS, pH 9.8, solid content 30.5 mass%, average particle size by dynamic light scattering method 60.2 nm)
・Aqueous titania sol (colloidal titania)
126.2 g of pure water was placed in a 1-liter container, and 17.8 g of metastannic acid (containing 15 g in terms of _SnO2 ), 284 g of titanium tetraisopropoxide (containing 80 g in terms of _TiO2 ), 84 g of oxalic acid dihydrate (containing 70 g in terms of oxalic acid), and 438 g of a 35% by mass tetraethylammonium hydroxide aqueous solution were added under stirring. The resulting mixed solution had a molar ratio of oxalic acid/titanium atom of 0.78 and a molar ratio of tetraethylammonium hydroxide/titanium atom of 1.04. 950 g of the mixed solution was held at 80°C for 2 hours, and then further reduced in pressure to 580 Torr and held for 2 hours to prepare a titanium mixed solution. The prepared titanium mixed solution had a pH of 4.7, an electrical conductivity of 27.2 mS/cm, and a _TiO2 concentration of 8.4% by mass.
950g of the titanium mixed solution and 950g of pure water were put into a 3-liter glass-lined autoclave vessel, and hydrothermal treatment was carried out at 140°C for 5 hours. After cooling to room temperature, the solution after hydrothermal treatment was taken out and was a pale milky white aqueous titania sol. The obtained aqueous titania sol had a pH of 3.9, an electrical conductivity of 19.7mS/cm, a _TiO2 concentration of 4.2% by mass, tetraethylammonium hydroxide of 4.0% by mass, and oxalic acid of 1.8% by mass, and a particle size of 16nm by dynamic light scattering method.
・Aqueous tin oxide sol (tin oxide sol)
37.5 kg of oxalic acid ((COOH) _2.2H2O ) was dissolved in 220 kg of pure water, placed in _a ^0.5 m3 GL vessel, and heated to 70°C with stirring, after which 150 kg of 35% hydrogen peroxide and 75 kg of metallic tin powder (AT-SnNO200N, manufactured by Yamaishi Metals Co., Ltd., containing 99.7% _SnO2 ) were added. The hydrogen peroxide and metallic tin were added alternately in 15 separate additions. First, 10 kg of 35% hydrogen peroxide was added, followed by 5 kg of metallic tin. This operation was repeated after waiting for the reaction to finish (10 to 15 minutes).
The time required for the addition was 2.5 hours, and after the addition was completed, the reaction was terminated by heating for 1 hour while maintaining the liquid temperature at 90° C. The ratio of hydrogen peroxide to metallic tin was H ₂ O ₂ /Sn molar ratio of 2.44. The obtained aqueous tin oxide had a specific gravity of 1.22, a pH of 1.49, SnO ₂ of 26.1 mass%, an oxalic acid concentration from the charge of 7.6 mass%, and a (COOH) ₂ /SnO ₂ molar ratio of 0.47.
The particle diameter of the tin oxide colloid was 10-15 nm under an electron microscope, and the particles were spherical and well-dispersed. 230 kg of stannic oxide sol was dispersed in 1100 kg of water, and then 3.0 kg of isopropylamine was added thereto. The liquid was then passed through a column packed with a hydroxyl-type anion exchange resin to make it alkaline. The sol was then heated and aged at 90°C, and passed through a column packed with anion exchange resin again to obtain 1431 kg of an alkaline aqueous tin oxide sol. The obtained sol was stable and very transparent, with a specific gravity of 1.034, a pH of 11.33, an _SnO2 content of 4.04% by mass, an isopropylamine content of 0.21% by mass, and a particle diameter of 20 nm as measured by dynamic light scattering.

(2) Zinc cyanurate particles (CA particles) were prepared.
Zinc cyanurate particles A: manufactured by Nissan Chemical Industries, Ltd., product name Starfine (registered trademark) (average particle size measured by laser diffraction method: 1.7 μm, major axis of primary particles measured by transmission electron microscope: 400-600 nm, minor axis: 50-70 nm, major axis/minor axis ratio: 5.7-12, specific surface area: 15 m ² /g, molar ratio (zinc oxide)/(cyanuric acid) of 2.5)
Zinc cyanurate particles B: Starfine (registered trademark), manufactured by Nissan Chemical Industries, Ltd. (average particle size measured by laser diffraction method: 55 μm, long axis of primary particles measured by transmission electron microscope: 1,000 to 2,000 nm, short axis: 100 to 300 nm, long axis/short axis ratio: 3.3 to 20, specific surface area: 10 m ² /g, molar ratio (zinc oxide)/(cyanuric acid) of 2.5)

(3) An oil-in-water resin emulsion was prepared.
Acrylic resin emulsion: manufactured by DIC Corporation, product name Boncoat 40-418EF, resin concentration 55.5% by mass, pH 7.3
Acrylic-styrene resin emulsion A: manufactured by DIC Corporation, product name Boncoat CG-8680, resin concentration 50.0% by mass, pH 8.4
Acrylic-styrene resin emulsion B: Japan Coating Resin Co., Ltd., product name Movinyl DM-60, resin concentration 48.3% by mass, pH 7.5
Acrylic (polysiloxane composite) resin emulsion: manufactured by DIC Corporation, product name Ceranate WHW-822, resin concentration 35.0% by mass, pH 8.1
Acrylic-silicone resin emulsion: Japan Coating Resin Co., Ltd., product name LDM7523, resin concentration 47.2% by mass, pH 8.0
Urethane resin emulsion A: manufactured by DIC Corporation, product name Hydran HM-171, resin concentration 35.8% by mass, pH 8.2
Urethane resin emulsion B: manufactured by DSM Coating Resins, product name NeoRez R-967, resin concentration 39.7% by mass, pH 8.0
Epoxy resin emulsion: manufactured by DIC Corporation, product name EPICLON H-502-42W, resin concentration 39.3% by mass, pH 9.1
Epoxy-ester resin emulsion: manufactured by DIC Corporation, product name Watersol EFD-5530, resin concentration 37.0% by mass, pH 9.1
Alkyd resin emulsion: manufactured by DIC Corporation, product name Watersol S-118, resin concentration 60.0% by mass, pH 9.2
Acetic acid-acrylic resin emulsion: manufactured by DIC Corporation, product name Boncoat CF-2800, resin concentration 50.0% by mass, pH 4.7
Vinyl acetate resin emulsion: Showa Denko K.K., product name Polysol S-65, resin concentration 50.5% by mass, pH 5.0
Vinyl chloride resin emulsion: manufactured by Nissin Chemical Industry Co., Ltd., product name Vinyblan VE-701, resin concentration 30.9% by mass, pH 7.7
Olefin-based (ethylene-based) resin emulsion: manufactured by Naruse Chemical Co., Ltd., product name PE-381, resin concentration 50.0% by mass, pH 8.0
Fluorine-based resin emulsion: manufactured by E-Tech Co., Ltd., product name SIFCLEARF-104, resin concentration 46.8% by mass, pH 7.8
Ester resin emulsion: manufactured by Unitika Ltd., product name Eliteru KA-3556, resin concentration 29.2% by mass, pH 8.0

(4) An inorganic oxide powder slurry was prepared.
(4-1) Preparation of fumed silica A slurry 50 g of fumed silica A and 450 g of pure water were placed in a 500 ml polypropylene container, and a mixed slurry ( _SiO2 concentration 10 mass%) was prepared while stirring with a stirrer equipped with a turbine blade. Next, 150 g of the slurry A and 180 g of glass beads having a diameter of 0.7 to 1.0 mm were placed in a 250 ml polypropylene container, and the container was placed on a ball mill rotating table set at a rotation speed of 165 rpm and wet-milled for 30 hours to obtain a fumed silica A slurry.
(4-2) Preparation of titania powder slurry 50 g of titania powder and 450 g of pure water were placed in a 500 ml polypropylene container, and a mixed slurry ( _TiO2 concentration 10 mass%) was prepared while stirring with a stirrer equipped with a turbine blade. Next, 150 g of the slurry and 180 g of glass beads having a diameter of 0.7-1.0 mm were placed in a 250 ml polypropylene container, and the container was placed on a ball mill rotating table set at a rotation speed of 165 rpm and wet-milled for 30 hours to obtain a titania powder slurry.
(4-3) Preparation of fumed silica B slurry 50 g of fumed silica B and 450 g of pure water were placed in a 500 ml polypropylene container, and a mixed slurry ( _SiO2 concentration 10 mass%) was prepared while stirring with a stirrer equipped with a turbine blade. Next, 150 g of the slurry and 180 g of glass beads having a diameter of 0.7-1.0 mm were placed in a 250 ml polypropylene container, and the container was placed on a ball mill rotating table set at a rotation speed of 165 rpm and wet-milled for 30 hours to obtain fumed silica B slurry.
(4-4) Preparation of Silica Powder C Slurry 50 g of Silica Powder C and 450 g of pure water were placed in a 500 ml polypropylene container, and a mixed slurry ( _SiO2 concentration 10 mass%) was prepared while stirring with a stirrer equipped with a turbine blade. Next, 150 g of the slurry and 180 g of glass beads with a diameter of 0.7-1.0 mm were placed in a 250 ml polypropylene container, and the container was placed on a ball mill rotating table set to a rotation speed of 165 rpm and wet-milled for 30 hours to obtain Silica Powder C slurry.

(5) The average particle size of the inorganic oxide particles was measured by the following procedure.
(5-1) The average particle size of the colloidal inorganic oxide particles was measured by dynamic light scattering.
The dispersion of colloidal inorganic oxide particles was diluted with pure water, and then the parameters of each inorganic oxide were used to measure the dispersion using a dynamic light scattering measuring device: Zetasizer manufactured by Malvern Instruments Ltd.
(5-2) The average particle size of inorganic oxide powders (silica powder, titania powder) was measured by laser diffraction method.
The inorganic oxide powder was dispersed in pure water to prepare a dispersion, and then the measurement was performed using a product name SALD-7500 nano manufactured by Shimadzu Corporation. Here, as the substitution value for the refractive index, [1.45-0.00i] was used for the silica powder, and [2.55-0.00i] was used for the titania powder.

(6) Among the inorganic oxide particles, the specific surface area and the loose bulk density of the inorganic oxide powders (silica powder and titania powder) were measured.
(6-1) Specific Surface Area A suitable amount of inorganic oxide powder was placed in a quartz measurement cell and dried at 300° C. for 1 hour, and the specific surface area was measured by the BET method using Monosorb manufactured by Yuasa Ionics Co., Ltd.
(6-2) Loose bulk density The loose bulk density was measured using a Powder Tester PT-X manufactured by Hosokawa Micron Corp. An inorganic oxide powder was placed in the sieve of the Powder Tester PT-X, and the powder was dropped through a chute while being vibrated, and the density was measured when the powder was received in a 100 ^cm3 container.
(6-3) Zeta Potential Measurement 1 g of inorganic oxide powder was added to 100 g of pure water and dispersed with a magnetic stirrer to obtain an inorganic oxide powder slurry. An appropriate amount of this was placed in a measurement cell, and the zeta potential was measured by electrophoretic light scattering using ELSZ-2000 manufactured by Otsuka Electronics Co., Ltd.
The zeta potential was measured using an automatic titrator (ELSZ-PT manufactured by Otsuka Electronics Co., Ltd.) and using 0.1 mol/L hydrochloric acid (manufactured by Kanto Chemical Co., Ltd.) and 0.1 mol/L sodium hydroxide (manufactured by Kanto Chemical Co., Ltd.) as titration reagents to adjust the pH of the inorganic oxide powder slurry to a range of 2 to 10, and the zeta potential was measured at each pH. The measurement results are shown in FIG. 1.

(7) The average particle size of the dispersed particles was measured by laser diffraction.
A dispersion liquid containing inorganic oxide particles and zinc cyanurate particles was diluted with pure water, and then the measurement was performed using a product name SALD-7500 nano manufactured by Shimadzu Corporation, where [1.70-0.2i] was used as the substitution value for the refractive index.

(8) The Brookfield viscosity of the coating composition was measured according to the following method.
The coating composition was poured into a 100 mL resin container, and the viscosity was measured with a B-type viscometer (BII type viscometer manufactured by Toki Sangyo Co., Ltd.) using a No. 2 rotor.

[Example 1]
99 g of aqueous silica sol and 261 g of pure water were placed in a 500 ml polypropylene container, and 40 g of zinc cyanurate particles A were added while stirring with a stirrer equipped with a turbine blade to prepare a mixed slurry ( _SiO2 concentration 10.0 mass%, zinc cyanurate concentration 10.0 mass%). Next, 150 g of the mixed slurry and 180 g of glass beads having a diameter of 0.7-1.0 mm were placed in a 250 ml polypropylene container, and the container was placed on a ball mill rotating table set to a rotation speed of 165 rpm and wet-pulverized for 30 hours to obtain a dispersion liquid 1, which was used as paint additive 1. It was confirmed that paint additive 1 maintained a good dispersion state by visually observing no precipitated layer after standing at room temperature for 12 hours.
The resulting paint additive 1 had a solids content (silica + zinc cyanurate) concentration of 20 mass %, and an average particle size measured by laser diffraction method of 135 nm.
Into a 250 ml polypropylene container, 42.7 g of pure water, 0.5 g of 28% _NH3 , 29.5 g of the paint additive 1, and 99.6 g of an acrylic resin emulsion (product name Boncoat 40-418EF) were added, and the mixture was stirred for 1 hour with a stirrer equipped with a turbine blade to obtain paint composition 1.
The resulting coating composition 1 had a solids concentration of 35.5% by mass, a pH of 9.1, and a Brookfield viscosity of 21 mPa·s.

[Example 2]
16 g of fumed silica A and 344 g of pure water were placed in a 500 ml polypropylene container, and 40 g of zinc cyanurate particles A were added while stirring with a stirrer equipped with a turbine blade to prepare a mixed slurry ( _SiO2 concentration 4.0 mass%, zinc cyanurate concentration 10.0 mass%). Next, 150 g of the mixed slurry and 180 g of glass beads having a diameter of 0.7-1.0 mm were placed in a 250 ml polypropylene container, and the container was placed on a ball mill turntable set to a rotation speed of 165 rpm and wet-milled for 30 hours to obtain a dispersion liquid 2, which was used as paint additive 2. It was confirmed that paint additive 2 maintained a good dispersion state by visually observing no precipitated layer after standing at room temperature for 12 hours.
The resulting paint additive 2 had a solids concentration (silica + zinc cyanurate) of 14 mass %, a pH of 6.3, and an average particle size of the dispersed particles measured by laser diffraction method of 306 nm.
24.9 g of pure water, 0.5 g of 28% _NH3 , 29.5 g of the coating additive 2, 17.7 g of a 10% by mass fumed silica slurry wet-ground in a ball mill for 30 hours, and 99.6 g of an acrylic resin emulsion (product name Boncoat 40-418EF) were added to a 250 ml polypropylene container, and the mixture was stirred for 2 hours with a stirrer equipped with a turbine blade to obtain coating composition 2.
The resulting coating composition 2 had a solids concentration of 35.5% by mass, a pH of 8.9 and a Brookfield viscosity of 56 mPa·s.

[Example 3]
16 g of titania powder and 344 g of pure water were placed in a 500 ml polypropylene container, and 40 g of zinc cyanurate particles A were added while stirring with a stirrer equipped with a turbine blade to prepare a mixed slurry ( _TiO2 concentration 4.0 mass%, zinc cyanurate concentration 10.0 mass%). Next, 150 g of the mixed slurry and 180 g of glass beads having a diameter of 0.7-1.0 mm were placed in a 250 ml polypropylene container, and the container was placed on a ball mill turntable set to a rotation speed of 165 rpm and wet-pulverized for 30 hours to obtain a dispersion liquid 3, which was used as a paint additive 3. It was confirmed that the paint additive 3 maintained a good dispersion state by visually observing no precipitated layer after standing at room temperature for 12 hours.
The resulting paint additive 3 had a solids concentration (titania + zinc cyanurate) of 14 mass %, a pH of 6.2, and an average particle size of the dispersed particles measured by laser diffraction method of 1,456 nm.
Into a 250 ml polypropylene container, 24.9 g of pure water, 0.5 g of 28% _NH3 , 29.5 g of the coating additive 3, 17.7 g of a 10 mass % titania powder slurry wet-ground in a ball mill for 30 hours, and 99.6 g of an acrylic resin emulsion (product name Boncoat 40-418EF) were added, and the mixture was stirred for 2 hours with a stirrer equipped with a turbine blade to obtain coating composition 3.
The resulting coating composition 3 had a solids concentration of 35.5% by mass, a pH of 9.3 and a B-type viscosity of 71 mPa·s.

[Comparative Example 1]
336 g of pure water was placed in a 500 ml polypropylene container, and 64 g of zinc cyanurate particles A was added while stirring with a stirrer equipped with a turbine blade to prepare a zinc cyanurate particle A slurry (zinc cyanurate concentration 16.0 mass %).
Into a 250 ml polypropylene container, 53.8 g of pure water, 0.5 g of 28% _NH3 , 18.4 g of zinc cyanurate particle A slurry (solid content 16 mass%), and 99.6 g of acrylic resin emulsion (product name Boncoat 40-418EF) were added, and the mixture was stirred for 2 hours with a stirrer equipped with a turbine blade to obtain a comparative coating composition 1.
The resulting Comparative Coating Composition 1 had a solids concentration of 33.8% by mass, a pH of 9.6 and a B-type viscosity of 27 mPa·s.

[Comparative Example 2]
336 g of pure water was placed in a 500 ml polypropylene container, and 64 g of zinc cyanurate particles A was added while stirring with a stirrer equipped with a turbine blade to prepare a slurry (zinc cyanurate concentration 16.0 mass %) of zinc cyanurate particles A. Next, 150 g of the zinc cyanurate particle A slurry and 180 g of glass beads having a diameter of 0.7 to 1.0 mm were placed in a 250 ml polypropylene container, and the container was placed on a ball mill turntable set to a rotation speed of 165 rpm and wet-pulverized for 48 hours to obtain a comparative dispersion 2 (zinc cyanurate dispersion).
The average particle size of the obtained comparative dispersion 2 was 1,592 nm as measured by laser diffraction method.
Into a 250 ml polypropylene container were added 53.8 g of pure water, 0.5 _g of 28% NH3, 18.4 g of the above zinc cyanurate dispersion (solid content 16 mass%), and 99.6 g of an acrylic resin emulsion (product name Boncoat 40-418EF), and the mixture was stirred for 2 hours with a stirrer equipped with a turbine blade to obtain a comparative coating composition 2.
The resulting Comparative Coating Composition 2 had a solids concentration of 33.8% by mass, a pH of 9.5 and a B-type viscosity of 25 mPa·s.

[Reference Example 1]
16 g of fumed silica A and 344 g of pure water were placed in a 500 ml polypropylene container, and 40 g of zinc cyanurate particles A were added while stirring with a stirrer equipped with a turbine blade to prepare a mixed slurry ( _SiO2 concentration: 4.0 mass%, zinc cyanurate concentration: 10.0 mass%).
The resulting mixed slurry had a pH of 6.3 and an average particle size of 11,245 nm as measured by laser diffraction.
In a 250 ml polypropylene container, 41.5 g of pure water, 0.5 g of 28% _NH3 , 29.5 g of the mixed slurry, 1.8 g of fumed silica A, and 99.6 g of an acrylic resin emulsion (trade name Boncoat 40-418EF) emulsion were added, and the mixture was stirred for 2 hours with a stirrer equipped with a turbine blade to obtain Reference Coating Composition 1.
The resulting Reference Coating Composition 1 had a solids concentration of 35.5% by mass, a pH of 8.6 and a Brookfield viscosity of 450 mPa·s.

[Reference Example 2]
16 g of fumed silica A and 344 g of pure water were placed in a 500 ml polypropylene container, and 40 g of zinc cyanurate particles A were added and mixed while stirring with a stirrer equipped with a turbine blade, to obtain a mixed slurry (reference dispersion 2) ( _SiO2 concentration: 4.0 mass%, zinc cyanurate concentration: 10.0 mass%).
The resulting mixed slurry (Reference Dispersion 2) had a solid content (silica + zinc cyanurate) concentration of 14 mass %, and the average particle size of the dispersed particles measured by laser diffraction method was 11,245 nm.
24.9 g of pure water, 0.5 g of 28% _NH3 , 29.5 g of the above mixed slurry (Reference Dispersion 2), and 99.6 g of an acrylic resin emulsion (product name Boncoat 40-418EF) were added to a 250 ml polypropylene container, and stirred for 1 hour with a stirrer equipped with a turbine blade to obtain Reference Coating Composition 2.
The resulting Reference Coating Composition 2 had a solids concentration of 38.5% by mass, a pH of 8.6, and a Brookfield viscosity of 450 mPa·s.

[Example 4]
Coating composition 1 prepared in the same manner as in Example 1 was diluted with pure water to a solids concentration of 22 mass %, to obtain coating composition 4 having a solids concentration of 22.0 mass % and a pH of 9.1.
[Reference Example 3]
Reference coating composition 1 prepared in the same manner as in Reference Example 1 was diluted with pure water to a solids concentration of 22% by mass to obtain Reference coating composition 3 having a solids content of 22.0% by mass and a pH of 8.6.

[Example 5]
16 g of fumed silica B and 344 g of pure water were placed in a 500 ml polypropylene container, and 40 g of zinc cyanurate particles A were added while stirring with a stirrer equipped with a turbine blade to prepare a mixed slurry ( _SiO2 concentration 4.0 mass%, zinc cyanurate concentration 10.0 mass%). Next, 150 g of the mixed slurry and 180 g of glass beads having a diameter of 0.7-1.0 mm were placed in a 250 ml polypropylene container, and the container was placed on a ball mill rotating table set to a rotation speed of 165 rpm and wet-milled for 30 hours to obtain dispersion liquid 5. It was confirmed that dispersion liquid 5 maintained a good dispersion state by visually observing no precipitated layer after standing at room temperature for 12 hours.
The solid content (silica + zinc cyanurate) concentration of the obtained dispersion 5 was 14 mass%, pH 6.3, and the average particle diameter of the dispersed particles measured by a laser diffraction method was 1,707 nm. The obtained dispersion 5 was used as paint additive 5.
24.9 g of pure water, 0.5 g of 28% _NH3 , 29.5 g of the coating additive 5, 17.7 g of 10 mass % fumed silica B slurry wet-ground in a ball mill for 30 hours, and 99.6 g of an acrylic resin emulsion (product name Boncoat 40-418EF) were added to a 250 ml polypropylene container, and the mixture was stirred for 2 hours with a stirrer equipped with a turbine blade to obtain coating composition 5.
The resulting coating composition 5 had a solids concentration of 35.5% by mass, a pH of 9.3 and a B-type viscosity of 17 mPa·s.

[Example 6]
16 g of silica powder C and 344 g of pure water were placed in a 500 ml polypropylene container, and 40 g of zinc cyanurate particles A were added while stirring with a stirrer equipped with a turbine blade to prepare a mixed slurry ( _SiO2 concentration 4.0 mass%, zinc cyanurate concentration 10.0 mass%). Next, 150 g of the mixed slurry and 180 g of glass beads having a diameter of 0.7-1.0 mm were placed in a 250 ml polypropylene container, and the container was placed on a ball mill rotating table set to a rotation speed of 165 rpm and wet-pulverized for 30 hours to obtain dispersion liquid 6. It was confirmed that dispersion liquid 6 maintained a good dispersion state by visually observing no precipitated layer after standing at room temperature for 12 hours.
The solid content (silica + zinc cyanurate) concentration of the obtained dispersion 6 was 14 mass%, pH 6.3, and the average particle size of the dispersed particles measured by a laser diffraction method was 1,204 nm. The obtained dispersion 6 was used as paint additive 6.
24.9 g of pure water, 0.5 g of 28% _NH3 , 29.5 g of the coating additive 6, 17.7 g of 10 mass % silica powder C slurry wet-ground in a ball mill for 30 hours, and 99.6 g of acrylic resin emulsion (product name Boncoat 40-418EF) were added to a 250 ml polypropylene container, and the mixture was stirred for 2 hours with a stirrer equipped with a turbine blade to obtain coating composition 6.
The resulting coating composition 6 had a solids concentration of 35.5% by mass, a pH of 9.0 and a B-type viscosity of 45 mPa·s.

[Example 7]
112.5g of aqueous alumina sol and 101.3g of pure water were placed in a 500ml polypropylene container, and 11.3g of zinc cyanurate particles A were added while stirring with a stirrer equipped with a turbine blade to prepare a mixed slurry (Al ₂ O ₃ concentration 5.1% by mass, zinc cyanurate concentration 5% by mass). Next, 150g of the mixed slurry and 180g of glass beads having a diameter of 0.5-0.7mm were placed in a 250ml polypropylene container, and the container was placed on a ball mill rotating table set to a rotation speed of 165 rpm and wet-pulverized for 30 hours to obtain Dispersion 7. It was confirmed that Dispersion 7 maintained a good dispersion state by visually observing no precipitated layer after standing at room temperature for 12 hours.
The solid content (alumina + zinc cyanurate) concentration of the obtained dispersion 7 was 10.1 mass %, and the average particle size of the dispersed particles measured by a laser diffraction method was 112 nm. The obtained dispersion 7 was used as paint additive 7.
Into a 250 ml polypropylene container were added 13.1 g of pure water, 0.5 _g of 28% NH3, 59.1 g of the above-mentioned paint additive 7, and 99.6 g of an acrylic resin emulsion (product name Boncoat 40-418EF), and the mixture was stirred for 1 hour with a stirrer equipped with a turbine blade to obtain paint composition 7.
The resulting coating composition 7 had a solids concentration of 35.5% by mass, a pH of 6.2, and a Brookfield viscosity of 100 mPa·s.

[Example 8]
150g of aqueous zirconia sol and 53.5g of pure water were placed in a 500ml polypropylene container, and 22.5g of zinc cyanurate particles A were added while stirring with a stirrer equipped with a turbine blade, to prepare a mixed slurry ( _ZrO2 concentration 20.2% by mass, zinc cyanurate concentration 10% by mass). Next, 150g of the mixed slurry and 180g of glass beads having a diameter of 0.5-0.7 mm were placed in a 250ml polypropylene container, and the container was placed on a ball mill rotating table set to a rotation speed of 165 rpm, and wet-milled for 30 hours to obtain dispersion 8. It was confirmed that dispersion 8 maintained a good dispersion state after standing at room temperature for 12 hours without visually confirming any precipitated layer.
The solid content (zirconia + zinc cyanurate) concentration of the obtained dispersion 8 was 30.2 mass %, and the average particle diameter of the dispersed particles measured by a laser diffraction method was 53 nm. The obtained dispersion 8 was used as paint additive 8.
Into a 250 ml polypropylene container, 42.7 g of pure water, 0.5 g of 28% _NH3 , 29.5 g of the above-mentioned paint additive 8, and 99.6 g of an acrylic resin emulsion (product name Boncoat 40-418EF) were added, and the mixture was stirred for 1 hour with a stirrer equipped with a turbine blade to obtain paint composition 8.
The resulting coating composition 8 had a solids concentration of 37.3% by mass, a pH of 9.1, and a Brookfield viscosity of 20 mPa·s.

[Example 9]
200g of aqueous titania sol and 2.5g of pure water were placed in a 500ml polypropylene container, and 22.5g of zinc cyanurate particles A were added while stirring with a stirrer equipped with a turbine blade, to prepare a mixed slurry ( _TiO2 concentration 3.7% by mass, zinc cyanurate concentration 10% by mass). Next, 150g of the mixed slurry and 180g of glass beads having a diameter of 0.5-0.7mm were placed in a 250ml polypropylene container, and the container was placed on a ball mill rotating table set to a rotation speed of 165 rpm, and wet-milled for 30 hours to obtain dispersion 9. It was confirmed that dispersion 9 maintained a good dispersion state, with no visually observed precipitated layer after standing at room temperature for 12 hours.
The solid content (titania + zinc cyanurate) concentration of the obtained dispersion 9 was 13.7 mass %, and the average particle size of the dispersed particles measured by a laser diffraction method was 151 nm. The obtained dispersion 9 was used as paint additive 9.
30.5 g of pure water, 0.5 g of 28% _NH3 , 29.5 g of the above-mentioned paint additive 9, and 111.8 g of acrylic-styrene resin emulsion B (product name Movinyl DM-60) were added to a 250 ml polypropylene container and stirred for 1 hour with a stirrer equipped with a turbine blade to obtain paint composition 9.
The resulting coating composition 9 had a solids concentration of 34.1% by mass, a pH of 9.8, and a Brookfield viscosity of 22.8 mPa·s.

[Example 10]
201.5 g of aqueous tin oxide sol and 1.0 g of pure water were placed in a 500 ml polypropylene container, and 22.5 g of zinc cyanurate particles A were added while stirring with a stirrer equipped with a turbine blade to prepare a mixed slurry ( _SnO2 concentration 3.6 mass%, zinc cyanurate concentration 10 mass%). Next, 150 g of the mixed slurry and 180 g of glass beads having a diameter of 0.5-0.7 mm were placed in a 250 ml polypropylene container, and the container was placed on a ball mill rotating table set to a rotation speed of 165 rpm and wet-pulverized for 30 hours to obtain a dispersion liquid 10. It was confirmed that the dispersion liquid 10 maintained a good dispersion state by visually observing no precipitated layer after standing at room temperature for 12 hours.
The solid content (tin oxide + zinc cyanurate) concentration of the obtained dispersion 10 was 13.6 mass %, and the average particle size of the dispersed particles measured by a laser diffraction method was 91 nm. The obtained dispersion 10 was used as paint additive 10.
Into a 250 ml polypropylene container were added 30.5 g of pure water, 0.5 g of 28% _NH3 , 29.5 g of the above-mentioned paint additive 10, and 111.8 g of acrylic-styrene resin emulsion B (product name Movinyl DM-60), and the mixture was stirred for 1 hour with a stirrer equipped with a turbine blade to obtain paint composition 10.
The resulting coating composition 10 had a solids concentration of 34.1% by mass, a pH of 9.8, and a Brookfield viscosity of 21 mPa·s.

[Comparative Example 4]
336 g of pure water was placed in a 500 ml polypropylene container, and 64 g of zinc cyanurate particles A were added while stirring with a stirrer equipped with a turbine blade to prepare a zinc cyanurate slurry (zinc cyanurate concentration: 16.0% by mass).
42.7 g of pure water, _0.5 g of 28% NH, 19.4 g of aqueous zirconia sol, 18.5 g of zinc cyanurate slurry (solid content 16% by mass), and 99.6 g of acrylic resin emulsion (product name Boncoat 40-418EF) were added to a 250 ml polypropylene container and stirred for 2 hours with a stirrer equipped with a turbine blade to obtain Comparative Coating Composition 4.
The resulting Comparative Coating Composition 4 had a solids concentration of 35.5% by mass, a pH of 9.4 and a Brookfield viscosity of 13 mPa·s.

[Example 11]
99 g of aqueous silica sol and 261 g of pure water were placed in a 500 ml polypropylene container, and while stirring with a stirrer equipped with a turbine blade, 32 g of zinc cyanurate particles A and 8 g of cyanuric acid powder (manufactured by Nissan Chemical Industries, Ltd.) were added to change the (zinc oxide)/(cyanuric acid) molar ratio of zinc cyanurate particles A to 1.5, to prepare a mixed slurry ( _SiO2 concentration 10 mass%, zinc cyanurate concentration 10 mass%). Next, 150 g of the mixed slurry and 180 g of glass beads having a diameter of 0.7-1.0 mm were placed in a 250 ml polypropylene container, and the container was placed on a ball mill rotating table set to a rotation speed of 165 rpm and wet-pulverized for 30 hours to obtain a dispersion liquid 11, which was used as a paint additive 11. It was confirmed that the paint additive 11 maintained a good dispersion state, with no visually observed precipitated layer after standing at room temperature for 12 hours.
The resulting paint additive 11 had a solids content (silica + zinc cyanurate) concentration of 20 mass %, and an average particle size measured by laser diffraction method of 78 nm.
Into a 250 ml polypropylene container, 42.7 g of pure water, 0.5 g of 28% _NH3 , 29.5 g of the coating additive 11, and 99.6 g of an acrylic resin emulsion (product name Boncoat 40-418EF) were added, and the mixture was stirred for 1 hour with a stirrer equipped with a turbine blade to obtain coating composition 11.
The resulting coating composition 11 had a solids concentration of 35.5% by mass, a pH of 9.0, and a Brookfield viscosity of 20 mPa·s.

[Example 12]
99 g of aqueous silica sol and 261 g of pure water were placed in a 500 ml polypropylene container, and while stirring with a stirrer equipped with a turbine blade, 26.8 g of zinc cyanurate particles A and 13.2 g of zinc oxide (two types of zinc oxide manufactured by Sakai Chemical Industry Co., Ltd.) were added to change the (zinc oxide)/(cyanuric acid) molar ratio of zinc cyanurate particles A to 4.5, to prepare a mixed slurry ( _SiO2 concentration 10 mass%, zinc cyanurate concentration 10 mass%). Next, 150 g of the mixed slurry and 180 g of glass beads having a diameter of 0.7-1.0 mm were placed in a 250 ml polypropylene container, and the container was placed on a ball mill rotating table set to a rotation speed of 165 rpm and wet-pulverized for 30 hours to obtain a dispersion liquid 12, which was used as a paint additive 12. It was confirmed that the paint additive 12 maintained a good dispersion state, with no visually observed precipitated layer after standing at room temperature for 12 hours.
The resulting paint additive 12 had a solids content (silica + zinc cyanurate) concentration of 20 mass %, and an average particle size measured by laser diffraction method of 157 nm.
In a 250 ml polypropylene container, 42.7 g of pure water, 0.5 g of 28% _NH3 , 29.5 g of the coating additive 12, and 99.6 g of an acrylic resin emulsion (product name Boncoat 40-418EF) were added, and the mixture was stirred for 1 hour with a stirrer equipped with a turbine blade to obtain a coating composition 12.
The resulting coating composition 12 had a solids concentration of 33.8% by mass, a pH of 9.1, and a Brookfield viscosity of 21 mPa·s.

[Example 13]
99 g of aqueous silica sol and 261 g of pure water were placed in a 500 ml polypropylene container, and 40 g of zinc cyanurate particles B were added while stirring with a stirrer equipped with a turbine blade to prepare a mixed slurry (SiO2 concentration 10.0 mass%, zinc cyanurate concentration 10.0 mass%). Next, 150 g of the mixed slurry and 180 g of glass beads having a diameter of 0.7-1.0 mm were placed in a 250 ml polypropylene container, and the container was placed on a ball mill turntable set to a rotation speed of 165 rpm and wet-pulverized for 30 hours to obtain a dispersion liquid 13, which was used as the paint additive 13. It was confirmed that the paint additive 13 maintained a good dispersion state, with no visually observed precipitated layer after standing at room temperature for 12 hours.
The resulting paint additive 13 had a solids content (silica + zinc cyanurate) concentration of 20 mass %, and an average particle size measured by laser diffraction method of 134 nm.
42.7 g of pure water, 0.5 g of 28% NH3, 29.5 g of the paint additive 1, and 99.6 g of an acrylic resin emulsion (product name: Boncoat 40-418EF) were added to a 250 ml polypropylene container, and the mixture was stirred for 1 hour with a stirrer equipped with a turbine blade to obtain paint composition 1.
The resulting coating composition 13 had a solids concentration of 33.8% by mass, a pH of 9.1, and a Brookfield viscosity of 19 mPa·s.

[Comparative Example 3]
To a 250 ml polypropylene container were added 85.4 g of pure water and 114.6 g of acrylic resin emulsion (product name 40-418EF), and the mixture was stirred for 1 hour with a stirrer equipped with a turbine blade, to obtain Comparative Coating Composition 3.
The resulting Comparative Coating Composition 3 had a solids concentration of 31.8% by mass, a pH of 9.6 and a Brookfield viscosity of 17 ma·s.

[Example 14]
32.2 g of pure water, 29.3 g of the paint additive 1, and 110.6 g of acrylic-styrene resin emulsion A (product name Boncoat CG-8680) were added to a 250 ml polypropylene container and stirred for 1 hour with a stirrer equipped with a turbine blade to obtain paint composition 14.
The resulting coating composition 14 had a solids concentration of 35.5% by mass, a pH of 7.4, and a Brookfield viscosity of 50 mPa·s.

[Example 15]
28.4 g of pure water, 29.3 g of the coating additive 1, and 114.5 g of acrylic-styrene resin emulsion B (product name: Movinyl DM-60) were added to a 250 ml polypropylene container, and the mixture was stirred for 1 hour with a stirrer equipped with a turbine blade to obtain coating composition 15.
The resulting coating composition 15 had a solids concentration of 35.5% by mass, a pH of 7.9, and a Brookfield viscosity of 25 mPa·s.

[Example 16]
29.3 g of the paint additive 1 and 158 g of an acrylic (polysiloxane composite) resin emulsion (product name: Ceranate WHW-822) were added to a 250 ml polypropylene container, and the mixture was stirred for 1 hour with a stirrer equipped with a turbine blade to obtain paint composition 16.
The resulting coating composition 16 had a solids concentration of 32.7% by mass, a pH of 7.9, and a Brookfield viscosity of 31 mPa·s.

[Example 17]
25.8 g of pure water, 29.3 g of the paint additive 1, and 117.2 g of an acrylic-silicone resin emulsion (product name: Movinyl LDM7523) were added to a 250 ml polypropylene container and stirred for 1 hour with a stirrer equipped with a turbine blade to obtain paint composition 17.
The resulting coating composition 17 had a solids concentration of 35.5% by mass, a pH of 7.7, and a Brookfield viscosity of 20 mPa·s.

[Example 18]
29.3 g of the paint additive 1 and 154.5 g of urethane resin emulsion A (product name Hydran HW-171) were added to a 250 ml polypropylene container and stirred for 1 hour with a stirrer equipped with a turbine blade to obtain paint composition 18.
The resulting coating composition 18 had a solids concentration of 33.3 mass %, a pH of 8.4, and a Brookfield viscosity of 16 mPa·s.

[Example 19]
3.7 g of pure water, 29.3 g of the paint additive 1, and 139.3 g of urethane resin emulsion B (product name NeoRezR-967) were added to a 250 ml polypropylene container and stirred for 1 hour with a stirrer equipped with a turbine blade to obtain paint composition 19.
The resulting coating composition 19 had a solids concentration of 35.5% by mass, a pH of 8.4, and a Brookfield viscosity of 19 mPa·s.

[Example 20]
2.3 g of pure water, 29.3 g of the coating additive 1, and 140.7 g of an epoxy resin emulsion (product name Epicron H-502-42W) were added to a 250 ml polypropylene container, and the mixture was stirred for 1 hour with a stirrer equipped with a turbine blade to obtain coating composition 20.
The resulting coating composition 20 had a solids concentration of 35.5 mass %, a pH of 9.2, and a Brookfield viscosity of 197 mPa·s.

[Example 21]
29.3 g of the paint additive 1 and 149.5 g of an epoxy-ester resin emulsion (product name: Watersol EFD-5530) were added to a 250 ml polypropylene container and stirred for 1 hour with a stirrer equipped with a turbine blade to obtain paint composition 21.
The resulting coating composition 21 had a solids concentration of 34.2% by mass, a pH of 8.8, and a Brookfield viscosity of 32 mPa·s.

[Example 22]
50.7 g of pure water, 29.3 g of the paint additive 1, and 92.2 g of an alkyd resin emulsion (product name: Watersol S-118) were added to a 250 ml polypropylene container, and the mixture was stirred for 1 hour with a stirrer equipped with a turbine blade to obtain paint composition 22.
The resulting coating composition 22 had a solids concentration of 35.5 mass %, a pH of 8.8, and a Brookfield viscosity of 678 mPa·s.

[Example 23]
32.2 g of pure water, 29.3 g of the paint additive 1, and 110.6 g of an acetic acid-acrylic resin emulsion (product name: Boncoat CF-2800) were added to a 250 ml polypropylene container, and the mixture was stirred for 1 hour with a stirrer equipped with a turbine blade to obtain paint composition 23.
The resulting coating composition 23 had a solids concentration of 35.5% by mass, a pH of 5.6, and a Brookfield viscosity of 65 mPa·s.

[Example 24]
33.4 g of pure water, 29.3 g of the paint additive 1, and 109.5 g of a vinyl acetate resin emulsion (product name Polysol S-65) were added to a 250 ml polypropylene container, and the mixture was stirred for 1 hour with a stirrer equipped with a turbine blade to obtain paint composition 24.
The resulting coating composition 24 had a solids concentration of 35.5% by mass, a pH of 7.2, and a Brookfield viscosity of 14 mPa·s.

[Example 25]
26.5 g of pure water, 21.3 g of the paint additive 1, and 130.0 g of vinyl chloride resin emulsion (product name Vinyblan VE-701) were added to a 250 ml polypropylene container and stirred for 1 hour with a stirrer equipped with a turbine blade to obtain paint composition 25.
The resulting coating composition 25 had a solids concentration of 25.0% by mass, a pH of 7.8, and a Brookfield viscosity of 8.0 mPa·s.

[Example 26]
32.3 g of pure water, 29.3 g of the paint additive 1, and 110.6 g of an olefin resin emulsion (product name PE-381) were added to a 250 ml polypropylene container and stirred for 1 hour with a stirrer equipped with a turbine blade to obtain paint composition 26.
The resulting coating composition 26 had a solids concentration of 35.5% by mass, a pH of 7.8, and a Brookfield viscosity of 58 mPa·s.

[Example 27]
24.7 g of pure water, 29.3 g of the coating additive 1, and 118.2 g of a fluorine-based resin emulsion (product name SIFCLEAR F-104) were added to a 250 ml polypropylene container, and the mixture was stirred for 1 hour with a stirrer equipped with a turbine blade to obtain coating composition 27.
The resulting coating composition 27 had a solids concentration of 35.5% by mass, a pH of 8.2, and a Brookfield viscosity of 6.0 mPa·s.

[Example 28]
17.8 g of pure water, 20.1 g of the paint additive 1, and 130.0 g of an ester resin emulsion (product name: Elitel KA-3556) were added to a 250 ml polypropylene container and stirred for 1 hour with a stirrer equipped with a turbine blade to obtain paint composition 28.
The resulting coating composition 28 had a solids concentration of 25.0% by mass, a pH of 8.3, and a Brookfield viscosity of 29 mPa·s.

[Comparative Example 5]
To a 250 ml polypropylene container were added 128.3 g of pure water and 71.7 g of acrylic resin emulsion (product name 40-418EF), and the mixture was stirred for 1 hour with a stirrer equipped with a turbine blade, to obtain Comparative Coating Composition 5.
The resulting Comparative Coating Composition 5 had a solids concentration of 19.9% by mass, a pH of 9.0 and a Brookfield viscosity of 11 mPa·s.

[Comparative Example 6]
Comparative coating composition 1 prepared in the same manner as in Comparative Example 1 was diluted with pure water to a solids concentration of 22% by mass, to obtain a comparative coating composition 6 having a solids concentration of 22.0% by mass.
The resulting Comparative Coating Composition 6 had a solids concentration of 22.0% by mass, a pH of 8.9 and a Brookfield viscosity of 15 mPa·s.

[Comparative Example 7]
Comparative coating composition 1 prepared in the same manner as in Comparative Example 2 was diluted with pure water to a solids concentration of 22% by mass, to obtain a comparative coating composition 7 having a solids concentration of 22.0% by mass.
The resulting Comparative Coating Composition 7 had a solids concentration of 22.0% by mass, a pH of 8.9 and a Brookfield viscosity of 18 mPa·s.

[Example 29]
Coating composition 15 prepared in the same manner as in Example 15 was diluted with pure water to a solids concentration of 22% by mass to obtain coating composition 29 having a solids concentration of 22.0% by mass, pH = 7.9, and B-type viscosity of 25 mPa·s.

[Example 30]
Coating composition 16 prepared in the same manner as in Example 16 was diluted with pure water to a solids concentration of 22% by mass, to obtain coating composition 30 having a solids concentration of 22.0% by mass, pH = 7.9, and B-type viscosity of 31 mPa·s.

[Example 31]
Coating composition 18 prepared in the same manner as in Example 18 was diluted with pure water to a solids concentration of 22% by mass, to obtain coating composition 31 having a solids concentration of 22.0% by mass, pH = 8.4, and B-type viscosity of 16 mPa·s.

[Example 32]
Coating composition 20 prepared in the same manner as in Example 20 was diluted with pure water to a solids concentration of 22% by mass, to obtain coating composition 32 having a solids concentration of 22.0% by mass, pH = 9.2, and B-type viscosity of 197 mPa·s.

[Example 33]
Coating composition 22 prepared in the same manner as in Example 22 was diluted with pure water to a solids concentration of 22% by mass, to obtain coating composition 33 having a solids concentration of 22.0% by mass, pH = 8.8, and B-type viscosity of 678 mPa·s.

[Example 34]
Coating composition 23 prepared in the same manner as in Example 23 was diluted with pure water to a solids concentration of 22% by mass, to obtain coating composition 34 having a solids concentration of 22.0% by mass, pH = 6.3, and B-type viscosity of 30 mPa·s.

[Example 35]
Coating composition 24 prepared in the same manner as in Example 24 was diluted with pure water to a solids concentration of 22% by mass, to obtain coating composition 35 having a solids concentration of 22.0% by mass, pH = 7.4, and B-type viscosity of 11 mPa·s.

[Example 36]
Coating composition 26 prepared in the same manner as in Example 26 was diluted with pure water to a solids concentration of 22% by mass, thereby obtaining coating composition 36 having a solids concentration of 22.0% by mass, pH = 7.5, and B-type viscosity of 46 mPa·s.

[Example 37]
Coating composition 27 prepared in the same manner as in Example 27 was diluted with pure water to a solids concentration of 22% by mass, to obtain coating composition 37 having a solids concentration of 22.0% by mass, pH = 7.9, and B-type viscosity of 5 mPa·s.

Using the coating compositions 1 to 3 and 5 to 28 of Examples 1 to 3, the comparative coating compositions 1 to 4 of Comparative Examples 1 to 4, and the reference coating compositions 1 and 2 of Reference Examples 1 and 2, coatings and coating films on aluminum plates were evaluated according to the procedure described below.
In addition, coating/coating films on PET films were evaluated using coating compositions 4, 29 to 37, 29 to 37, comparative coating compositions 5 to 7, and reference coating composition 3 in Reference Example 3 according to the procedure described below.

[Examples 38 to 46]
Using the coating compositions 1, 15, 16, 18, 20, 23, 24, 26, and 27 of Examples 1, 15, 16, 18, 20, 23, 24, 26, and 27, coating and coating films on Cu plates were evaluated according to the procedure described below.
[Comparative Examples 8 to 10]
Using the comparative coating compositions 3, 1, and 2 of Comparative Examples 3, 1, and 2, coating on a Cu plate and evaluation of the coating film were carried out according to the procedure described below.

[Examples 47 to 53]
Using the coating compositions 1, 16, 18, 20, 22, 26, and 27 of Examples 1, 16, 18, 20, 22, 26, and 27, coating and coating films on SUS plates were evaluated according to the procedure described below.
[Comparative Examples 11 to 13]
Using the comparative coating compositions 3, 1 and 2 of Comparative Examples 3, 1 and 2, coating on SUS plates and evaluation of the coating film were carried out according to the procedure described below.

[Examples 54 to 63]
Using the coating compositions 1, 15, 16, 18, 20, 22 to 24, 26, and 27 of Examples 1, 15, 16, 18, 20, 22 to 24, 26, and 27, coating and coating films on mild steel plates were evaluated according to the procedure described below.
[Comparative Examples 14 and 15]
Using the comparative coating compositions 1 and 2 of Comparative Examples 1 and 2, coating of mild steel plates and evaluation of the coating films were carried out according to the procedure described below.

[Examples 64 to 73]
Using the coating compositions 1, 15, 16, 18, 20, 22 to 24, 26, and 27 of Examples 1, 15, 16, 18, 20, 22 to 24, 26, and 27, coating and coating films on zinc-plated steel sheets were evaluated according to the procedure described below.
[Comparative Examples 16 and 17]
Using the comparative coating compositions 1 and 2 of Comparative Examples 1 and 2, coating of a galvanized steel sheet and evaluation of the coating film were carried out according to the procedure described below.

[Examples 74 to 82]
Using the coating compositions 1, 15, 18, 20, 22-24, 26, and 27 of Examples 1, 15, 18, 20, 22-24, 26, and 27, coating and coating films on cedar boards were evaluated according to the procedure described below.
[Comparative Examples 18 to 20]
Using the comparative coating compositions 3, 1, and 2 of Comparative Examples 3, 1, and 2, coating and coating films on cedar boards were evaluated according to the procedure described below.

(9) The following aluminum plates were prepared for coating:
An aluminum plate (manufactured by Hikari Co., Ltd., JIS type A1050P) having a plate thickness of 0.5 mm and dimensions of 70 mm width × 150 mm length was used.
(Coating method)
Coating compositions 1 to 3, 5 to 28, comparative coating compositions 1 to 4, and reference coating compositions 1 to 2 were applied to the surface of an aluminum plate at a speed of 2 m/min by bar coating, and the plate was baked for 30 seconds in an electric furnace set at 230° C. to obtain an aluminum plate with a coating film. The specific method of bar coating is as follows.
Bar coating: Each coating composition was dropped onto an aluminum plate and coated with an RDS.24 bar coater to a wet coating thickness of 61 μm.

(10) The following film substrates (PET) were prepared for coating:
A PET film (manufactured by Toyobo Co., Ltd., product name Cosmoshine A4100) that had been treated to make it easy to adhere was used, having a plate thickness of 100 μm and dimensions of 297 mm width × 420 mm length.
(Coating method)
Coating composition 4, coating compositions 29 to 37, comparative coating compositions 5 to 7 and reference coating composition 3 were applied to the adhesive layer surface of the PET film at a speed of 2 m/min by bar coating, and dried for 5 minutes on a hot plate set at 60° C. to obtain a PET film with a coating film. The specific method of bar coating is as follows.
Bar coating: Each coating composition was dropped onto a PET film and coated with a No. 2 bar coater to a wet coating thickness of 4.6 μm.

(11) The following Cu plates to be coated were prepared:
A Cu plate (manufactured by Hikari Co., Ltd., JIS type C1220P) having a plate thickness of 0.5 mm and dimensions of 100 mm width × 365 mm length was used.
(Coating method)
Coating compositions 1, 15, 16, 18, 20, 23, 24, 26, 27 and comparative coating compositions 1 to 3 were applied to the surface of a Cu plate at a speed of 2 m/min by bar coating, and the plate was baked for 30 seconds in an electric furnace set at 230° C. to obtain a Cu substrate with a coating film. The specific method of bar coating is as follows.
Bar coating: Each coating composition was dropped onto a Cu plate and coated with an RDS.24 bar coater to a wet coating thickness of 61 μm.

(12) The following SUS plates were prepared for coating:
A stainless steel plate (manufactured by Hikari Co., Ltd., JIS type SUS430) having a plate thickness of 0.5 mm and dimensions of 100 mm width x 300 mm length was used.
(Coating method)
Coating compositions 1, 16, 18, 20, 22, 26, and 27, and comparative coating compositions 1 to 3 were applied to the surface of SUS plates at a speed of 2 m/min by bar coating, and the plates were baked for 30 seconds in an electric furnace set at 230° C. to obtain SUS plates with a coating film. The specific method of bar coating is as follows.
Bar coating: Each coating composition was dropped onto a SUS plate and coated with an RDS.24 bar coater to a wet coating thickness of 61 μm.

(13) The following mild steel sheets to be coated were prepared:
A mild steel plate (manufactured by TP Giken Co., Ltd., JIS type SPCC bright steel plate) having a plate thickness of 0.8 mm and dimensions of 70 mm width x 150 mm length was used.
(Coating method)
Coating compositions 1, 15, 16, 18, 20, 22 to 24, 26, and 27, and comparative coating compositions 1 and 2 were applied to the surface of mild steel sheets at a speed of 2 m/min by bar coating, and baked for 30 seconds in an electric furnace set at 230° C. to obtain mild steel sheets with a coating film. The specific method of bar coating is as follows.
Bar coating: Each coating composition was dropped onto a mild steel plate and coated with an RDS.24 bar coater to a wet coating thickness of 61 μm.

(14) The following zinc-plated steel sheets to be coated were prepared:
A zinc-plated steel sheet (manufactured by Standard Test Piece Co., Ltd., JIS type SS400, hot-dip galvanized (no chemical conversion treatment)) having a plate thickness of 6 mm and dimensions of 70 mm width x 150 mm length was used.
(Coating method)
Coating compositions 1, 15, 16, 18, 20, 22 to 24, 26, and 27, and comparative coating compositions 1 and 2 were applied to the surface of zinc-plated steel sheets at a speed of 2 m/min by bar coating, and the sheets were baked for 30 seconds in an electric furnace set at 230° C. to obtain zinc-plated steel sheets with a coating film. The specific method of bar coating is as follows.
Bar coating: Each coating composition was dropped onto a zinc-plated steel sheet and coated with an RDS.24 bar coater to a wet coating thickness of 61 μm.

(15) The following wood materials were prepared for coating:
A cedar board (manufactured by Standard Test Piece Co., Ltd., red and white grain, four-sided planer finish) with a board thickness of 5 mm and dimensions of 100 mm width x 150 mm length was used.
(Coating method)
Coating compositions 1, 15, 18, 20, 22, 23, 24, 26, 27, and comparative coating compositions 1 to 3 were applied to the surface of the cedar board substrate by brush painting so that the coating amount after drying was 30 g/m ² , and dried for 3 minutes at 80 ° C. to form the first layer. Next, the same coating composition as that used for the first layer was applied to the surface of the first layer so that the coating amount after drying was 70 g/m ² , and dried for 10 minutes at 80 ° C. to obtain a cedar board with a coating film having a two-layer structure.

(16) Appearance test of coated aluminum plate, coated Cu plate, coated SUS plate, coated mild steel plate, coated galvanized steel plate, coated cedar board, and coated PET film For each of the coated aluminum plate, coated Cu plate, coated SUS plate, coated mild steel plate, coated galvanized steel plate, coated cedar board, and coated PET film, the area of the portion where the coating film was formed relative to the area of the aluminum plate, Cu plate, SUS plate, mild steel plate, galvanized steel plate, cedar board, or PET film was visually observed and evaluated based on the following evaluation criteria.
<Evaluation criteria>
Good: 90% or more of the area where a coating film was formed was observed.
Fairly poor: The coating film formation area was observed to be 50% to 89%.
Poor: The coating film formation area was observed to be 10% to 49%.

(17) Pencil Hardness Test With reference to JIS K5600, the pencil hardness of each of the coated aluminum plate, the coated Cu plate, the coated SUS plate, the coated mild steel plate, the coated zinc-plated steel plate and the coated PET film was measured according to the following method.
Using a manual pencil scratch hardness tester manufactured by Yasuda Seiki Seisakusho Co., Ltd., a pencil lead manufactured by Hi-uni Co., Ltd., manufactured by Mitsubishi Pencil Co., Ltd. was pressed against the surface of the coating film and moved, and the hardness of the pencil at which peeling of the coating film occurred was measured.
In addition, when an aluminum substrate is used, it is desirable for the pencil hardness to be 3B or more, when a copper substrate is used, it is desirable for the pencil hardness to be 5B or more, when an iron substrate (SUS, mild steel plate, zinc-plated steel plate) is used, it is desirable for the pencil hardness to be 3B or more, and when a PET film is used, it is desirable for the pencil hardness to be 6B or more.
<Criteria>
[Soft] 6B, 5B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H [Hard]

(18) Adhesion test using the cross-cut method
With reference to JIS K5600, the adhesion (tightness) of the coating film to the substrates (aluminum plate, PET film, CU plate, SUS plate, mild steel plate, galvanized steel plate, cedar plate, and PET film) was evaluated by the cross-cut method according to the following method for each of the coated aluminum plate, coated Cu plate, coated SUS plate, coated mild steel plate, coated galvanized steel plate, and cedar plate.
100 grid patterns were cut at intervals of 1 mm on the coating film surface, and a tape was placed in contact with the grid portions for 20 mm. The tape was then gripped by its end and peeled off in 0.5 to 1.0 seconds, and the presence or absence of peeling on the coating film and the number of peelings (number of grids) were visually confirmed and evaluated according to the following criteria.
<Criteria>
A: The number of squares that did not peel off was 90 or more. B: The number of squares that did not peel off was 60 or more and less than 90. C: The number of squares that did not peel off was 40 or more and less than 60. D: The number of squares that did not peel off was less than 40.

(19) Haze Measurement The haze of the coated PET film was measured using NDH-5000 manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with the measurement method of JIS K7105.

The results obtained are summarized in Tables 1 to 7.

As shown in Table 1 [Table 1-1 to Table 1-4], according to the present invention, a coating film was formed over the entire aluminum plate substrate, had a hardness of generally 3B or more, and had excellent adhesion to the substrate.
In detail, as shown in [Table 1-1] and [Table 1-2] (Examples 1 to 3, Examples 5 to 10), even when various silica powders, colloidal alumina, colloidal zirconia, colloidal titania, and tin oxide sol were used, a coating film was formed on the entire aluminum plate substrate and had excellent adhesion to the substrate.
Furthermore, as shown in [Table 1-3] (Examples 11 to 13), even when the particle size of the zinc cyanurate particles or the (zinc oxide)/(zinc cyanurate) molar ratio of the zinc cyanurate particles was changed, a coating film was formed over the entire aluminum plate substrate, had a hardness of 2B or more, and was excellent in adhesion to the substrate.
Furthermore, as shown in [Table 1-4] and [Table 1-5] (Examples 14 to 21, Examples 22 to 28), according to the present invention, even when various resin emulsions were used, a coating film was formed on the entire aluminum plate substrate, and was able to form a coating film that had both hardness and adhesion to the substrate.
On the other hand, when inorganic oxide powder is not used, in both Comparative Example 1 in which zinc cyanurate slurry and resin emulsion are mixed, and Comparative Example 2 in which zinc cyanurate slurry is wet-ground to prepare a dispersion and mixed with resin emulsion, the results are significantly inferior to those of the Examples in terms of both the appearance of the coating film (bad) and the adhesion (D). In addition, in the case of Comparative Example 3 in which only resin emulsion is used, the appearance of the coating film is good, but the adhesion is rated D. Furthermore, in the case of simply mixing colloidal metal oxide particles and zinc cyanurate without preparing a dispersion (Comparative Example 4), the appearance of the coating film is good, but the adhesion (C) is poor.
In addition, in the dispersion liquid containing the inorganic oxide powder and the zinc cyanurate particles, in Reference Examples 1 and 2 in which the average particle size of the dispersed matter measured by the laser diffraction method exceeded 10,000 nm, both the appearance (poor) and the adhesion (D) of the coating film were significantly inferior to those of the Examples.

As shown in Table 2 [Table 2-1 to Table 2-3] (Example 4, Example 29 to Example 33, Example 34 to Example 37), according to the present invention, even when various resin emulsions were used, a coating film was formed on the entire PET substrate, had a hardness of 2B or more, and was excellent in adhesion to the substrate. Furthermore, according to the present invention, a large increase in HAZE value was suppressed, and therefore adhesion to the substrate could be improved without significantly impairing the transparency of the PET substrate.
On the other hand, in the case of Comparative Example 5 in which the zinc cyanurate slurry was mixed with the resin emulsion and Comparative Example 6 in which the zinc cyanurate slurry was wet-pulverized to prepare a dispersion and then mixed with the resin emulsion, both the appearance of the coating film (bad) and the adhesion (D) were significantly inferior to those of the Examples, when inorganic oxide particles were not used. In Comparative Example 4 in which only the resin emulsion was used, the appearance of the coating film was good, but the adhesion was rated D.
In addition, in Reference Example 3 in which the average particle size of the dispersed matter measured by the laser diffraction method in the dispersion liquid containing the inorganic oxide powder and the zinc cyanurate particles exceeded 10,000 nm, both the appearance (poor) and the adhesion (C) of the coating film were significantly inferior to those of the Examples.

As shown in Table 3 [Table 3-1 to Table 3-2] (Examples 38 to 40, Examples 41 to 46), according to the present invention, a coating film was formed on the entire Cu plate substrate, had a hardness of 5B or more, and had excellent adhesion to the substrate.
On the other hand, when inorganic oxide particles were not used, in Comparative Example 8 in which only a resin emulsion was used, the coating film appearance was good, but the adhesion was rated D. In Comparative Example 9 in which a zinc cyanurate slurry was mixed with a resin emulsion, and in Comparative Example 10 in which a zinc cyanurate slurry was wet-pulverized to form a dispersion liquid and then mixed with a resin emulsion, both the coating film appearance (poor) and adhesion (D (Comparative Example 9) and B (Comparative Example 10)) were significantly inferior to those of the Examples.

As shown in Table 4 [Table 4-1 to Table 4-2] (Examples 47 to 49, Examples 50 to 53), according to the present invention, a coating film was formed on the entire SUS plate substrate, had a hardness of 3B or more, and had excellent adhesion to the substrate.
On the other hand, in the case of not using inorganic oxide particles, in Comparative Example 11 in which only a resin emulsion was used, the coating film appearance was good, but the adhesion was rated D. In Comparative Example 12 in which a zinc cyanurate slurry and a resin emulsion were mixed, and in Comparative Example 13 in which a zinc cyanurate slurry was wet-pulverized to form a dispersion liquid and this was mixed with a resin emulsion, both the coating film appearance (poor) and adhesion (D) were significantly inferior to those of the Examples.

As shown in Table 5 [Table 5-1 to Table 5-2] (Examples 54 to 56, Examples 57 to 63), according to the present invention, a coating film was formed on the entire mild steel plate substrate, had a hardness of 3B or more, and had excellent adhesion to the substrate.
On the other hand, in the case of not using inorganic oxide particles, Comparative Example 14 in which the zinc cyanurate slurry was mixed with the resin emulsion, and Comparative Example 15 in which the zinc cyanurate slurry was wet-pulverized to form a dispersion liquid and then mixed with the resin emulsion, both the appearance (poor) and adhesion (D) of the coating film were significantly inferior to those of the Examples.

As shown in Table 6 [Table 6-1 to Table 6-2] (Examples 64 to 67, Examples 68 to 73), according to the present invention, a coating film was formed on the entire galvanized steel sheet substrate, had a hardness of HB or more, and was excellent in adhesion to the substrate.
On the other hand, in the case of Comparative Example 16 in which the zinc cyanurate slurry was mixed with the resin emulsion and Comparative Example 17 in which the zinc cyanurate slurry was wet-pulverized to form a dispersion liquid and then mixed with the resin emulsion, when inorganic oxide particles were not used, the results were significantly inferior to those of the Examples in both the appearance of the coating film (poor) and the adhesion (C (Comparative Example 16) and B (Comparative Example 17)).

As shown in Table 7 [Table 7-1 to Table 7-2] (Examples 74 to 76, Examples 77 to 82), according to the present invention, a coating film that is formed on the entire wood and has excellent adhesion to the substrate can be formed.
On the other hand, in the case where inorganic oxide particles were not used, Comparative Example 18 using only a resin emulsion and Comparative Example 20 in which a zinc cyanurate slurry was wet-pulverized to prepare a dispersion liquid and then mixed with a resin emulsion, the coating film had a good appearance but was poor in adhesion (B). In Comparative Example 19 in which a zinc cyanurate slurry was mixed with a resin emulsion, both the coating film appearance (poor) and adhesion (C) were significantly poorer than those of the Examples.

FIG. 1 is a graph showing an approximation curve calculated from the measured value of the zeta potential (mV) of inorganic oxide particles versus the pH value (pH 2 to 10 (horizontal axis)) of an aqueous dispersion slurry of inorganic oxide powder: silica powder (fumed silica A, fumed silica B, silica powder C) or titania powder (titania powder).
As shown in FIG. 1 and Table 8, the inorganic oxide particles used in this example: silica powder (fumed silica A, fumed silica B, silica powder C) and titania powder (titania powder) all had no isoelectric point in the range of pH 5 to pH 12, and had a zeta potential of −5 mV to −50 mV in that pH range.
As described above, in each of the paint additives using these powders, paint additive 1 (fumed silica A), paint additive 2 (fumed silica B), paint additive 3 (silica powder C), and paint additive 4 (titania powder), no precipitated layer was visually observed after standing at room temperature for 12 hours, and it was confirmed that a good dispersion state was maintained. It was confirmed that a dispersion liquid with excellent dispersibility can be obtained by using inorganic oxide particles that do not have an isoelectric point at pH 5 to pH 12 and have a zeta potential of -5 mV to -50 mV in this pH region.

Claims (26)

Dispersoid particles including inorganic oxide particles and zinc cyanurate particles, and a liquid medium ;
Resin ;
A coating composition for a surface to be coated which is at least one selected from the group consisting of an aluminum substrate, an iron substrate, a copper substrate, a gold substrate, a silver substrate, a platinum substrate, a mirror material, a glass substrate, a silicon substrate, wood, a resin film, and a resin molded product ,
the zinc cyanurate particles have a major axis of 400 nm to 3,000 nm and a minor axis of 10 nm to 300 nm, and a ratio of the major axis to the minor axis of 1.3 to 300, as measured by a transmission electron microscope;
the dispersoid particles have an average particle size of 80 nm to 5,000 nm as measured by a laser diffraction method,
the liquid medium is water,
The resin is in the form of a resin emulsion, a water-soluble polymer, or a colloidal dispersion,
the dispersoid particles contain inorganic oxide particles:zinc cyanurate particles in a mass ratio of 1:0.01 to 1:100,
the ratio of the dispersoid particles to the resin is 1:0.1 to 1:20 in terms of the mass ratio of (dispersoid particles):(resin),
The proportion of total solids in the coating composition is 1 to 50 mass%; and
In the coating composition, the total mass of the dispersoid particles including inorganic oxide particles and zinc cyanurate particles and the resin is 22 to 37.3 mass%.
Coating composition. The resin is in the form of a resin emulsion, the form being an oil-in-water emulsion or a water-in-oil emulsion, and the resin is an acrylic resin, an acrylic-styrene resin, an acrylic-silicone resin, a vinyl acetate resin, a styrene resin, an olefin resin, an ethylene-vinyl acetate resin, an ester resin, an epoxy resin, a phenol resin, an amide resin, a vinyl alcohol resin, a fluorine resin, a urethane resin, a melamine resin, a phthalic acid resin, a silicone resin, an alkyd resin, and a vinyl chloride resin. The coating composition according to claim 1, which is a resin emulsion containing one or more resin components selected from the group consisting of vinyl chloride resins. The coating composition according to claim 1, wherein the resin is in the form of a water-soluble polymer or a colloidal dispersion, and the resin is a water-soluble resin or a colloidal dispersion containing one or more resin components selected from the group consisting of acrylic resins, acrylic-styrene resins, acrylic-silicone resins, vinyl acetate resins, styrene resins, olefins, ethylene-vinyl acetate resins, ester resins, epoxy resins, phenolic resins, amide resins, vinyl alcohol resins, fluorine resins, urethane resins, melamine resins, phthalic acid resins, silicone resins, alkyd resins , and vinyl chloride resins. The coating composition according to any one of claims 1 to 3, wherein the inorganic oxide particles are an oxide of at least one element selected from the group consisting of Si, Al, Ti, Zr, Fe, Cu, Zn, Li, Na, K, Mg, Ca, Cs, Sr, Ba, B, Ga, Y, Nb, Mo, In, Sn, Sb, Ta, W, Ge, Pb, P, As, Rb, Bi and Ce . The coating composition according to claim 4, wherein the inorganic oxide particles are a composite oxide or a mixed oxide of two or more elements selected from the group consisting of Si, Al, Ti, Zr, Fe, Cu, Zn, Li, Na, K, Mg, Ca, Cs, Sr, Ba, B, Ga, Y, Nb, Mo, In, Sn , Sb, Ta, W, Ge, Pb, P, As, Rb, Bi and Ce. 5. The coating composition according to claim 1, wherein the inorganic oxide particles are colloidal oxides of at least one element selected from the group consisting of Si, Al, Ti, Zr, Fe, Cu, Zn, Li, Na, K, Mg, Ca, Cs, Sr, Ba, B, Ga , Y, Nb, Mo, In, Sn, Sb, Ta, W, Ge, Pb, P, As, Rb, Bi and Ce. 7. The coating composition according to claim 6, wherein the inorganic oxide particles are colloidal composite oxides or colloidal mixed oxides of two or more elements selected from the group consisting of Si, Al, Ti, Zr, Fe, Cu, Zn, Li, Na, K, Mg, Ca, Cs, Sr, Ba, B, Ga, Y, Nb, Mo, In, Sn, Sb, Ta, W, Ge, Pb, P, As, Rb, Bi and Ce. The coating composition according to any one of claims 1 to 4, wherein the inorganic oxide particles are a powder (inorganic oxide powder) of an oxide of at least one element selected from the group consisting of Si, Al, Ti, Zr, Fe, Cu, Zn, Li, Na, K, Mg, Ca, Cs, Sr, Ba, B, Ga, Y, Nb, Mo, In, Sn, Sb, Ta, W, Ge, Pb, P, As, Rb, Bi and Ce. The coating composition according to claim 8, wherein the inorganic oxide particles are a powder of a composite oxide or a powder of a mixed oxide of two or more elements selected from the group consisting of Si, Al, Ti, Zr, Fe, Cu, Zn, Li, Na, K, Mg, Ca, Cs, Sr, Ba, B, Ga, Y, Nb, Mo, In, Sn, Sb, Ta, W, Ge, Pb, P, As, Rb, Bi and Ce. 10. A coating film of the coating composition according to any one of claims 1 to 9, formed on at least one substrate selected from the group consisting of an aluminum substrate, an iron-based substrate, a copper-based substrate, a gold-based substrate, a silver-based substrate, a platinum-based substrate, a mirror material, a glass substrate, a silicon substrate , wood, a resin film, and a resin molding. A coating film of the coating composition according to any one of claims 1 to 9 , having a thickness of 0.1 µm to 100 µm. The coating film according to claim 11 , wherein the coating film is a spin-coated film, a bar-coated film, a roll-coated film, or a dip-coated film. 10. A method for producing a coating composition according to claim 1 , comprising a step of mixing a dispersion in which dispersoid particles containing inorganic oxide particles and zinc cyanurate particles are dispersed in a liquid medium with a resin using a submerged disperser. The method for producing a coating composition according to claim 13, wherein the solid content concentration of the dispersoid particles in the dispersion is 0.1 to 50 mass %. 15. A method for producing a coating composition according to claim 13 or 14, comprising a step of mixing, using a submerged disperser, a dispersion in which dispersoid particles containing inorganic oxide particles and zinc cyanurate particles are dispersed in a liquid medium, the resin, and a slurry of inorganic oxide powder having a solid content concentration of 0.5 to 50 mass% . The method for producing a coating composition according to claim 15, wherein the ratio of the solid content in the dispersion to the solid content in the slurry of the resin and the inorganic oxide powder is 1:0.1 to 20:0.1 to 1 in terms of a mass ratio of (solid content in the dispersion):(resin):(solid content in the slurry). The manufacturing method according to any one of claims 13 to 16 , wherein the submerged disperser is a stirrer, a rotary shear type stirrer, a colloid mill, a roll mill, a high-pressure jet type disperser, an ultrasonic disperser, a vessel-driven mill, a media stirring mill, or a kneader. The method for producing a coating composition according to any one of claims 13 to 17, further comprising a step of mixing the mixture of inorganic oxide particles and zinc cyanurate particles or a slurry thereof using a grinding device prior to the step of mixing using the submerged disperser. The method according to claim 18 , wherein the grinding device is a ball mill, a bead mill, or a sand mill. A coating additive for use in the coating composition according to claim 1,
A paint additive in which dispersoid particles including inorganic oxide particles and zinc cyanurate particles are dispersed in a liquid medium,
The inorganic oxide particles are inorganic oxide powders,
The inorganic oxide powder has a specific surface area of 1 to 800 m ² /g and a loose bulk density of 0.03 to 3.0 g/cm ³ ;
The paint additive , wherein the dispersoid particles have an average particle size of 200 nm to 5,000 nm as measured by a laser diffraction method . The coating additive of claim 20, wherein the inorganic oxide powder is an oxide of at least one element selected from the group consisting of Si, Al, Ti, Zr, Fe, Cu, Zn, Li, Na, K, Mg, Ca, Cs, Sr, Ba, B, Ga, Y, Nb, Mo, In, Sn , Sb , Ta, W, Ge, Pb, P, As, Rb, Bi and Ce. The paint additive according to claim 20 or 21 , wherein the dispersoid particles in the paint additive have a solid content concentration of 0.1 to 50 mass %. 23. The method for producing a paint additive according to claim 20, further comprising the step of mixing, using a grinding device, a mixture of inorganic oxide powder obtained by grinding inorganic oxide particles in advance and zinc cyanurate particles or a slurry thereof. A coating additive for use in the coating composition according to claim 1,
A paint additive in which dispersoid particles including inorganic oxide particles and zinc cyanurate particles are dispersed in a liquid medium,
The inorganic oxide particles are colloidal metal oxide particles other than particles mainly composed of colloidal silica,
The dispersoid particles have an average particle size of 80 nm to 2,000 nm as measured by a laser diffraction method .
Paint additives . 25. The paint additive of claim 24, wherein the colloidal metal oxide particles comprise an oxide of at least one element selected from the group consisting of Al, Ti, Zr, Fe, Cu, Zn, Li, Na, K, Mg, Ca, Cs, Sr, Ba, B, Ga, Y, Nb, Mo, In, Sn , Sb , Ta, W, Ge, Pb, P, As, Rb, Bi, and Ce. The paint additive according to claim 24 or 25 , wherein the dispersoid particles in the paint additive have a solid content concentration of 0.1 to 50 mass %.

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