TWI620803B - Fluororesin composition, coating film and article - Google Patents

Abstract

An object of the present invention is to provide a fluororesin composition capable of forming a coating film having excellent heat-resistant adhesion, cold-resistant adhesion, water resistance, and high transparency and surface hardness.

The fluororesin composition of the present invention contains a hydroxy-containing fluorinated copolymer (A) having a hydroxyl value of 30 to 200 mgKOH / g, an acrylic copolymer (B), and a hot-line shield having an average particle diameter of 1 to 200 nm. (heat ray shielding) pigment (C), ultraviolet absorber (D), silane coupling agent (E), colloidal silicon dioxide (F), and organic solvent (G), and the haze (haze) is 2.0% or less, all The light transmittance is above 70%.

Description

Fluororesin composition, coating film and article

The present invention relates to a fluororesin composition, a coating film, and an article.

In order to suppress the intrusion of ultraviolet rays or infrared rays, it is known to form a coating film on the glass surface of a building such as a house, a building, or a car. The window glass surface has this kind of coating film, which can prevent the temperature inside the building from rising excessively.

The coating film needs not only a function of shielding ultraviolet rays or infrared rays, but also other functions. For example, the transparency of the field of view must not be obstructed. In addition, weather resistance and water resistance are required because they are directly exposed to sunlight or wind and rain.

The coating film formed on the glass surface is a coating composition comprising, for example, a coating composition containing an infrared or ultraviolet shielding material containing a metal oxide such as tin-doped indium oxide (ITO), an organic resin, and various additives, and the like. Formation (Patent Documents 1 to 2).

Patent Document 3 discloses that a metal oxide semiconductor, a near-infrared absorber, an ultraviolet absorber, and a synthetic resin transparent to visible light are mixed in an organic solvent, coated on a transparent substrate, and dried to remove the organic solvent. UV rays formed by the agent. Infrared shield.

Patent Document 4 discloses that a fluororesin composition for a coating material containing a fluororesin having a hydroxyl value of 30 to 200 mgKOH / g and a heat ray having an average particle diameter of 1 to 200 nm to shield inorganic fine particles is coated on a glass plate and dried to form transparency, Hot wire shielding film with excellent chemical resistance and weather resistance.

[Advanced technical literature] [Patent Literature]

[Patent Document 1] Japanese Unexamined Patent Publication No. 8-134432

[Patent Document 2] Japanese Patent Application Laid-Open No. 10-279329

[Patent Document 3] Japanese Patent No. 4016385

[Patent Document 4] Japanese Patent Laid-Open No. 2009-24145

[Invention Summary]

However, although the conventional coating film improves the shielding effect of ultraviolet and infrared rays, when the temperature changes are large, there is a problem that the coating film is peeled from the window glass. In addition, when the window glass is cleaned, there is a problem of injury when the coating film is wiped.

The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a fluororesin composition capable of forming a coating film having excellent heat-resistant adhesion, cold-resistant adhesion, and water resistance, and having a high transparency and surface hardness.

The inventors have formulated a specific component in a hydroxyl-containing curable fluoropolymer to form a coating film having excellent heat resistance, cold resistance, water resistance, and high surface hardness and transparency. Then completed the present invention.

In other words, the present invention is a fluororesin composition, which contains: a hydroxyl-containing fluorinated copolymer (A) having a hydroxyl value of 30 to 200 mgKOH / g, an acrylic copolymer (B), and an average particle diameter of 1 to 200 nm. Heat ray shielding pigment (C), ultraviolet absorber (D), silane coupling agent (E), colloidal silicon dioxide (F) and organic solvent (G).

The fluororesin composition is preferably one having a haze of 2.0% or less and a total light transmittance of 70% or more.

The acrylic copolymer (B) is preferably compatible with the hydroxyl-containing fluorinated copolymer (A).

The number average molecular weight of the hydroxyl-containing fluorinated copolymer (A) is preferably 50,000 or less.

The hot-line shielding pigment (C) is preferably at least one selected from the group consisting of tin-doped indium pigment, antimony-doped tin oxide pigment, lanthanum hexaboride pigment, and zinc oxide pigment. .

The ultraviolet absorber (D) is preferably selected from the group consisting of a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, a cyanoacrylate-based ultraviolet absorber, and a coumarin-based ultraviolet absorber. At least one group of ultraviolet absorbers.

The fluororesin composition preferably further contains a hardener (H).

The fluororesin composition preferably further contains a leveling agent (I).

The fluororesin composition preferably further contains a hydrophilizing agent (J).

This invention is a coating film characterized by being formed using the said fluororesin composition.

The present invention is an article characterized by having a transparent substrate and a coating film formed on the transparent substrate using the fluororesin composition.

The transparent substrate is preferably glass.

The present invention is explained in detail below.

When the fluororesin composition of the present invention is used, a coating film having excellent heat resistance, cold resistance, and water resistance and high surface hardness and transparency can be produced.

[Mode for Carrying Out the Invention]

The present invention contains a hydroxyl-containing fluorinated copolymer (A), an acrylic copolymer (B) having a hydroxyl value of 30 to 200 mgKOH / g, a heat-ray shielding pigment (C) having an average particle diameter of 1 to 200 nm, and an ultraviolet absorber. (D), silane coupling agent (E), colloidal silica (F), and organic solvent (G).

Therefore, it is possible to produce a coating film which is excellent in heat-resistant adhesiveness, cold-resistant adhesiveness, and water resistance, and has high surface hardness and transparency.

Hereinafter, each component which comprises the fluororesin composition of this invention is demonstrated.

(A) Hydroxyl-containing fluorinated copolymer

The fluororesin composition of the present invention can form a coating film excellent in weather resistance, moisture resistance, heat resistance, and insulation by containing a hydroxyl-containing fluorinated copolymer (A) having a hydroxyl value of 30 to 200 mgKOH / g.

From the viewpoint of improving the water resistance or adhesion of the obtained coating film, the hydroxyl value is preferably 35 mgKOH / g or more, and more preferably 40 mgKOH / g or more. From the viewpoint of improving solvent solubility and adhesion, it is preferably 150 mgKOH / g or less, and more preferably 100 mgKOH / g or less.

The said hydroxyl value is a value measured by the method based on JISK0070.

The hydroxyl-containing fluorinated copolymer preferably contains a polymerization unit based on a fluorine-containing monomer and a polymerization unit based on a hydroxyl-containing monomer.

Examples of the hydroxyl-containing monomer include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4- Hydroxy-containing vinyl ethers such as hydroxybutyl vinyl ether, 4-hydroxy-2-methylbutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether; 2-hydroxy Hydroxyl-containing allyl ethers, such as ethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether, and the like. Among these, vinyl ethers containing a hydroxyl group are preferred, and 4-hydroxybutyl vinyl ether and 2-hydroxyethyl vinyl ether are particularly preferred because they have excellent polymerization reactivity and hardenability of a functional group. Better.

Other hydroxyl-containing monomers include, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and the like Alkyl esters and the like.

The fluorine-containing monomer, that is, a monomer for forming a fluoropolymer into which the above-mentioned hydroxyl group is introduced, includes, for example, tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride, and fluorovinyl ether. Etc. One kind or two or more kinds can be used.

Among them, at least one selected from the group consisting of tetrafluoroethylene, chlorotrifluoroethylene, and vinylidene fluoride is preferable, and tetrafluoroethylene is more preferable.

The fluorine-containing polymer into which the above-mentioned hydroxyl group is introduced includes, for example, a polymerization unit that constitutes the polymer, and the following are examples.

(1) Perfluoroolefin polymers based on perfluoroolefin units: Specific examples include individual polymers of tetrafluoroethylene (TFE) or TFE, hexafluoropropylene (HFP), and perfluoro (alkyl alkenyl ether) (PAVE) and the like, and copolymers of other monomers copolymerizable therewith.

The other copolymerizable monomers described above include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, trimethyl vinyl acetate, vinyl hexanoate, and versatic acid ethylene. Esters, vinyl laurate, vinyl stearate, vinyl cyclohexyl carboxylate, vinyl benzoate, vinyl p-t-butyl benzoate, and other carboxylic acid vinyl esters; methyl vinyl ether, Alkyl vinyl ethers such as ethyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether; fluorine-based olefins such as ethylene, propylene, n-butene, and isobutylene; vinylidene fluoride (VdF (vinylidene fluoride), chlorotrifluoroethylene (CTFE), fluoroethylene (VF), and fluorine-based monomers such as fluorovinyl ether, but are not limited thereto.

Among these, TFE-based polymers mainly composed of TFE are preferable because they are excellent in pigment dispersibility, weather resistance, copolymerization, and chemical resistance.

Specific perfluoroolefin-based polymers containing a hardening functional group include, for example, a copolymer of TFE / isobutylene / hydroxybutyl vinyl ether / other monomers, TFE / ethylene tert-carbonate / hydroxybutyl vinyl ether / Copolymers of other monomers, copolymers of TFE / VdF / hydroxybutyl vinyl ether / other monomers, etc. Particularly preferred are copolymers of TFE / isobutylene / hydroxybutyl vinyl ether / other monomers, Copolymers of TFE / ethylene tert-carbonate / hydroxybutyl vinyl ether / other monomers.

TFE-based hardening polymer compositions for coatings include, for example, ZEFFLE GK series manufactured by Daikin Industries, Ltd.

(2) TFE polymer mainly composed of chlorotrifluoroethylene (CTFE) units: Specific examples include, for example, a copolymer of CTFE / hydroxybutyl vinyl ether / other monomers.

CTFE-based hardening polymer compositions for coatings include, for example, Lumiflon made by Asahi Glass, Fluonate made by DIC, Cefral Coat made by Central Glass, and Zaflon made by Toa Kosei.

(3) VdF polymer based on vinylidene fluoride (VdF) units: Specific examples include copolymers of VdF / TFE / hydroxybutyl vinyl ether / other monomers.

(4) A fluorine-containing alkyl polymer having a fluoroalkyl unit as a main component: Specific examples include CF ₃ CF ₂ (CF ₂ CF ₂ ) _n CH ₂ CH ₂ OCOCH = CH ₂ (n = 3 and 4 mixture) / 2-hydroxyethyl methacrylate / Stearyl acrylate copolymer and the like.

Examples of the fluorine-containing alkyl polymer include Unidyne or Ftone manufactured by Daikin Industries, Ltd., and Zonyl manufactured by Dupon.

Among these, in consideration of weather resistance and moisture resistance, a perfluoroolefin-based polymer is preferred.

The hydroxyl-containing fluorinated copolymer (A) can be produced by a method disclosed in, for example, Japanese Patent Application Laid-Open No. 2004-204205.

The hydroxyl-containing fluorinated copolymer (A) is preferably one having a number average molecular weight of 50,000 or less. When the number average molecular weight is too small, the hardness of the obtained coating film is insufficient. When the number average molecular weight is too large, the viscosity of the coating composition becomes high and the appearance of the coating film becomes poor. Therefore, it is preferably 1,000 or more, more preferably 3,000 or more, and more preferably 5000. the above. It is more preferably 30,000 or less, and still more preferably 20,000 or less.

The number average molecular weight is a value obtained in terms of polystyrene by a gel permeation chromatography (GPC) method.

The content of the hydroxyl-containing fluorinated copolymer (A) is 100% by mass with respect to the total amount of the nonvolatile matter in the fluororesin composition, and preferably 20 to 90% by mass.

(B) acrylic copolymer

The fluororesin composition of the present invention contains an acrylic copolymer (B), therefore, the hardness of the obtained coating film becomes higher, and the finished appearance becomes better.

The acrylic copolymer (B) is preferably compatible with the hydroxyl-containing fluorine-containing copolymer (A).

Compatibility with the above-mentioned hydroxyl-containing fluorinated copolymer (A) means that it has good miscibility, does not separate, and the transparency of the coating film is not significantly impaired.

The acrylic copolymer (B) is preferably one which does not contain a fluorine atom.

Acrylic copolymers are, for example, those conventionally used in coatings, and among them, a single polymer or copolymer selected from (i) (meth) acrylic acid alkyl esters having 1 to 10 carbon atoms and (ii) side chains are preferred. And / or at least one group of (meth) acrylate copolymers having a hardenable functional group at the main chain end.

Examples of the acrylic polymer of (i) include meth (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate A separate polymer or copolymer of (meth) acrylic monomers such as t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, or Copolymer with ethylenically unsaturated monomers copolymerizable with these.

Among these, isobutyl (meth) acrylate, t-butyl (meth) acrylate, and 2-ethylhexyl are preferred from the viewpoint of excellent compatibility with the hydroxyl-containing fluorinated copolymer (A). Individual polymers and copolymers of (meth) acrylates or cyclohexyl (meth) acrylates, and copolymers of ethylenically unsaturated monomers copolymerizable therewith.

The above copolymerizable ethylenically unsaturated monomers include, for example, (Meth) acrylates having an aromatic group, (meth) acrylates having a fluorine atom or a chlorine atom at the α position, fluoroalkyl (meth) acrylates having an alkyl group substituted with a fluorine atom, vinyl group Ethers, vinyl esters, aromatic vinyl monomers such as styrene, olefins such as ethylene, propylene, isobutylene, vinyl chloride, vinylidene chloride, fumaric acid diesters, Maleic acid diesters, (meth) acrylonitrile, and the like.

The acrylic polymer of the above (ii) includes, for example, a copolymer of the (meth) acrylic monomer described in the above (i) and a monomer having a curable functional group.

Examples of the monomer having a curable functional group include monomers having a hydroxyl group, a carboxyl group, an epoxy group, and an amine group.

Specific examples of the acrylic polymer of (ii) include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl vinyl ether, and (meth) Monomers containing curable functional groups such as acrylic acid, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, and the like ( Copolymers of alkyl esters of meth) acrylic acid having 1 to 10 carbons, or copolymers thereof with the above ethylenically unsaturated monomers, but are not limited thereto.

The content of the alkyl polymer having 1 to 10 carbon atoms of the acrylic polymer-based (meth) acrylic acid of (i) and (ii) above, in solvent solubility, weather resistance, water resistance, chemical resistance, hardness, and fluorine From the viewpoint of excellent compatibility of the resin, it is preferably 5 mass% or more, and more preferably 10 mass% or more. Further, from the viewpoint of excellent adhesion, weather resistance, and chemical resistance, it is preferably 98% by mass or less, and particularly preferably 96% by mass or less.

In particular, alkyl esters of 1 to 10 carbon atoms of (meth) acrylic acid, when t-butyl (meth) acrylate is used, the content of t-butyl (meth) acrylate, solvent solubility and weather resistance , Adhesion, hardness, compatibility with fluororesin, water resistance, and chemical resistance are excellent. Therefore, it is preferably 10% by mass or more, and more preferably 20% by mass or more. From the viewpoint of compatibility with a fluororesin, flexibility, and the like, it is preferably 98% by mass or less, and particularly preferably 95% by mass or less.

In this case, preferred copolymerizable ethylenically unsaturated monomers used in combination have excellent solvent solubility, chemical resistance, and adhesion, and there are, for example, (meth) acrylates having an aromatic group. (Meth) acrylates having a fluorine atom or chlorine atom in the alpha position, fluoroalkyl (meth) acrylates in which alkyl groups are replaced by fluorine atoms, vinyl ethers, vinyl esters, styrene, etc. Aromatic vinyl monomers, olefins such as ethylene, propylene, isobutylene, vinyl chloride, vinylidene chloride, fumaric acid diesters, maleic acid diesters, (meth) acrylonitrile, and the like.

In this case, the monomer having a hardenable functional group used in combination has excellent adhesion, chemical resistance, and hardenability, and examples thereof include monomers having a hydroxyl group, a carboxyl group, an epoxy group, and an amine group. . Specific examples include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl vinyl ether, (meth) acrylic acid, and glycidyl (meth) acrylic acid. Monomer containing a curable functional group such as an ester, 2-aminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, and the like.

The content of the monomer having a hardening functional group is excellent in water resistance, solvent solubility, chemical resistance, weather resistance, compatibility with a fluororesin, and adhesion, and therefore, it is preferably 50% by mass or less. It is more preferably 40% by mass or less, and from the viewpoints of water resistance, chemical resistance, and adhesion, it is preferably 2% by mass or more, and particularly preferably 4% by mass or more.

Commercial products of the acrylic polymer (i) include, for example, Hitaloid 1005, Hitaloid 1206, Hitaloid 2330-60, Hitaloid 4001, Hitaloid 1628A, etc. (all manufactured by Hitachi Chemical Industries, trade names); DIANAL LR-1065, DIANAL LR-90, DIANAL LR-620, DIANAL LR-660, DIANAL LR-670, etc. (all manufactured by Mitsubishi Rayon, trade names); PARALOID B-44, PARALOID B-66, PARALOID A-21, PARALOID B-82 (All Rohm & Haas company, trade name); ELVACITE 2000, etc. (Dupon company, trade name) and so on.

Commercial products of the acrylic copolymer (ii) include, for example, Hitaloid 3004, Hitaloid 3018, Hitaloid 3046C, Hitaloid 6500B, Hitaloid 6500, etc. (all manufactured by Hitachi Chemical Industries, trade names); ACRYDIC A810-45, ACRYDIC A814, ACRYDIC 47-540, etc. (both DIC (stock), trade name); DIANAL LR-620, DIANAL LR-660, DIANAL LR-670, DIANAL SS-1084, DIANAL SS-792, etc. (all manufactured by Mitsubishi Rayon Corporation, (Trade name); I starQ166, I starQ185, etc. (both are manufactured by Mitsui To pressure Chemical Co., Ltd., trade names); Hariakuron 8360G-55, Hariakuron 8360HS-130, Hariakuron 8160, etc. (all are manufactured by Harima Kasei Corporation, trade names).

The number average molecular weight of the acrylic copolymer (B) is preferably 1,000 to 200,000. If it is less than 1,000, there is a concern that the weather resistance will decrease, and if it exceeds 200,000, there will be a concern that the solvent solubility will decrease.

The number average molecular weight is more preferably 2,000 or more, and more preferably 100,000 or less.

The number average molecular weight is a value obtained by measurement by a gel permeation chromatography (GPC) method.

The hydroxy value of the acrylic copolymer (B) is preferably 0 to 200 mgKOH / g. From the viewpoint of improving the water resistance or adhesion of the obtained coating film, it is more preferably 30 mgKOH / g or more, still more preferably 40 mgKOH / g or more, and particularly preferably 50 mgKOH / g or more. From the viewpoint of better solvent solubility or adhesion of the obtained coating film, it is more preferably 150 mgKOH / g or less, and still more preferably 100 mgKOH / g or less.

The said hydroxyl value is a value measured by the method based on JISK0070.

The glass transition temperature (Tg) of the acrylic copolymer (B) is preferably 20 to 110 ° C. From the viewpoint that the hardness of the obtained coating film becomes higher, it is more preferably 40 ° C or more, and still more preferably 60 ° C or more.

The glass transition temperature (Tg) is a value measured by a method of glass transition temperature (2nd run) obtained by a differential scanning calorimeter (DSC).

The content of the acrylic copolymer (B) is relative to The total solid content of the hydroxyl-containing fluorinated copolymer (A) and the acrylic copolymer (B) is preferably 10 to 90% by mass based on the solid content. From the viewpoint of improving the hardness and adhesion of the obtained coating film, it is more preferably 20 to 50% by mass.

(C) Hot-line shielding pigment

Since the fluororesin composition of the present invention contains a hot-ray shielding pigment (C), it can effectively shield infrared rays and can form a coating film with good transparency.

The hot-line shielding pigment (C) is preferably selected from tin-doped indium oxide (ITO) pigments, antimony-doped tin oxide (ATO) pigments, lanthanum hexaboride (LaB ₆ ) pigments, and oxides. At least one type of zinc pigment.

The zinc oxide pigment may contain dopants such as aluminum, gallium, indium, yttrium, boron, scandium, and thallium. The hot-line shielding pigment (C) is more preferably selected from the group consisting of tin-doped indium oxide (ITO) pigment and antimony-doped tin oxide (ATO) pigment in terms of shielding infrared, near-infrared and far-infrared rays with high efficiency. At least one species of group.

The heat-ray shielding pigment (C) can be used alone or in combination of two or more.

The average particle diameter of the heat ray shielding pigment (C) is 1 to 200 nm. In order to obtain certain shielding properties and transparency, the average particle diameter is preferably 10 nm or more, more preferably 20 nm or more, more preferably 150 nm or less, and even more preferably 100 nm or less.

The above average particle size is obtained by diluting a pigment dispersion liquid with acetone to a solid content concentration of about 0.01 to 1.0% by mass, and then using a dynamic light scattering method to determine the particle size. Measured by laser light scattering method.

The content of the hot-line shielding pigment (C) is 5 to 70% by mass based on the total solid content of the hydroxyl-containing fluorinated copolymer (A) and the acrylic copolymer (B). From the viewpoint that infrared rays, near-infrared rays, and far-infrared rays can be shielded efficiently, the content is more preferably 10% by mass or more. From the viewpoint of high visible light transmittance, it is more preferably 50% by mass or less.

(D) Ultraviolet absorbent

Since the fluororesin composition of the present invention contains an ultraviolet absorber (D), it can form a coating film excellent in weather resistance and shielding ultraviolet rays harmful to the human body.

Examples of the ultraviolet absorber include a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, a cyanoacrylate-based ultraviolet absorber, and an oxaldianilide-based ultraviolet absorber. And other organic ultraviolet absorbers such as titanium oxide, barium sulfate, zinc oxide, silicon dioxide, magnesium oxide, aluminum oxide, iron oxide, cerium oxide and the like.

Among them, from the viewpoint that the ultraviolet shielding property of the obtained coating film becomes high, it is preferably selected from the group consisting of benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, and cyanoacrylate At least one of a group of ultraviolet absorbers and coumarin-based ultraviolet absorbers.

Examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone and 2-hydroxy-4-octyloxybenzophenone.

The benzotriazole-based ultraviolet absorber includes, for example, phenylpropanoic acid 3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy C7-9 Side chain and linear alkyl ester (Tinuvin 384-2: trade name, manufactured by BASF), 3- [3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxybenzene Propyl] isooctyl propionate (Tinuvin 384: trade name, manufactured by BASF), 2- (2'-hydroxy-3 ', 5'-di-tert-pentylphenyl) -2H-benzotriazole ( Tinuvin 328: trade name, manufactured by BASF), 2- [2-hydroxy-3,5-bis (1,1-dimethylbenzyl) phenyl] -2H-benzotriazole (Tinuvin 900: trade name , Manufactured by BASF), 2- [2-hydroxy-3- (1,1-dimethylbenzyl) -5- (1,1,3,3-tetramethylbutyl) phenyl] -2H- Benzotriazole (Tinuvin 928: trade name, manufactured by BASF), 3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propanoic acid methyl ester Ester / polyethylene glycol 300 condensate (Tinuvin 1130: trade name, manufactured by BASF) and the like.

Examples of the triazine-based ultraviolet absorber include 2- (4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl) -4,6-bis (2, 4-dimethylphenyl) -1,3,5-triazine (Tinuvin 400: trade name, manufactured by BASF), 2- (4-[(2-hydroxy-3-tridecyloxypropyl) Oxy] -2-hydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, Tinuvin 479 (trade name, manufactured by BASF), and the like.

Examples of the cyanoacrylate-based ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate (Uvinul 3039: trade name, manufactured by BASF) and the like.

The coumarin-based ultraviolet absorber includes, for example, 3-phenyl-7- (4'-methyl-5'-n-butoxybenzotriazolyl-2-) coumarin and the like.

Among these, the above-mentioned ultraviolet absorbent (D) is more preferably a triazine-based ultraviolet absorbent from the viewpoint that a coating film having high transparency and ultraviolet shielding properties can be formed.

The said ultraviolet absorber (D) can be used individually or in combination of 2 or more types.

The content of the ultraviolet absorber (D) is preferably 0.1 to 10% by mass based on the total solid content of the hydroxyl-containing fluorinated copolymer (A) and the acrylic copolymer (B). The content is more preferably 1% by mass or more, and even more preferably 8% by mass or less.

When the content of the ultraviolet absorber (D) is two or more, the total amount of them is used.

(E) Silane coupling agent

Since the fluororesin composition of the present invention contains a silane coupling agent (E), a coating film having a high surface hardness can be formed.

The silane coupling agent (E) includes, for example, a silane coupling agent containing an epoxy group, an amine group, an isocyanate group, a hydrogen sulfide group, or a (meth) acrylate group. Specifically, for example, a γ-glycidoxypropyl group Trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxy Silane, γ-hydrothiopropyltriethoxysilane, OCNC ₃ H ₆ Si (OCH ₃ ) ₃ , OCNC ₃ H ₆ Si (OC ₂ H ₅ ) ₃ and the like.

Among them, OCNC ₃ H ₆ Si (OCH ₃ ) _{3 is} preferable from the viewpoint of good adhesion and compatibility.

The said silane coupling agent (E) can be used individually or in combination of 2 or more types.

The content of the silane coupling agent (E) is preferably 0.1 to 30% by mass based on the total solid content of the hydroxyl-containing fluorinated copolymer (A) and the acrylic copolymer (B). From the viewpoint that the adhesiveness becomes higher, the content is more preferably 5.0% by mass or more, and still more preferably 20% by mass or less.

(F) Colloidal silica

Since the fluororesin composition of the present invention contains colloidal silicon dioxide (F), the transparency and hardness of the obtained coating film can be improved.

The average particle diameter of the colloidal silicon dioxide (F) is preferably 1 to 200 nm.

The average particle diameter is preferably 5 nm or more from the viewpoint that the dispersion stability of the coating material or the hardness of the obtained coating film becomes good. From the viewpoint of good transparency, the thickness is preferably 100 nm or less, and more preferably 60 nm or less.

The average particle size is a value obtained by measuring the colloidal silica solution with acetone to a solid content concentration of about 0.01 to 1.0% by mass, and then measuring it by a laser light scattering method using a dynamic light scattering method particle size analyzer.

Examples of the colloidal silica (F) include organosol IPA-ST, MEK-ST, and MEK-AC-22 (all manufactured by Nissan Chemical Industries, Ltd.).

The content of the colloidal silicon dioxide (F) is based on the total solid content of the hydroxyl-containing fluorinated copolymer (A) and the acrylic copolymer (B), and is preferably 1.0 to 12% by mass based on the solid content. Colloidal silica The content of (F) is preferably 2.0% by mass or more, and more preferably 10% by mass or less from the viewpoint that the surface hardness of the obtained coating film becomes higher and the permeability is improved.

(G) Organic solvents

The organic solvent (G) used in the fluororesin composition of the present invention includes, for example, ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, cellulose acetate, propylene glycol methyl ether acetate, and the like. Esters; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; cyclic ethers such as tetrahydrofuran, dioxane; N, N-dimethylformamide, N , N-dimethylacetamide and other amines; aromatic hydrocarbons such as xylene, toluene, solvent naphtha; propylene glycol methyl ether, ethylcellulose and other glycol ethers; carbitol Diethylene glycol esters such as acetate; n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n- Aliphatic hydrocarbons such as dodecane, mineral spirits, etc .; these mixed solvents, etc. These can be used alone or in combination of two or more.

Among them, esters are preferred.

(H) Hardener

The fluororesin composition of the present invention may contain a hardener (H).

The hardener (H) is preferably, for example, an isocyanate-based hardener, a melamine resin, a silicate compound, an isocyanate group-containing silane compound, or the like.

The above-mentioned hardener (H), of which xylylenediamine is preferred Polyisocyanate compounds derived from at least one type of isocyanate selected from the group consisting of isocyanate (XDI) and bis (isocyanate methyl) cyclohexane (hydrogenated XDI, H6XDI), hexamethylene diisocyanate (HDI) -based At least one selected from the group consisting of a segment isocyanate compound, a polyisocyanate compound derived from hexamethylene diisocyanate (HDI), and a polyisocyanate compound derived from isophorone diisocyanate (IPDI).

As the hardener (H), at least one kind of isocyanate (hereinafter also referred to as an isocyanate (hereinafter referred to as an isocyanate (Isocyanate (Isocyanate (Isocyanate (Isocyanate)) i)) When the polyisocyanate compound (hereinafter also referred to as the polyisocyanate compound (I)) is derived, the adhesion between the coating film and the glass obtained from the coating composition of the present invention becomes more excellent.

The polyisocyanate compound (I) includes, for example, an adduct obtained by addition polymerization of the isocyanate (i) and a ternary or higher aliphatic polyol, and a cyanurate structure composed of the isocyanate (i) ( nurate structure) and biuret composed of the isocyanate (i).

The adduct preferably has, for example, the following general formula (1):

(In the formula, R ¹ represents an aliphatic hydrocarbon group having 3 to 20 carbon atoms. R ² represents a phenylene group or a cyclohexyl group. K is an integer of 3 to 20).

R ¹ in the above general formula (1) is a hydrocarbon group based on the above 3-membered aliphatic polyhydric alcohol, more preferably an aliphatic hydrocarbon group having 3 to 10 carbon atoms, and even more preferably an aliphatic hydrocarbon group having 3 to 6 carbon atoms. .

When R ² is phenylene, it may be 1,2-phenylene (o-phenylene), 1,3-phenylene (m-phenylene), and 1,4-phenylene (p -Phenylene). Among them, 1,3-phenylene (m-phenylene) is preferred. In addition, all of R ² in the general formula (1) may be the same phenylene group, or two or more of them may be mixed.

When R ² is a cyclohexyl group, it may be any of 1,2-cyclohexyl, 1,3-cyclohexyl and 1,4-cyclohexyl. Among them, 1,3-cyclohexyl is preferred. In addition, all of R ² in the general formula (1) may be the same cyclohexyl group, or two or more of them may be mixed.

The k is a number corresponding to the valence of the aliphatic polyhydric alcohol having 3 or more members. The above k is more preferably an integer of 3 to 10, and still more preferably an integer of 3 to 6.

The cyanate structure (nurate structure) has one or two or more molecules in the following general formula (2):

Represents a cyanurate ring.

The trimer isocyanate structure includes, for example, a trimer obtained by the trimerization reaction of the isocyanate, a pentamer obtained by the pentamerization reaction, a heptamer obtained by the heptamerization reaction, and the like.

Among them, the following general formula (3) is preferred:

The terpolymer represented by (wherein R ^{2 is the} same as R ² in the general formula (1)) is preferred. That is, the trimeric isocyanate structure is preferably a terpolymer of at least one isocyanate selected from the group consisting of xylylene diisocyanate and bis (isocyanate methyl) cyclohexane.

The biuret has the following general formula (4):

(In the formula, R ² is the same as R ² in the general formula (1).) The compound having a structure represented by the general formula (1) can be subjected to trimerization of the isocyanate under different conditions from those in the case of obtaining the trimeric isocyanate structure. And get.

The polyisocyanate compound (I) is preferably at least one isocyanate selected from the group consisting of xylylene diisocyanate and bis (isocyanate methyl) cyclohexane, and A trivalent or higher aliphatic polyhydric alcohol is obtained by addition polymerization.

When the polyisocyanate compound (I) is an adduct of the isocyanate (i) and a ternary or higher aliphatic polyol, the ternary or higher aliphatic polyol includes, for example, glycerin and trimethylolpropane (TMP) , 1,2,6-hexanetriol, trimethylolethane, 2,4-dihydroxy-3-hydroxymethylpentane, 1,1,1-ginseng (bishydroxymethyl) propane, 2, Tertiary alcohols such as 2-bis (hydroxymethyl) butanol-3; 4-alcohols such as pentaerythritol, diglycerol; 5-alcohols such as arabinitol, ribitol, xylitol (pentapentyl alcohol, pentite) 6-alcohols (hexite), such as sorbitol, mannitol, galactitol, allodulcit, and the like. Especially preferred are trimethylolpropane and pentaerythritol.

The xylylene diisocyanate (XDI) used as a constituent of the adduct includes, for example, 1,3-xylylene diisocyanate (m-xylylene diisocyanate) and 1,2-benzene Dimethyl diisocyanate (o-xylylene diisocyanate), 1,4-xylylene diisocyanate (p-xylylene diisocyanate), of which 1,3-xylylene diisocyanate is preferred Isocyanate (m-xylylene diisocyanate).

The bis (isocyanatemethyl) cyclohexane (hydrogenated XDI, H6XDI) used as a constituent of the adduct is, for example, 1,3-bis (isocyanatemethyl) cyclohexane, 1,2-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane, of which 1,3- is preferred Bis (isocyanatemethyl) cyclohexane.

The addition of at least one kind of isocyanate selected from the group consisting of xylylene diisocyanate and bis (isocyanate methyl) cyclohexane with an aliphatic polyhydric alcohol having a valence of 3 or more as described above can be used to obtain a suitable compound The adduct used in the invention.

The adducts suitable for use in the present invention include, for example, the following general formula (5):

(In the formula, R ³ represents a phenylene group or a cyclohexyl group.) A compound represented by at least one kind of isocyanate selected from the group consisting of xylylene diisocyanate and bis (isocyanate methyl) cyclohexane. Polyisocyanate compound obtained by addition polymerization of methylolpropane (TMP).

The phenyl group or cyclohexyl group represented by R ³ in the general formula (5) is as described above for R ^{2 in} the general formula (1).

Commercial products of the polyisocyanate compound represented by the above general formula (5) include, for example, Takenate D110N (made by Mitsui Chemicals Co., Ltd., an addition product of XDI and TMP, NCO content of 11.8%), Takenate D120N (made by Mitsui Chemicals Co., Ltd.) Bonus of H6XDI, TMP Material, NCO content 11.0%) and so on.

Specific examples when the polyisocyanate compound (I) is a trimeric isocyanate structure include Takenate D121N (Mitsui Chemical Co., Ltd., H6XDI nurate, NCO content 14.0%), Takenate D127N (Mitsui Chemical Co., Ltd., H6XDI) nurate, terpolymer of H6XDI, NCO content 13.5%) and so on.

When a block isocyanate based on hexamethylene diisocyanate (HDI) (hereinafter sometimes referred to as a block isocyanate) is used as the hardener, the fluororesin composition of the present invention can have a sufficient pot life. .

The block isocyanate is preferably obtained by reacting a polyisocyanate compound (hereinafter also referred to as a polyisocyanate compound (II)) derived from hexamethylene diisocyanate with a blocking agent.

The polyisocyanate compound (II) includes, for example, an adduct obtained by addition polymerization of a hexamethylene diisocyanate with a ternary or higher aliphatic polyol, and a cyanurate composed of hexamethylene diisocyanate. Structure (nurate structure) and biuret composed of hexamethylene diisocyanate.

The adduct preferably has, for example, the following general formula (6):

(Wherein R ⁴ is an aliphatic hydrocarbon group having 3 to 20 carbon atoms. K is an integer of 3 to 20).

R ⁴ in the above general formula (6) is a hydrocarbon group based on the above 3-membered aliphatic polyhydric alcohol, more preferably an aliphatic hydrocarbon group having 3 to 10 carbon atoms, and even more preferably an aliphatic hydrocarbon group having 3 to 6 carbon atoms.

The k is a number corresponding to the valence of the aliphatic polyhydric alcohol having 3 or more members. The above k is more preferably an integer of 3 to 10, and still more preferably an integer of 3 to 6.

The cyanate structure (nurate structure) has one or two or more molecules in the following general formula (2):

Represents a cyanurate ring.

The trimer isocyanate structure includes, for example, a trimer obtained by the trimerization reaction of the isocyanate, a pentamer obtained by the pentamerization reaction, and a heptamer obtained by the heptamerization reaction.

Among them, the following general formula (7) is preferred:

The terpolymer shown is preferred.

The biuret has the following general formula (8):

The compound having the indicated structure can be obtained by trimerizing a hexamethylene diisocyanate under conditions different from those in the case where the trimeric isocyanate structure is obtained.

The above-mentioned blocker is preferably a compound having an active hydrogen. The active hydrogen-containing compound is preferably, for example, at least one selected from the group consisting of alcohols, oximes, lactams, active methylene compounds, and pyrazole compounds.

As described above, the above-mentioned block isocyanate is obtained by reacting a polyisocyanate compound derived from hexamethylene diisocyanate with a blocking agent, and the above-mentioned blocking agent is composed of alcohols, oximes, lactams, and At least one selected from the group consisting of a methylene compound and a pyrazole compound, which is one of the preferred embodiments of the present invention.

In order to obtain the polyisocyanate compound (II) for the above-mentioned block isocyanate as an adduct of hexamethylene diisocyanate and a ternary or higher aliphatic polyol, the ternary or higher aliphatic polyol is specifically, for example, There are glycerol, trimethylolpropane (TMP), 1,2,6-hexanetriol, trimethylolethane, 2,4-dihydroxy-3-hydroxymethylpentane, 1,1,1- Ginseng (bishydroxymethyl) propane, 2,2-bis (hydroxymethyl) butanol-3 and other tertiary alcohols; pentaerythritol, diglycerol and other tetrahydric alcohols; arabinitol, ribitol, xylitol, etc 5-valent alcohols (pentite); sorbitol, mannitol, galactitol, allodulcit (hexaditol) (hexite), etc. Especially preferred are trimethylolpropane and pentaerythritol.

The hexamethylene diisocyanate is subjected to addition polymerization as described above with a ternary or higher aliphatic polyol to obtain the above-mentioned adduct.

A compound having an active hydrogen which reacts with the above-mentioned polyisocyanate compound (II). Specifically, for example, alcohols such as methanol, ethanol, n-propanol, isopropanol, and methoxypropanol; oximes such as acetone oxime, 2-butanone oxime, and cyclohexanone oxime; ε-hexane Lactamines such as Lactamine; Active methylene compounds such as Methylacetate, Ethylmalonate; 3-methylpyrazole, 3,5-dimethylpyrazole, 3,5- One or two or more of these pyrazole compounds, such as diethylpyrazole, are used.

Among them, active methylene compounds and oximes are preferred, and active methylene compounds are more preferred.

Commercial products of the above-mentioned block isocyanates include duranate K6000 (made by Asahi Kasei Chemicals Co., Ltd. and active methylene of HDI). Base compound block isocyanate), duranate TPA-B80E (manufactured by Asahi Kasei Chemicals Co., Ltd.), duranate MF-B60X (manufactured by Asahi Kasei Chemicals Co., Ltd.), duranate 17B-60PX (manufactured by Asahi Kasei Chemicals Co., Ltd.), coronate 2507 (Japanese Polyurethane Industrial Co., Ltd. Company), coronate 2513 (manufactured by Japan Polyurethane Industry Co., Ltd.), coronate 2515 (manufactured by Japan Polyurethane Industry Co., Ltd.), Sumidur BL-3175 (manufactured by Sumitomo Bayer Urethane), Luxate HC1170 (manufactured by Orin. Chemicals), Luxate HC2170 (manufactured by Orin. Chemicals) and the like.

As the hardener, a polyisocyanate compound (hereinafter sometimes referred to as a polyisocyanate compound (III)) derived from hexamethylene diisocyanate (HDI) can be used. Examples of the polyisocyanate compound (III) include the polyisocyanate compound (II).

Specific examples of the polyisocyanate compound (III) include coronate HX (manufactured by Japan Polyurethane Industrial Co., Ltd., hexamethylene diisocyanate cyanurate structure, NCO content of 21.1%), Sumidur N3300 (manufactured by Sumika Bayer Urethane Co., Ltd.) , Hexamethylene diisocyanate melamine structure), Takenate D170N (manufactured by Mitsui Chemicals Co., Ltd., hexamethylene diisocyanate melamine structure), Sumidur N3800 (Sumika Bayer Urethane) System, hexamethylene diisocyanate, melamine structure prepolymer form) and so on.

Isophorone diisocyanate (IPDI) -derived polyisocyanate compound (hereinafter sometimes referred to as polyisocyanate compound (IV)).

The polyisocyanate compound (IV) includes, for example, an adduct obtained by addition polymerization of isophorone diisocyanate and a ternary or higher aliphatic polyol, and a tricyanate composed of isophorone diisocyanate. Biuret composed of a structure (nurate structure) and isophorone diisocyanate.

The adduct has, for example, the following general formula (9):

(In the formula, R ⁵ represents an aliphatic hydrocarbon group having 3 to 20 carbon atoms. R ⁶ represents the following general formula (10):

Represented groups. k is an integer represented by 3 to 20).

R ⁵ in the above general formula (9) is a hydrocarbon group based on the above 3-membered aliphatic polyhydric alcohol, more preferably an aliphatic hydrocarbon group having 3 to 10 carbon atoms, and even more preferably an aliphatic hydrocarbon group having 3 to 6 carbon atoms. .

The k is a number corresponding to the valence of the aliphatic polyhydric alcohol of 3 yuan or more. The aforementioned k is preferably an integer of 3 to 10, and more preferably an integer of 3 to 6.

The cyanate structure (nurate structure) has one or two or more molecules in the following general formula (2):

Represents a cyanurate ring.

The trimeric isocyanate structure includes, for example, a trimer obtained by the trimerization reaction of the isophorone diisocyanate, a pentamer obtained by the pentamation reaction, and a heptamer obtained by the heptamerization reaction. Things.

Among them, the following general formula (11) is preferred:

(Wherein, R ⁶ Xi same as in the general formula (9) R ⁶⁾ Biaoshi of trimer. That is, the cyanurate structure is preferably a terpolymer of isophorone diisocyanate.

The biuret has the following general formula (12):

(In the formula, R ⁶ is the same as the compound represented by R ⁶ in general formula (9).) Isophorone di can be used under conditions different from those in the case where the cyanurate structure is obtained. It is obtained by trimerization of isocyanate.

The polyisocyanate compound (IV) is preferably at least one selected from the group consisting of the adduct and the cyanurate structure. In other words, the polyisocyanate compound (IV) is preferably an adduct obtained by addition polymerization of isophorone diisocyanate and a ternary or higher aliphatic polyol, and a trimer composed of isophorone diisocyanate. At least one selected from the group of cyanate ester structures.

When the polyisocyanate compound (IV) is an adduct of isophorone diisocyanate and an aliphatic polyol having a valence of 3 or more, the aliphatic polyol having a valence of 3 or more, specifically, for example, glycerol or trimethylol Propane (TMP), 1,2,6-hexanetriol, trimethylolethane, 2,4-dihydroxy-3-hydroxymethylpentane, 1,1,1-ginseng (dihydroxymethyl) ) Trihydric alcohols such as propane, 2,2-bis (hydroxymethyl) butanol-3, etc .; Quaternary alcohols such as pentaerythritol, diglycerol, etc .; Pentavalent alcohols such as arabitol, ribitol, xylitol (pentyl Pentite); sorbitol, mannitol, galactitol, alabol (allodulcit) and other 6-membered alcohols (hexite) and the like. Especially preferred are trimethylolpropane and pentaerythritol.

Addition polymerization of isophorone diisocyanate and the aliphatic polyhydric alcohol having a valence of 3 or more as described above can obtain an adduct suitable for the present invention.

The adducts to which the present invention is more suitable have, for example, the following general formula (13):

(In the formula, R ⁷ is represented by the following general formula (10):

Represented groups. ), Which is a polycyanate compound obtained by addition polymerization of isophorone diisocyanate and trimethylolpropane (TMP).

Commercial product of polyisocyanate compound (TMP adduct of isophorone diisocyanate) represented by the above general formula (10), for example For example, Takenate D140N (Mitsui Chemical Co., Ltd., NCO content: 11%).

Commercially available products of the cyanurate structure composed of isophorone diisocyanate include Desmodur W Z4470 (manufactured by Sumika Bayer Urethane Co., Ltd., NCO content: 11%).

Among these, the hardener (H) is more preferably a polyisocyanate compound (polyisocyanate compound (III)) derived from hexamethylene diisocyanate (HDI).

The content of the hardener (H) is 1 equivalent to the hydroxyl group in the hydroxyl-containing fluorinated copolymer, preferably 0.1 to 5 equivalents, and more preferably 0.5 to 1.5 equivalents.

The fluororesin composition of the present invention may further contain a flattening agent (I). By containing a flattening agent, the surface of the coating film becomes smooth, the appearance is good, and the coating film becomes less likely to be damaged.

The leveling agent (I) is, for example, a known one of a silicone type or an acrylic polymer type.

Examples of the silicone-based leveling agent include polyester-modified polydimethylsiloxane, polyether-modified polydimethylsiloxane, polyester-modified polymethylalkylsiloxane, and polyether-modified polymethylalkylsiloxane. Oxane, aralkyl modified polymethylalkylsiloxanes, etc. Specifically, for example, BYK-300, BYK-301, BYK-302, BYK-330, BYK-310, BYK-315, BYK-320, BYK-322, etc. manufactured by BYK-Chemie Corporation, Kyoeisha Chemical Co., Ltd. Polyflow 400X, 401, 402, etc., and DISPARLON 1711EF, 1751N, 1761, etc. manufactured by Nanben Chemical Co., Ltd.

Examples of acrylic leveling agents include BYK-350, BYK-361N, BYK-3440, etc. manufactured by BYK-Chemie, polyflow 7, 50E, 75, 95, etc. manufactured by Kyoeisha Chemical Co., and DISPARLON 1970, 230 manufactured by Nanben Chemical Co., Ltd. , LF-1980, 1982, etc.

The content of the flattening agent (I) is preferably 0.01 to 5% by mass, and more preferably 0.05 to 3% by mass relative to the total solid content of the hydroxyl-containing fluorinated copolymer (A) and the acrylic copolymer (B). %.

The fluororesin composition of the present invention may further contain a hydrophilizing agent (J). Contains a hydrophilizing agent to form a coating film that is easy to remove dirt.

For example, the hydrophilizing agent (J) is located on the surface of the hardened coating film and can retain hydroxyl groups. Specifically, for example, there are MS-51, MS-56, manufactured by Mitsubishi Chemical Corporation, and zeffle GH-701 (made by Daikin Industries, Ltd.). Fluoropolysiloxane)).

The content of the hydrophilizing agent (J) is preferably 0.01 to 50% by mass and more preferably 0.5 to 10 with respect to the total solid content of the hydroxyl-containing fluorinated copolymer (A) and the acrylic copolymer (B). quality%.

The fluororesin composition of the present invention may contain other components in addition to the above components, if necessary.

Other components include pigments, sedimentation stabilizers, hardening accelerators, defoamers, light stabilizers, tackifiers, adhesion improvers, and matting agents.

The fluororesin composition of the present invention is prepared by mixing or dispersing the components (A) to (G), and the components (H), (I), (J), and other components as necessary. The above mixing and dispersing are not particularly limited, and for example, a paint shaker, a ball mill can be used Using a known device such as a kneader or a kneader.

The solid content concentration of the fluororesin composition of the present invention is not particularly limited, and can be appropriately adjusted in accordance with the use method.

The haze of the fluororesin composition of the present invention is preferably 2.0% or less. When the haze exceeds 2.0%, there is a concern that the transparency is insufficient. The haze is more preferably 1.5% or less.

The above haze is formed on a floating glass (JIS R3202 standard test plate glass, manufactured by Japan Test Panel Co., Ltd.) with a length of 150 mm, a width of 70 mm, and a thickness of 3 mm. The fluororesin composition of the present invention is used to form a coating film with a dry film thickness of 15 μm The value obtained is measured with a haze meter.

The total light transmittance of the fluororesin composition of the present invention is preferably 70% or more. When the total light transmittance is less than 70%, the transmittance of visible light is reduced, and when a coating film is formed on glass, brightness may be impaired. The above-mentioned total light transmittance is more preferably 80% or more.

The above-mentioned total light transmittance is formed on a floating glass (JIS R3202 standard test plate glass, manufactured by Japan Test Panel Co., Ltd.) with a length of 150 mm, a width of 70 mm, and a thickness of 3 mm. The fluororesin composition of the present invention is used to form a dry film thickness of 15 μm. For those who apply a film, the obtained value is measured with a light transmittance meter.

The method for forming a coating film using the fluororesin composition of the present invention is not particularly limited, and the fluororesin composition of the present invention is usually applied to a substrate and cured to form a coating film.

The above coating is not particularly limited, and a known method may be used, and examples thereof include roll coating, curtain coating, spray coating, die coating, gravure coating, flow coating by a casting method, bristle coating, and sponge Coating, etc.

The above-mentioned curing system may be performed by a known method by blending the components of the fluororesin composition, and appropriately selecting drying, heating, or radiation irradiation.

The thickness of the coating film is preferably 1 to 50 μm. From the viewpoint of excellent transparency and shielding properties of ultraviolet rays and infrared rays, the thickness is more preferably 3 μm or more, more preferably 40 μm or less, and still more preferably 30 μm or less.

The surface hardness of the coating film is preferably F or more, and more preferably H or more, in a pencil hardness test according to JIS K5400.8.4 (1 kg load).

As described above, the fluororesin composition of the present invention contains a specific component. Therefore, it is possible to form a coating film having excellent heat-resistant adhesion, cold-resistant adhesion, water resistance, and high surface hardness and transparency. A coating film formed using such a fluororesin composition of the present invention is also one aspect of the present invention.

The substrate to which the fluororesin composition of the present invention is applicable is not particularly limited, and a transparent substrate is preferred. Specific examples of the transparent substrate include plastic substrates such as polyethylene terephthalate, acrylic resin, polycarbonate resin, and fluororesin, glass, and other articles requiring transparency. Among them, when glass is used as a base material and the coating film is formed using the fluororesin composition of the present invention, a coating film having excellent heat resistance, cold resistance, and water resistance, and high surface hardness and transparency can be formed.

Such an article having a transparent substrate and a coating film made of the fluororesin composition on the transparent substrate is also one aspect of the present invention.

The transparent substrate is preferably glass.

The glass having a coating film formed using the fluororesin composition of the present invention is suitable for use as a window glass. The window glass may be provided in the The coated side is the outside of the house.

The fluororesin composition of the present invention may be applied to a window glass of a building to form the coating film. The coating film may be formed on a surface outside the house of the window glass. This reason is, for example, that the weather resistance is high, and a person who installs a coating film on the outside can easily dissipate the absorbed heat to the outside, so the heat shielding efficiency becomes high.

When the fluororesin composition of the present invention is used, it can be applied on the window glass of a building on the spot and dried at room temperature to form heat-resistant adhesive, cold-resistant adhesive, and water-resistant on the window glass. Coating film with high hardness and transparency.

The fluororesin composition of the present invention can be used as a main agent of a two-liquid coating composition.

When the fluororesin composition of the present invention contains a hardener (H), the fluororesin composition of the present invention may be composed of a hardener (H) and a main agent containing the above components other than the hardener (H). Liquid coating composition.

[Example]

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

(Example 1)

20 mass parts of the following acrylic resin composition was added to 80 mass parts of ZEFFLE GK570 (made by Daikin Industries, Ltd.).

Next, the following hot-line shielding pigment dispersion liquid and ultraviolet absorber a. Ultraviolet absorbent b, silane coupling agent, colloidal silicon dioxide a, flattening agent, and butyl acetate were added in the amounts as shown in Table 1. To the obtained mixture, the amount of the hardener a described in Table 1 was further added to obtain a coating composition.

(Examples 2 to 7 and Comparative Examples 1 to 5)

Each coating composition was obtained in the same manner as in Example 1 except that the components described in Tables 1 and 2 were blended in the amounts shown in Tables 1 and 2.

Each component is specifically as follows.

(A) Hydroxyl-containing fluorinated copolymer: ZEFFLEGK570 (tetrafluoroethylene copolymer, hydroxyl value 60mgKOH / g, solid content 65% by mass, solvent butyl acetate, Daikin Industry Co., Ltd.)

(B) Acrylic copolymer: Acrylic copolymer composed of acrylic resin composition (hydroxyethyl methacrylate (HEMA), t-butyl methacrylate (t-BMA) (composition ratio HEMA / t-BMA = 10/90 weight ratio), solid content 65% by mass, hydroxyl value 60mg. KOH / g, solvent butyl acetate)

(C) Hot-line shielding pigment dispersion: 40% by mass of ATO, 8% by mass of additive, mixed solvent of methyl ethyl ketone and diacetone alcohol, average particle size of 73 nm

(D) Ultraviolet absorbent

a: Tinuvin 400 (triazine-based compound, manufactured by BASF)

b: Tinuvin 479 (hydroxytriazine-based compound, manufactured by BASF)

(E) Silane coupling agent: OCNC ₃ H ₆ Si (OCH ₃ ) ₃

(F) Colloidal silica

a: organosol IPA-ST (average particle diameter: 11 nm, solid content concentration: 30% by mass, manufactured by Nissan Chemical Industries, Ltd.)

b: organosol MEK-ST (average particle size: 10 nm, solid content concentration: 40% by mass, manufactured by Nissan Chemical Industries, Ltd.)

c: organosol MEK-AC-22 (average particle diameter: 13nm, solid content concentration: 44.6% by mass, manufactured by Nissan Chemical Industries, Ltd.)

(G) Solvent: Butyl acetate (except those contained in other ingredients)

(H) Hardener

a: Sumidur N3300 (hexamethylene diisocyanate cyanurate structure, 22% NCO content, manufactured by Sumika Bayer Urethane)

b: Takenate D140N, (addition of IPDI and TMP, 11% NCO content, made by Mitsui Chemicals Co., Ltd.)

(I) Leveling agent: BYK-310 (manufactured by BYK-Chemie)

Using the obtained coating composition, the following items were evaluated. The results are shown in Tables 1-2.

<Haze and total light transmittance>

The obtained coating composition was applied to one side of a floating glass (JIS R3202 standard test plate glass, manufactured by Japan Test Panel Co., Ltd.) having a length of 150 mm, a width of 70 mm, and a thickness of 3 mm, and dried at 23 ° C for 7 days to form a thickness of 15 μm Coating film. For the glass plate on which the coating film is formed, a haze meter and a light transmittance meter (Haze Guard II: manufactured by Toyo Seiki Co., Ltd., ASTM D1003 method) The haze and total light transmittance were measured and evaluated using the following criteria.

Haze

◎: 1.0% or less

○: More than 1.0% and less than 1.5%

△: More than 1.5% and less than 2.0%

×: more than 2.0% and less than 10.0%

××: more than 10.0%

Total transmittance

◎: 80% or more

○: Above 70% and below 80%

△: Above 60% and below 70%

×: Less than 60%

<Surface hardness>

The obtained coating composition was applied to one side of a floating glass (JIS R3202 standard test plate glass, manufactured by Japan Test Panel Co., Ltd.) having a length of 150 mm, a width of 70 mm, and a thickness of 3 mm, and was dried at 23 ° C. for 7 days to form a thickness of 15 μm. Coating film. The resulting coating film surface was subjected to a pencil hardness test in accordance with JIS K 5400.8.4. (1 kg load).

<Adhesiveness>

The obtained coating composition was applied to one side of a floating glass (JIS R3202 standard test plate glass, manufactured by Japan Test Panel Co., Ltd.) having a length of 150 mm, a width of 70 mm, and a thickness of 3 mm, and was dried at 23 ° C. for 7 days to form a thickness of 15 μm. Coating film. The obtained coating film surface was subjected to a cross-cut test in accordance with JIS K 5600.5.6, and evaluated using the following criteria.

◎: Classification of JIS K 5600.5.6 "Table 1 Test results classification" 0

○: Classification 1 of JIS K 5600.5.6 "Classification of test results in Table 1"

△: Classification 2 of JIS K 5600.5.6 "Table 1 Test results classification"

×: Classification 3 of JIS K 5600.5.6 "Table 1 Test results classification"

××: Classification 4 and Classification 5 of JIS K 5600.5.6 "Classification of Test Results in Table 1"

<Water resistance>

The obtained coating composition was applied to one side of a floating glass (JIS R3202 standard test plate glass, manufactured by Japan Test Panel Co., Ltd.) having a length of 150 mm, a width of 70 mm, and a thickness of 3 mm, and was dried at 23 ° C. for 7 days to form a thickness of 15 μm. Coating film. The glass plate on which the coating film was formed was immersed in pure water at 23 ° C. for 5 days, and then taken out of the water. After gently wiping off water vapor, the haze and total light transmittance were measured. After taking out from the water for another 30 minutes, the adhesion of the coating film was evaluated. Evaluation of haze, total light transmittance, and adhesion was performed in the same manner as described above.

<Cold and hot cycle>

Using the obtained coating composition, similarly to the above, it was coated on one side of a floating glass (JIS R3202 standard test plate glass, manufactured by Japan Test Panel Co., Ltd.) with a length of 150 mm, a width of 70 mm, and a thickness of 3 mm to obtain a thickness of 15 μm. Coated glass plate. For the obtained glass plate, a small hot and cold punching device TSE-11-A manufactured by espec Co., Ltd. was used, and the cycle was evaluated at 60 ° C for 18 hours and -20 ° C for 3 hours. After repeating 10 cycles, the haze and total light transmittance were evaluated. And adhesion. Evaluation of haze, total light transmittance, and adhesion was performed in the same manner as described above.

<Weather resistance>

Using the obtained coating composition, similarly to the above, it was coated on one side of a floating glass (JIS R3202 standard test plate glass, manufactured by Japan Test Panel Co., Ltd.) with a length of 150 mm, a width of 70 mm, and a thickness of 3 mm to obtain a thickness of 15 μm. Coated glass plate. The obtained glass plate was subjected to a weather resistance promotion test using a xenon lamp weather resistance tester Ci series hybrid exposure system (manufactured by Toyo Seiki Co., Ltd.). Specifically, 25 cycles (10 hours) of the accelerated test cycle were used as one test under the following conditions, and a total of 100 hours of tests were performed while confirming the passage on the way. After the test, the total light transmittance, haze, and adhesion were evaluated using the same method as described above.

(Hybrid exposure system test conditions)

Hydrogen peroxide water concentration: 1.0%

Filter combination: inside CIRA, outside typeS

(Segment (1))

Irradiance: 80W / m ²

Black panel temperature: 50 ℃

Test tank air temperature: 30 ℃

Standard relative humidity: 70%

Hydrogen peroxide water spray: ON

Clip time: 3 minutes

(Snippet (2))

Irradiance: 80W / m ²

Black panel temperature: 50 ℃

Test tank air temperature: 30 ℃

Standard relative humidity: 70%

Hydrogen peroxide water spray: OFF

Clip time: 2 minutes

The segment (1) and the segment (2) are repeated, and 2 hours are used as a cycle.

<Heat-shielding property>

Using the obtained coating composition, similarly to the above, it was coated on one side of a floating glass (JIS R3202 standard test plate glass, manufactured by Japan Test Panel Co., Ltd.) with a length of 150 mm, a width of 70 mm, and a thickness of 3 mm to obtain a thickness of 15 μm. Coated glass plate.

When the solar radiation heat gain rate (0.88) of the glass plate before the coating film formation is set to 1, the ratio of the solar heat gain rate of the glass plate after the coating film formation is calculated as the shielding coefficient.

The solar heat gain coefficient is calculated in accordance with JIS R 3106. Specifically, a spectrophotometer U-4100 (manufactured by Hitachi, Ltd.) was used, and the side where the coating film was formed was used as the incident light side to measure the transmittance and reflectance of the coating film on a glass plate at a wavelength of 300 to 2500 nm. The weighting coefficient described in JIS R 3106 Schedule 2 calculates the solar transmittance and solar reflectance, and uses the obtained values to calculate the solar radiant heat acquisition rate.

A smaller value of the shading coefficient indicates a higher shading performance.

(Examples 8 to 10)

A coating composition was obtained in the same manner as in Example 1 except that the composition described in Table 3 was set.

"(J) Hydrophilizing agent" in the table uses "ZEFFLE GH-701 (made by Daikin Industries, Ltd.)".

The obtained coating composition was applied to one side of a floating glass (window glass, manufactured by Nippon Glass Glass Co., Ltd.) having a length of 1100 mm, a width of 800 mm, and a thickness of 3 mm, and was dried at 23 ° C. for 7 days to form a coating film having a thickness of 15 μm. The glass plate on which the coating film is formed is installed in the west side window of Daikin Industrial Office, from March 1, 2010 to March 21, 2013. In Examples 8 and 9, the coating film surface was set on the outside of the house, and Example 10 was set on the inside of the house.

After the predetermined period has elapsed, remove the glass plate, wipe and clean the paper containing tap water on both sides of the glass plate. About the cleaned glass plate, the same method as Example 1 was used to evaluate total light transmittance and haze. The appearance of the coating film was visually observed.

L ^* 1, a ^* 1, b ^* 1 were measured with a color meter (CR-300, manufactured by Konica Minolta) for the glass plate before installation, as an initial value. For the unwashed glass plate that was removed after the predetermined period was set , And also measure L ^* 2, a ^* 2, b ^* 2 by the following formula: Find the color difference (△ E1) before and after setting.

For the glass plate after washing, L ^* 3, a ^* 3, and b ^* 3 were measured in the same manner, and the following formula was used: Find the color difference (△ E2) between the glass plate before installation and the glass plate after cleaning.

Moreover, the glass plate before and after washing was visually evaluated.

The results are shown in Table 3.

[Industrial availability]

In the fluororesin composition according to the present invention, a coating film having excellent heat resistance, cold resistance, and water resistance, and having high surface hardness and transparency can be formed.

Claims (11)

A fluororesin composition, characterized in that it contains a hydroxyl-containing fluorinated copolymer (A) having a hydroxyl value of 30 to 200 mgKOH / g, an acrylic copolymer (B), and a hot-line shielding having an average particle diameter of 1 to 200 nm heat ray shielding) pigment (C), ultraviolet absorber (D), silane coupling agent (E), colloidal silicon dioxide (F), and organic solvent (G), and the haze is 2.0% or less, fully transparent The photometric rate is above 70%. For example, the fluororesin composition according to item 1 of the patent application scope, wherein the acrylic copolymer (B) is compatible with the fluorinated copolymer (A) containing a hydroxyl group. For example, the fluororesin composition according to item 2 of the scope of patent application, wherein the number average molecular weight of the fluorinated copolymer (A) containing a hydroxyl group is 50,000 or less. For example, the fluororesin composition according to item 1, 2, or 3 of the patent application scope, wherein the hot wire shielding pigment (C) is selected from tin-doped indium pigments doped with tin, tin oxide doped with antimony, six At least one of the group consisting of a lanthanum boride pigment and a zinc oxide pigment. For example, the fluororesin composition according to item 1, 2, or 3 of the application scope, wherein the ultraviolet absorber (D) is selected from the group consisting of benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, and triazine-based ultraviolet absorbers At least one of a group consisting of an agent, a cyanoacrylate-based ultraviolet absorber, and a coumarin-based ultraviolet absorber. For example, the fluororesin composition according to claims 1, 2 or 3, further contains a hardener (H). If you apply for a fluororesin composition in the scope of patents 1, 2, or 3, It further contains a leveling agent (I). For example, the fluororesin composition according to item 1, 2, or 3 of the patent application scope further contains a hydrophilizing agent (J). A coating film characterized by being formed using a fluororesin composition such as items 1, 2, 3, 4, 5, 6, 7, or 8 in the scope of patent application. An article is characterized in that it has a transparent substrate and a coating film formed on the transparent substrate using a fluororesin composition such as the items in the scope of application for patents 1, 2, 3, 4, 5, 6, 7, or 8. For example, the article under the scope of patent application, wherein the transparent substrate is glass.