WO2005097497A1

WO2005097497A1 - Laminates

Info

Publication number: WO2005097497A1
Application number: PCT/JP2005/006999
Authority: WO
Inventors: Katsuhiro Mori; Junji Momoda
Original assignee: Tokuyama Corporation
Priority date: 2004-04-06
Filing date: 2005-04-05
Publication date: 2005-10-20
Also published as: JPWO2005097497A1; JP4757795B2

Abstract

Laminates produced by laminating a thiourethane resin substrate or an allyl resin substrate with a cured layer formed by curing a coating composition which comprises (A) composite metal oxide fine particles produced by coating a composite metal oxide consisting of tin oxide and zirconium oxide with antimony pentaoxide or silicon oxide, (B) an epoxy-containing silicon compound or a partial hydrolyzate thereof, (C) an organic solvent, and (D) an acetylacetonato complex. The laminates are characterized by low water sensitivity, so that the cured layer little causes whitening even when the cured layer is formed either by conducting the application of the coating composition and the curing thereof at high humidity or in such a state that the coating composition contains water absorbed thereinto. Further, the laminates are excellent in weather resistance and are therefore little lowered in the tight adhesion of the cured layer to the substrate even when kept under the irradiation with light for a long time.

Description

Description laminate

The present invention relates to a laminate in which a cured product layer of a coating composition is formed on the surface of a thiourethane resin substrate or an aryl resin substrate, and more particularly, to adhesion, abrasion resistance, and weather resistance. The present invention relates to a laminate having excellent properties and the like, and suitable as an eyeglass lens. Background technology>

Synthetic resin lenses have features that glass lenses do not have, such as lightness, safety, ease of processing, and fashionability, and have rapidly spread in recent years, but have the disadvantage that they are easily scratched. Generally, a silicone-based coating layer (so-called hard coat layer) is provided on the lens surface.

Conventionally, such a silicone-based coating layer is formed by applying a coating composition mainly composed of silica fine particles, a polymerizable organic silane compound, a polymerization catalyst, an aqueous acid solution, and a solvent to the surface of a synthetic resin lens, and then heating the coating composition. Then, the composition was formed by curing the composition and volatilizing the solvent (for example, see Japanese Patent Publication No. 57-27335). However, the hard coat layer formed by curing such a coating composition has a low refractive index, and when formed on the surface of a synthetic resin lens having a high refractive index, the difference in the refractive index from the synthetic resin lens. There is a problem that interference fringes are generated due to this, which causes poor appearance.

In order to solve this problem, various coating compositions for forming a high-refractive-index hard coat layer have been proposed. For example, silica fine particles blended in the above-mentioned coating composition can be treated with a refractive index Coating compositions that have been replaced with various complex metal oxides having a high content, specifically, the following coating compositions have been proposed.

(1) Coating composition replaced with a composite metal oxide containing Sb, Ti, Zr, Sn, etc. (Japanese Patent Laid-Open No. 5-246805) (2) Coating composition replaced with composite oxide containing Ti, Ce, Sn, etc. (JP-A-10-245523)

(3) Coating composition replaced with a composite metal oxide containing Ti, Sn and Zr (JP-A-9-149215)

(4) Coating composition replaced with composite metal oxide containing Ti and Sb (Japanese Patent Application Laid-Open No. 2002-363442)

(5) Coating composition replaced with a complex metal oxide such as Sn, Zr, W, Si (Japanese Patent Laid-Open No. 2000-281973)

However, the coating compositions using the composite metal oxides of (1) to (5) have high sensitivity to moisture, so that a phenomenon in which the formed hard coat layer is whitened (turbid) is observed. Further, the weather resistance (or durability) of the formed hard coat layer is low, and for example, there is a problem that the adhesion between the hard coat layer and the synthetic resin lens decreases with time.

Accordingly, the present invention provides a laminate in which a cured product layer of a coating composition is formed on the surface of a resin substrate, in which whitening (cloudiness) of the cured product layer due to moisture is effectively suppressed and weather resistance is improved. An object of the present invention is to provide a laminate excellent in adhesiveness and in which a decrease in adhesion over time is effectively suppressed.

The present inventors have conducted intensive studies to solve the above-mentioned problems. As a result, a thiourethane resin substrate or an aryl resin substrate was selected as a resin substrate, and a composite metal oxide composed of tin oxide and zirconium oxide was used as a coating composition. By using a composite metal oxide fine particle coated with a resin and a material containing other specific components, and combining such a resin base material with a coating composition, the cured product layer caused by moisture is whitened. (White turbidity) was suppressed, and a laminate excellent in weather resistance or durability was found to be obtained, and the present invention was completed.

That is, according to the present invention, in a laminate in which a cured product layer of a coating composition is formed on the surface of a base material,

The coating composition comprises the following components (Α) to (D): (A) composite metal oxide fine particles obtained by coating a composite metal oxide composed of tin oxide and zirconium oxide with antimony pentoxide and gay oxide;

(B) an epoxy group-containing silicon compound or a partial hydrolyzate thereof;

(C) an organic solvent;

(D) acetyl acetonate complex;

Containing, and

A laminate is provided, wherein the resin substrate is a thiourethane resin substrate or an aryl resin substrate.

In the laminate of the present invention, the coating composition comprises the component (B)

Per 100 parts by mass, 25 to 250 parts by mass of the composite metal oxide fine particles of the component (A), 0 to 2500 parts by mass of the organic solvent of the component (C) 100 to 2500 parts by mass, and acetyla of the component (D) It is preferable to contain the setnato complex in an amount of 0.1 to 15 parts by mass.

Although the laminate of the present invention is useful as a plastic lens, particularly when used for a plastic lens, the refractive index of the thiourethane resin base material or the aryl resin base material is 1.55 or more; It is preferable that the base material or the aryl resin base material contains a dye.

According to the present invention, a coating composition containing the components (A) to (D) is applied to the surface of a polyurethane resin substrate or an aryl resin substrate, and heated to a temperature of 80 ° C or more. There is provided a method for producing a laminate, which comprises curing the coating composition to form a cured layer. Since the cured product layer of the coating composition is formed on the surface of the thiourethane resin substrate or the aryl resin substrate, the laminate of the present invention has the characteristics of low sensitivity to moisture and excellent weather resistance. For example, even when the coating composition is applied under high humidity or when the coating composition is applied in a state of absorbing water, a transparent cured layer without clouding can be obtained. Moreover, as shown in the examples described later, even after a long-term (200 hours) accelerated deterioration test, the adhesion between the cured material layer and the resin substrate does not decrease, and high adhesion is obtained. Is held. Thus, the laminate of the present invention is extremely excellent in both the sensitivity to moisture and the weather resistance. For example, when a cured product layer is formed on the surface of a polyurethane resin substrate or an aryl resin substrate using a coating composition of another composition, the sensitivity to moisture is low, and the turbidity of the cured product layer due to the influence of moisture is reduced. There is no occurrence, but the weather resistance is poor, and the adhesion between the cured product layer and the resin substrate is greatly reduced after the accelerated deterioration test. Also, (A)

When a coating composition containing the components (D) to (D) is used, even if a resin base other than the thiourethane resin base and the aryl resin base, for example, a polycarbonate resin base is used, the component (B) is used. By contact with a certain epoxy group-containing silicon compound or its partial hydrolyzate, the surface of the polycarbonate base material is dissolved, and the resin base material itself becomes slightly cloudy. In addition, the U-resistance, abrasion resistance, and adhesion are insufficient, making them unsuitable for use as plastic lenses.

In the present invention, the presence or absence of white turbidity (or whitening) of the laminate is visually observed by irradiating the laminate with light along the direction of the cured product layer. When light is irradiated in the direction perpendicular to the layer direction, the light path of light passing through the cloudy layer is extremely short because the cloudy layer is extremely thin, and the cloudiness is almost visually observed. Is not possible.

As described above, the laminate of the present invention is excellent in both sensitivity to moisture and weather resistance, and retains excellent properties such as transparency, adhesion, and abrasion for a long period of time. As a lens, its industrial value is high.

[Coating composition]

The coating composition used for producing the laminate of the present invention contains the above-mentioned components (I) to (D).

(Α) ingredient

The component (II) is a composite metal oxide fine particle obtained by coating a composite metal oxide composed of tin oxide and zirconium oxide with antimony pentoxide and gallium oxide. These composite metal oxide fine particles are usually used by being dispersed in a colloidal form using water, an alcoholic or other organic solvent as a dispersion medium.

Such composite metal oxide fine particles contain 70 to 99% by mass of a composite metal oxide composed of tin oxide and zirconium oxide, and a total of antimony pentoxide and silicon oxide. It is preferably contained in an amount of 1 to 30% by mass, more preferably 50 to 96% by mass of tin oxide, 3 to 49% by mass of zirconium oxide, and 1 to 29% of antimony pentoxide. It is preferred to contain 9% by mass and 0.1 to 29% by mass of manganese oxide.

The above-mentioned composite metal oxide fine particles may contain a trace amount of a metal oxide component other than tin-zirconium, but preferably contain substantially no titanium oxide. Titanium oxide has high sensitivity to moisture, tends to cause whitening of the cured product layer of the coating composition, and tends to reduce the weather resistance of the cured product layer.

As a dispersion medium of the above-mentioned composite metal oxide fine particles, alcoholic organic solvents such as methanol, ethanol, n-propanol, isopropanol, t-butyl alcohol, and n-butyl alcohol are preferable, and particularly, methanol and 2-propanol are preferable. Are preferred. In addition, the ratio of the composite metal oxide fine particles in the dispersion medium at this time is to increase the refractive index of the cured product layer of the coating composition, and that the composite metal oxide fine particles become unstable in the dispersion medium. In order to prevent the above, the content is preferably from 10% by mass to 50% by mass.

Further, in order to enhance the dispersion stability, it is also possible to use a composite metal oxide fine particle whose surface is treated with an amine compound and Z or carboxylic acid. Examples of the amine compound used in this case include ammonium or ethylamine, triethylamine, isopropylamine, n-propylamine, dimethylamine, dimethylamine, diisopropylamine, alkylamine such as dipropylamine, aralkylamine such as benzylamine, morpholine, pyridine, and the like. And alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and isopropanolamine. Examples of the carboxylic acid include acetic acid, oxalic acid, lactic acid, malic acid, citric acid, tartaric acid, salicylic acid, glycolic acid, benzoic acid, phthalic acid, malonic acid, and mandelic acid. Such a surface treatment agent is preferably used in an amount of 0.01 to 5 parts by mass per 100 parts by mass of the composite metal oxide fine particles.

The particle diameter of the composite metal oxide fine particles is not particularly limited, but the average particle diameter is preferably in the range of 1 to 300 nm so as not to impair the transparency of the obtained cured product layer. The

As described above, the composite metal oxide fine particles are generally used as a dispersion dispersed in a dispersion medium, and the dispersion pH may be 4.0 to 9.5. preferable. By adjusting the pH to such a range, it is possible to prevent a decrease in the transmittance of the dispersion liquid due to a decrease in the dispersibility of the composite metal oxide fine particles, and to improve the coating composition due to a decrease in the dispersion stability of the composite metal oxide fine particles. The storage stability can be prevented from lowering.

The compounding amount of the composite metal oxide fine particles described above may be appropriately determined according to the composition ratio of the metal oxide, the desired physical properties and the like according to the purpose of the finally obtained hardened material layer. (Epoxy group-containing gay compound or its partial carohydrate hydrolyzate) It is preferably in the range of 25 to 250 parts by mass, more preferably 40 to 200 parts by mass, per 100 parts by mass. . When the composite metal oxide fine particles are used in the above range, the amount of the composite metal oxide fine particles is preferably 20 to 70 parts by mass, more preferably 30 to 70 parts by mass, per 100 parts by mass of the finally formed cured layer. 665 parts by mass. If the amount of the composite metal oxide fine particles per cured layer is less than 20 parts by mass, the abrasion resistance of the cured layer, the refractive index of the cured layer, and the like may be insufficient. Further, when an inorganic vapor-deposited film (anti-reflection film) is formed on the cured product layer, the adhesion with the vapor-deposited film may be reduced. Furthermore, if the amount of the composite metal oxide fine particles per cured layer exceeds 70 parts by mass, cracks tend to occur in the cured layer.

The mass of the cured product layer finally formed is the mass of the composite metal oxide fine particles, the epoxy compound-containing silicon compound described later or a partial hydrolyzate thereof, and further compounded as necessary. This is the total mass of the solid content when the organic silicon compound other than (II) and the epoxy compound are polymerized and condensed. Since the organic solvent such as methanol added to the coating composition is generated during the formation of the cured product layer, it is not included in the mass of the finally obtained cured product layer.

(Β) ingredient

The epoxy group-containing silicon compound as the component (II) has a function as a binder. As such an epoxy group-containing silicon compound, a known per se epoxy compound may be used without any limitation. be able to. As a specific example, r-glycidol Cypropyl trimethoxysilane, r-glycidoxypropylmethyldimethoxysilane, T-glycidoxypropylmethyljetoxysilane, -glycidoxypip propyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane And partially or wholly hydrolyzed or partially condensed thereof. Among them, polyglycidoxypropyltrimethoxysilane, -glycidoxypropylmethyldimethoxysilane, and some or some of these are considered from the viewpoint of adhesion to a thiourethane resin substrate or an aryl resin substrate described later. It is preferable to use a product that is completely hydrolyzed or partially condensed. The epoxy group-containing silane compound may be used alone or in combination of two or more.

The compounding amount of the epoxy group-containing gay compound may be appropriately determined depending on the desired properties and the like according to the purpose of the finally obtained cured product layer, and the finally formed cured product layer 100 mass It is preferably from 30 to 80 parts by mass, more preferably from 35 to 70 parts by mass, per part. If the compounding amount of the epoxy group-containing gay compound is less than 30 parts by mass, cracks tend to occur in the cured product layer, and if it exceeds 80 parts by mass, the scratch resistance and the refractive index tend to be insufficient. Further, when an inorganic vapor-deposited film is formed on the cured product layer, the adhesion between the two may be reduced.

(C) component

The organic solvent of the component (C) dissolves the (B) epoxy group-containing silicon compound or a binder component (for example, an organic silicon compound) other than the component (B) that is blended as necessary. A known organic solvent can be used without any limitation as long as it is a solvent capable of favorably dispersing oxide fine particles and has volatility. Examples of such organic solvents include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, and n-pentanol; methyl acetate, ethyl acetate, propyl acetate, and the like. Estezoles such as ethyl propionate, methyl acetate acetate, ethyl acetate acetate, and ethyl lactate; ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, Ethylene glycol mono-t-butyl ether, propylene Glyco J monomethyl ether, propylene glycol monoethyl ether, pyrene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, pyrene glycol monoethyl ether Ethers such as acetate and dioxane; ketones such as acetone, acetylacetone and diacetone alcohol; halogenated hydrocarbons such as methylene chloride; hexane, heptane, cyclohexane, benzene, toluene, Hydrocarbons such as xylene; and the like. These organic solvents ii may be used alone, but it is preferable to use a mixture of two or more of them for the purpose of controlling the physical properties of the coating composition.

In addition, (B) an epoxy group-containing silicon compound and an organic gayne compound used as a binder component other than (B) are required to be soluble in an acid aqueous solution used for the purpose of hydrolyzing the cured product. Among these organic solvents, methanosol, isopropanol, t-butanol, acetylacetone, diacetone alcohol, ethylene glycol, and the like, from the viewpoint of easy volatility in forming the layer and smooth formation of the hardened layer, It is preferable to use mono-isopropyl ether.

The amount of the organic solvent used is not particularly limited, but usually the total amount is in the range of 100 to 2500 parts by mass, preferably 100 to 2500 parts by mass, particularly 140 to 500 parts by mass per component (B). (If an alcohol or the like is used as a dispersion medium for the fine particles of the composite metal oxide of the component (A), the amount of such a dispersion medium is preferably Included in the amount of organic solvent.)

(D) Ingredient

(D) Tiger acetyl acetonate complex is used as a curing catalyst for the above-mentioned epoxy group-containing cage compound (B), and has a solubility in a coating composition and a coating composition. Known ones can be used without any limitation if they are appropriately selected in consideration of the physical properties such as the storage stability of the product and the hardness of the formed hard layer. Illustratively, L i (I), Cu (II), Zn (I D, Co

(II), Ni (II), Be (II), Ce (III), Ta (III), Ti (III), Mn (III), La (III), Cr (III), V (III), Co (III), Fe

(III), AI (III), Ce (IV), Zr (IV), V (IV), etc. Acetyl acetonate complex. Particularly preferably,

Acetyl acetonate complexes having A I (III), Fe (III) and Li (I) as central metals can be mentioned. There is no problem whether these acetyl acetonate complexes are used alone or as a mixture of two or more.

The amount of the acetyl acetonate complex described in _b is not particularly limited, but is 0.1 to 15 parts by mass, and particularly 0.2 to 10 parts by mass, per 100 parts by mass of the component (B). Is preferred. Further, per 100 parts by mass of the finally formed cured product layer,

More preferably, it is in the range of 0.01 to 5.0 parts by mass, particularly 0.1 to 3.0 parts by mass. Its CD and other ingredients

The coating composition used in the present invention may contain various components in addition to the components (A) to (D) described above, as long as excellent characteristics such as moisture sensitivity and weather resistance are not impaired. it can.

In this case, an organic gayen compound or epoxy compound other than the above-mentioned component (ii) can be blended as a binder component.

Examples of such organic gay compounds include tetraethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and trimethylmethoxysilane. Phenyltrimethoxysilane, diphenyldimethoxysilane, cyclohexylmethyldimethoxysilane, η-provyltrimethoxysilane, η-butyltrimethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, η-hexyltrimethoxysilane, η-hexyltriethoxysilane —S-octyltriethoxysilane, η-decyltrimethoxysilane, 1,6-bistrimethoxysilane, 3 —Peridopropyl triethoxysilane, trifluoropropyl trimethoxysilane, perfluorooctylethyl triethoxysilane, -chloropropyl trimethoxysilane, vinyletri (-methoxyethoxy) silane, aryletrimethoxysilane, r- Acryloxypropyltrimethoxysilane, r-acryloxypropisoletriethoxysilane, methacryloxypropinoletrimethoxy Silane, T-methacryloxypropyltriethoxysilane, methacryloxypropyldimethoxymethylsilane, mercaptopropyltrialkoxysilane, r-aminopropyltrimethoxysilane, monoaminopropyltriethoxysilane, N-phenyl r -Aminopropyl trimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N- 2

(Aminoethyl) 3-aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropyl trimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, p-styryl Limethoxy silane, 3-isocyanatopropyltriethoxysilane and the like can be exemplified, and these can be used alone or in combination of two or more. Further, such an organic gay compound is preferably blended after hydrolysis. The compounding amount of the organic gay compound may be appropriately determined according to the physical properties and the like desired according to the purpose of the finally obtained cured product layer. Generally, the epoxy group-containing silicone compound of the component (B) Alternatively, it is preferably at most 150 parts by mass, more preferably at most 100 parts by mass, per 100 parts by mass of the partial hydrolyzate thereof. The amount is preferably 30 parts by mass or less per 100 parts by mass of the finally formed cured material layer.

As the epoxy compound other than the component (B) (that is, an epoxy compound having no silyl group), a known compound can be used. Examples of the specific examples thereof include 1, 6 Hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, Z ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether Glycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl ether, nonapropylene glycol diglycidyl ether, neo pliers Glycoregyl glycidyl ether, dipentylglycol of neopentylglycol hydroxypivalic acid esterizole, trimethylolpropanediglycidylether, trimethylolpropanetriglycidylether, glycerol diglycidylether, glycerol triglycidylether, Diglycerol triglycidyl ether, diglycerone Lutetra glycidyl ether, Ventaerythri! Rudiglycidyl ether, pentaerythritol triglycidyl ether, pentaerythryl I-tetratetraglycidyl ether, dipentaerythryl! Triglycidyl ether, sorbitol monotetraglycidyl ether, diglycidyl ether of tris (2-hydroxyethyl) isocyanate, triglycidyl ether of tris (2-hydroxyethyl) isocyanu U ^- Aliphatic epoxy compounds such as isophthalone diylisyl glycidyl ether and bis-1,2,2-hydroxycyclohexylpropane diglycidyl ether; resorcinol diglycidyl ether J-bis, bisphenol A diglycidyl ether , Bisphenol F diglycidyl ether, bisphenol S diglycidyl J ether, diglycidyl orthophthalate: ester, aromatic epoxy such as phenol nopolak polyglycidyl ether, cresol nopolak polyglycidyl ether These epoxy compounds can be used singly or in combination of two or more. Of the above, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether, and glycerol triglycidyl ether are particularly preferable. The compounding amount of such an epoxy compound may be appropriately determined in accordance with the physical properties desired according to the purpose of the finally obtained cured product layer. The epoxy group-containing gay element of the component (B) ^: Compound Alternatively, it is preferably at most 150 parts by mass, more preferably at most 100 parts by mass, per 100 parts by mass of the partial hydrolyzate thereof. Further, the amount is preferably 30 parts by mass or less per 100 parts by mass of the finally formed cured layer.

Further, an acid aqueous solution can be added for the purpose of hydrolyzing the above-mentioned epoxy group-containing gay compound of the component (B) and the organic gay compound other than the component (B). As the acid aqueous solution, known acids can be used without any limitation as long as they have a function of hydrolyzing and condensing the azorecoxysilyl group in the above compound. Examples of such an acid include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, and organic acids such as acetic acid and propionic acid. Among them, hydrochloric acid is preferably used from the viewpoints of storage stability and hydrolyzability of the coating composition. The concentration is suitably in the range of 0.01 N to 5 N. In addition, such an acidic aqueous solution for 5 nights was subjected to the above-mentioned epoxy group-containing cage (B). It is used in such an amount that hydrolysis of the compound is effectively promoted. For example, 100 parts by mass or less, preferably 5 to 80 parts by mass, per 100 parts by mass of the (B) epoxy group-containing silicon compound. Parts by mass, most preferably <10 to 50 parts by mass. Further, a curing catalyst other than the acetyl acetonate complex may be added as necessary. Examples of such a curing catalyst include perchloric acid, magnesium perchlorate, aluminum perchlorate, zinc perchlorate, Perchloric acids such as ammonium chlorate, organic metal salts such as sodium acetate, zinc naphthenate, cobalt naphthenate, zinc octoate, stannic chloride, aluminum chloride, ferric chloride, titanium chloride, zinc chloride, salt And Lewis acids such as antimony hydride.

Further, the coating composition used in the present invention includes a surfactant, an antistatic agent, an ultraviolet absorber, an antioxidant, a disperse dye, an oil-soluble dye, a fluorescent dye, a pigment, a photochromic compound, a hinderdamine, and a hindered polymer. Additives such as knol can be used alone or in combination of two or more.By adding these additives, the coating properties of the coating composition and the film performance after curing can be improved. I can do it.

[Resin base material]

In the laminate of the present invention, it is important to select a urethane resin substrate or an aryl resin substrate as the resin substrate. That is, when another resin base material is used, a cured product layer excellent in sensitivity characteristic to water / weather resistance cannot be formed even if the above-mentioned coating composition is used. Although the reason for this has not been clearly elucidated, it is likely that the above-described coating composition forms a chemical or physical cross-link with the surface of the thiourethane resin-based resin and the aryl resin-based material, Therefore, the adhesion between the cured product layer and the surface of the resin base material is remarkably improved, and such a cross-linking and the composite metal oxide in the coating composition are extremely stable against light and moisture. Yes, the cross-linking is formed stably even when it is kept for a long time in a poor environment, so it seems that excellent il resistance will be exhibited. For example, when a cured layer is formed on the surface of a polycarbonate resin substrate using the above-described coating composition, the adhesion between the cured layer and the resin substrate is insufficient from the beginning. These resin substrates used in the present invention have a refractive index of 1.55 or more. It is preferable that interference fringes due to a difference in refractive index from the coating composition can be prevented.

Thiourethane resin used as a resin base material (obtained by reacting thiol with isocyanate. Examples of thiol include 1,2-ethanedithiol, 1,6-hexanedithiol, 1,2,3-propane Trithiol, propane tris

(2-mercaptoacetate), 1,3-propanedithiol, tetrakis (mercaptomethyl) methane, petaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (2-mercaptopropionate), tetrakis (2 —Mercaptoethylthiomethyl) propane, 2-mercaptoethanol, 2,3-dimercaptopropanol, 3-mercapto-1,1,2-propanediol, di (2-mercaptoethyl) sulfide, 2,5— Dimercapto-1,4-dithiane, 2,5-Dimercaptotyl-1,4-dithiane, Tris

(Mercaptomethyl) isocyanurate, 1,4-dimercaptocyclohexane, 4-mercaptophenol, 1,2-benzenedithiol, 1,3,5-benzenetrithiol, 1,2-dimercaptomethylbenzene, 1,2 3-dimercaptomethylbenzene, 1,4-dimercaptomethylbenzene, 1,3,5-trimercaptomethylbenzene, bismercaptoethyl sulfide, 1,2-bis {(2-mercaptoethyl) thio} —3 —Mercaptopropane, 1,2-bis (mercaptomethylthio) ethane, tetrakis (mercaptoethylthiomethyl) methane and the like.

Examples of the isocyanate include tylene diphenyl diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,2-diisocyanatobenzene, and 1,3-diisocyanate. 1,4-diisocyanatomethylbenzene, 1,2-diisocyanatomethylbenzene, 1,3-diisocyanatomethylbenzene, 1,4-diisocyanatomethylbenzene, 4,4, diphenylenediocyanate Tri, 3,3'-dimethyl-4,4,1-diphenylenediisocyanate, xylylenediisocyanate, naphthylene 1,5-diisocyanate, tetramethylxylenediisocyanate, isophoronediisosocyanate, dicyclohexylmethanedi ^ T socyanate, hexamethylenedi socyanate, tetramethylki Rirenji <Soshianeto, 1, 3, 5-Torii And sodium cyanomethylcyclohexane.

The aryl resin used as the resin base material is a polymer obtained by polymerization of a monomer containing an aryl group. Specific examples of the aryl group-containing nomer include aryl diglycol carbonate, diaryl isophthalate and its oligomer, Examples include diaryl terephthalate and its oligomers.

[Manufacture of laminated body]

The laminate of the present invention is obtained by applying the coating composition to the surface of the above-mentioned resin base material (thiourethane resin base material or aryl resin base material) and curing the composition to form a cured product layer. Manufactured.

When applying the coating composition, the surface of the base material must be treated in advance with an alkali 5a treatment, acid treatment, surfactant treatment, uv ozone treatment, inorganic or organic fine particles in order to improve the adhesion between the base material and the cured product layer. It is effective to perform a polishing treatment by I2 or a plasma or corona discharge treatment. The coating composition can be applied by a diving method, a spin coating method, a spraying method or a flow method. In particular, for eyeglass lenses, the dive method is preferably used in order to efficiently coat both surfaces of many substrates.

Curing after application is usually carried out by air drying in dry air or air and then heat treatment. The heating temperature is generally 80 ° C. or higher, particularly 1 ° o ° C. or higher, and is a temperature at which the resin base material is not deformed, and one IS is preferably 150 ° C. or lower. The curing time is about 2 hours at 130 ° C and about 2 to 5 hours at 100 ° C to 120 ° C. The cured product layer 物 formed by curing can have a thickness of about 0.1 to 50 / m, but when this laminate is used for a mega lens, the thickness of the cured product layer is A range of 1 to 10 m is particularly preferred.

In the laminate obtained in this manner, if necessary, an antireflection film made of an inorganic substance is formed on the surface of the cured material layer. Sputtering method and the like. In the vacuum deposition method, an on-beam assist method in which an ion beam is simultaneously irradiated during the deposition may be used. Further, such an antireflection film may have either a single layer or a multilayer structure. Examples of inorganic substances forming an antireflection film, S i O U, S i O, Z r 0 2, _{T i 0 2, T i O} , T i 2 0 3, T i 2 0 5, AI 2 0 3, T a 2 O 5, C e0 2, MgO, Y 2 0 3, S n 0 2, M g oxides such as F _2> WO ₃ and the like. These inorganic oxides may be used alone or in combination of two or more.

Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

In Examples and Comparative Examples, the following sols were used as the sol of the composite metal oxide fine particles.

Composite metal oxide fine particle sol (a): used in Examples 1 to 10 and Comparative Example 3

Composite metal oxide particles composed of tin oxide and zirconium oxide, coated with antimony pentoxide and gallium oxide, and dispersed in methanol (HX series manufactured by Nissan Chemical Industries, Ltd.).

Tin oxide, zirconium oxide, antimony pentoxide, and manganese oxide (% by mass): 77.7 / 1/1/7/7. 0X3.6

Solids concentration; 30.1% by mass

pH; 7.3

Composite metal oxide fine particle sol (b): used in Comparative Examples 1 and 4.

Composite metal oxide particles composed of titanium oxide, tin oxide and zirconium oxide, coated with antimony pentoxide, and dispersed in methanol (HIT series manufactured by Nissan Chemical Industries, Ltd.).

Titanium oxide, tin monoxide, zirconium oxide, antimony pentoxide (% by mass): 5 to 15/1/5 to 25 1 to 5 1 to 5

Solid content: 30.0% by mass

pH; 7.5

Mixed metal oxide fine particle sol (c): Comparative example 2

A composite metal oxide fine particle composed of titanium oxide, zirconium oxide and silicon oxide dispersed in methanol (trade name "Opt Lake 113 OZJ", manufactured by Catalyst Chemical Industry Co., Ltd.).

Solid content: 30.0% by mass pH: 4.8 In addition, the method for evaluating the characteristics of the iodide layer of the lens (laminate) in each of Examples and Comparative Examples is as follows.

(a) Appearance

The transparency of the cured product layer was observed by visual inspection. That is, the sample lens is arranged in the light beam so that the optical axis of the sample lens is perpendicular to the direction of the light beam from the light source (color CAB INIII manufactured by Cabin Industry Co., Ltd.). Lens <7) Optical axis direction From the visual observation, the transparency of the cured product layer was evaluated by the degree of cloudiness. The evaluation criteria are as follows.

◎: The lens having the cured product layer was almost transparent, and no white bubbles were observed.

〇: Slight cloudiness is observed.

Δ: A considerable degree of cloudiness is observed.

X: Completely cloudy.

(b) Solvent resistance

A sample lens is immersed in methanol, isopropyl alcohol, toluene, acetone, or a 0.4 mass% NaOH aqueous solution for 24 hours, and the solvent resistance is improved by changing the surface state. evaluated. The evaluation criteria are as follows.

〇: No change from before impregnation.

X: Change is observed as compared to before impregnation.

(c) Scratch resistance

Using a steel wool (Pontstar # 0000 manufactured by Nippon Steel Wool Co., Ltd.), the surface of the sample lens (cured material layer surface) was rubbed 10 times back and forth with a load of 1 kg, and the degree of damage was visually evaluated in three steps. . The evaluation criteria are as follows.

A: Almost no scratch.

B: Slightly damaged.

C: The coating film has peeled off.

(d) Adhesion

Adhesion between the cured product layer and the lens substrate (resin substrate) according to JI SD-0202 All crosscut tape tests evaluated.

That is, using a cutter knife, cuts are made at intervals of about 1 mm on the lens surface (cured material surface) to form 100 squares. Cellophane adhesive tape on it

(Nichiban Co., Ltd. Cellotape) was strongly adhered, and it was pulled at once from the surface in the direction of 90 ° and peeled off, and the squares where the cured product layer remained were measured. The evaluation result is

(Number of remaining cells) / 100

(e) Weather resistance

In order to evaluate the weather resistance (durability [equivalent to durability]) of the cured product layer due to light irradiation, a deterioration promotion test was performed. After the deterioration promotion test, the adhesion was measured in the same manner as above, and the adhesion was measured. The weather resistance was evaluated.

The accelerated deterioration test was performed by accelerating the sample lens for 200 hours using Xenon Weather Meter X25 manufactured by Suga Test Instruments Co., Ltd.

(f) Storage stability

After the coating composition was prepared, it was stored at a temperature of 20 ° C. for 3 weeks and 5 weeks, and then cured using each coating composition to form a cured layer. The storage stability was evaluated by evaluating solvent resistance, scratch resistance, adhesion, and weather resistance.

—Example 11

(1) Adjustment of coating composition

r- glycidoxy pro built Increment Tokishishiran _{5 3} 0.1 parts by mass Methanol

700 parts by weight were mixed. While the solution was sufficiently stirred, 121.3 parts by mass of a 0.05 N aqueous hydrochloric acid solution was added thereto, and the mixture was continuously stirred for 3 hours. Next, 2.0 parts by mass of a silicon-based surfactant (trade name “L-17001 J”, manufactured by Nippon Rikiichi Co., Ltd.)

A I (I I I) acetyl acetate 7.3 parts by mass,

400 parts by mass of t-butyl alcohol,

Composite metal oxide fine particle sol (a) 1 250 parts by mass,

Was added and mixed, and the mixture was stirred for 5 hours, and then aged all day and night to obtain a coating composition (A). Further, a part of the coating composition (A) was subdivided, and distilled water was added thereto so that the content became 10% by mass, and the mixture was stirred for about 1 hour.

(Α ') was prepared. (2) Formation of cured layer

Prepare a urethane resin lens with a refractive index of 1.60 (Mitsui East 井 resin: MR8), immerse the urethane resin lens in a 10% aqueous solution of water at 40 ° C for 5 minutes, and carry out an air treatment. went.

The above-described alkali-treated thiourethane resin lens is dipped in the coating composition (A) or (Α ′) obtained above, and is pulled up at a speed of 30 cm / min to form a coating on the surface of the thiourethane resin lens. The coating composition was applied. The dive was performed under three conditions of relative humidity of 30% RH, 50% RH, and 7O% RH (each temperature was about 23 ° C). After application, the coating was dried at 70 ° C. for 2 O minutes, and then cured at 120 ° C. for 4 hours to obtain a cured product layer on the surface to obtain a :: lens.

The formed cured material layer was a colorless and transparent film having a thickness of about 2 microns and a refractive index of 1.60.

The lens (cured material layer) formed by diving the coating compositions (A) and (A,) under the condition of 30% RH is described in (a) Appearance,

(b) Solvent resistance, scratch resistance, (d) adhesion, and (e) weather resistance were all evaluated. For lenses formed by diving under 50% RH and 70% RH conditions, (A) Only the appearance was evaluated, and the results are shown in Table 1.

Furthermore, after holding the coating compositions (A) and (Α ′) at a temperature of 20 ° C. for 3 weeks and 5 weeks, a lens in which a cured layer was formed in the same manner as described above was also used. The storage stability was evaluated by evaluating each property in the same manner as described above. The results are shown in Tables 2 and 3. Example 2—

The same procedure as in Example 1 was conducted, except that a 1.67 polyurethane resin lens with a refractive index of 1.67 was used as the resin base material instead of a polyurethane resin lens with a refractive index of 1.67 (Mitsui Toatsu resin: MR7). , About 2 microns thick, colorless and transparent with a refractive index of 1.60 A lens having a compound layer on the surface was prepared, and various characteristics were evaluated in exactly the same manner as in Example 1. The results are shown in Tables 1 to 3. Example 3—

Except for using an aryl resin lens having a refractive index of 1.60 instead of the 1.60 thiourethane resin lens as the resin base material, the thickness was about 2 microns and the refractive index was 1 in the same manner as in Example 1. A lens having a colorless and transparent cured product layer on the surface was prepared, and various characteristics were evaluated in exactly the same manner as in Example 1. The results are shown in Tables 1 to 3. Example 4

530.1 parts by mass of r-glycidoxypropyltrimethoxysilane, 125 parts by mass of methanol, 200 parts by mass of acetylacetone, and 375 parts by mass of isopropyl alcohol were mixed. In exactly the same manner as in Example 1, a 0.05 N hydrochloric acid solution, a silicon-based surfactant, Al (III) acetyl acetonate, t-butyl alcohol and a composite metal oxide were added to this solution. The fine particle sol ( _a >) was mixed to obtain a coating composition (B). Furthermore, a water-added coating composition (Β ') was prepared in exactly the same manner as in Example 1.

Except that the above coating compositions (Β) and (Β ') were used, in the same manner as in Example 1, a thickness of about 2 microns and a refractive index of 1.600) a colorless and transparent cured layer was provided on the surface. Each lens was manufactured, and various characteristics were evaluated in exactly the same way as in Example 1. The results are shown in Tables 1 to 3. Example 5—

530.1 parts by mass of r-glycidoxypropyltrimethoxysilane, 400 parts by mass of methanol and 300 parts by mass of isopropyl alcohol were mixed. While sufficiently stirring this solution, 12.3 parts by mass of a 0.05 N aqueous hydrochloric acid solution was added thereto, and the mixture was continuously stirred for 3 hours. Then, to this mixture,

Silicon surfactant (attacked by Nippon Tunicer Co., Ltd., brand name "| _ 7001")

2.0 parts by mass, AI (III) acetyl acetate 7.3 parts by mass,

400 parts by mass of ethylene glycol monoisopropyl ether,

Composite metal oxide fine particle sol (a) 1 250 parts by mass,

Was added and mixed, and the mixture was stirred for 5 hours and then aged all day and night to obtain a coating composition (C). Further, a hydrogenation force coating composition (C ′) was prepared in exactly the same manner as in Example 1.

Using the above coating composition (C) or (C,), instead of a 1,60 polyurethane resin lens with a refractive index of 1.67, a polyurethane resin lens with a refractive index of 1.67 (made by Mitsui Toatsu) Resin: Except for using MR7), a lens with a thickness of about 2 microns and a refractive index of 1.60 a colorless and transparent cured layer on the surface was prepared and implemented in exactly the same manner as in Example 1. Various characteristics were evaluated in exactly the same manner as in Example 1, and the results are shown in Tables 1 to 3.

—Example 6—

471.0 parts by mass of r-glycidoxypropyltrimethoxysilane, 69.0 parts by mass of tetraethoxysilane and 40 parts by mass of methanol were mixed. While the liquid was sufficiently stirred, 13.66 parts by mass of a 0.05 N aqueous hydrochloric acid solution was added thereto, and the mixture was continuously stirred for 3 hours. Then, to this mixture,

Silicon-based surfactant (manufactured by Nippon Rikiichi Co., Ltd., trade name "L-7001J") 2.0 parts by mass,

A I (I I I) acetyl acetate 7.3 parts by mass,

t-butyl alcohol 380 parts by mass,

Composite metal oxide fine particle sol (a) 1 250 parts by mass,

Was added and mixed, stirred for 5 hours, and then aged all day long to obtain a coating composition (D). Further, a coating composition (D,) was prepared in exactly the same manner as in Example 1.

A colorless and transparent cured layer having a thickness of about 2 microns and a refractive index of 1.60 was provided on the surface in the same manner as in Example 1 except that the above-mentioned coating composition (D) or (D,) was used. A lens was manufactured, and various characteristics were evaluated in exactly the same manner as in Example 1. The results are shown in Tables 1 to 3. Example 7—

375.0 parts by mass of r-glycidoxypropyltrimethoxysilane, 155.0 parts by mass of T-glycidoxypropylmethyldimethoxysilane, 400 parts by mass of methanol and 300 parts by mass of isopropyl alcohol were mixed. While sufficiently stirring this solution, 11.4 parts by mass of a 0.05 N aqueous hydrochloric acid solution was added, and the mixture was continuously stirred for 3 hours. Then, to this mixture,

Silicone surfactant (manufactured by Nippon Unicar Co., Ltd., trade name "L-17001 J") 2.0 parts by mass,

A I (I I I) acetyl acetate 7.3 parts by mass,

Jaceton alcohol 410 parts by mass,

Composite metal oxide fine particle sol (a) 1 250 mass sound 13,

Was added and mixed, and the mixture was stirred for 5 hours and then aged all day and night to obtain a coating composition (E). Further, a water-added coating composition (Ε ′) was prepared in exactly the same manner as in Example 1.

Except that the above coating composition (Ε) or (Ε,) was used, a colorless and transparent cured layer having a thickness of about 2 microns and a refractive index of 1.6 was applied to the surface in the same manner as in Example 1. A lens provided was prepared, and various characteristics were evaluated in exactly the same manner as in Example 1. The results are shown in Tables 1 to 3. Example 8—

A coating composition (F) was obtained in the same manner as in Example 1, except that A I (III) acetyl acetonate was replaced with Fe (III) acetyl acetonate. Further, a water-containing coating paste (F ′) was prepared in exactly the same manner as in Example 1. Except that the above-mentioned coating composition (F) or (F,) was used, a colorless and transparent cured layer having a thickness of about 2 microns and a refractive index of 1.6 was formed on the surface in exactly the same manner as in Example 1. A lens provided was prepared, and various characteristics were evaluated in exactly the same manner as in Example 1. The results are shown in Tables 1 to 3.

—Comparative Example 11

Composite metal oxide fine particle sol (b) instead of composite metal oxide fine particle sol (a) Except for using, a coating composition (G) was obtained in the same manner as in Example 1. Further, a water-added coating composition (G,) was prepared in exactly the same manner as in Example 1. Except that the above-mentioned coating composition (G) or (G ') was used, a colorless and transparent cured product layer having a thickness of about 2 microns and a flexural ratio of 1.62 was obtained in the same manner as in Example 1. A lens provided on the surface was prepared, and various characteristics were evaluated in exactly the same manner as in Example 1. The results are shown in Tables 1 to 3. Comparative Example 2—

A coating composition (H) was obtained in the same manner as in Example 1, except that the composite metal oxide fine particle sol (c) was used instead of the composite metal oxide fine particle sol (a). Furthermore, a water-added coating composition (Η ′) was prepared in exactly the same manner as in Example 1. Except that the above coating composition (Η) or (Η,) was used, a colorless and transparent cured layer having a thickness of about 2 microns and a renewal rate of 1.62 was formed on the surface in the same manner as in Example 1. Were prepared, and various characteristics were evaluated in exactly the same manner as in Example 1. The results are shown in Tables 1 to 3. Comparative Example 3—

In the same manner as in Example 1 except that a polycarbonate resin lens having a refractive index of 1.59 was used instead of the urethane resin lens having a refractive index of 1.60, a thickness of about 2 micron and a refractive index of 1. A lens having a 60 cured layer on the surface was prepared, and various characteristics were evaluated in the same manner as in Example 1. The results are shown in Tables 1 to 3.

As is clear from Tables 1 to 3, when the cured product layer was laminated on the surface of the polyurethane resin substrate or the aryl resin substrate using the coating compositions in Examples 1 to 8, the initial appearance (white turbidity) was observed. Degree), solvent resistance, scratch resistance, adhesion, and weather resistance were all good. In addition, storage stability is good, and even when a cured layer is formed using the coating composition after 3 weeks and 5 weeks of storage, appearance, solvent resistance, scratch resistance, adhesion, Physical properties such as weather resistance were the same as the physical properties (initial physical properties) when a cured layer was formed immediately after preparing the coating composition. Furthermore, even when the water-added coating composition was used, the appearance of the laminate was very good.

On the other hand, in the case of Comparative Examples 1 and 2, the initial appearance, solvent resistance, scratch resistance, and adhesion were good, but the weather resistance was insufficient. This inferior weather resistance is the same in the storage stability test (see Tables 2 and 3). In addition, it is understood that when a water-added coating composition is used, the appearance of the coating composition is remarkably poor, and these coating compositions are sensitive to moisture and can be used only in a limited number of cows. Wear.

In addition, in Comparative Example 3 in which a cured product layer was formed using the coating composition of Example 1 on the surface of the polycarbonate resin lens I, physical properties such as solvent resistance, adhesion, and scratch resistance were insufficient. In addition, regarding the appearance, the surface of the polycarbonate resin lens is slightly clouded due to contact with the epoxy group-containing gay compound. Example 9

The polyurethane resin lens having a refractive index of 1.60 used in Example 1 was dyed with a dye (trade name: BPI® SunGray, trade name, manufactured by Toshiba Corporation) to obtain a dye-containing lens. Using the coating composition (A) prepared in Example 1, a cured layer was formed on the surface of the dye-containing lens in the same manner as in Example 1.

For such a dye-containing lens, the adhesion before and after the 200-hour accelerated test (before and after the heat resistance test) by Xenon Laser Meter X25 manufactured by Suga Test Co., Ltd. This was performed by determining a * and b * using a color computer (manufactured by Suga Test Instruments). Table 4 shows the results. Example 1 o-

The refractive index of 1. ⁶ 7 Chiouretan resin lens used in Example 5 were stained with a dye in the same manner as in Example 9, to obtain a dye-containing lenses. A cured product layer was formed on the surface of the dye-containing lens in the same manner as in Example 5. A cured product layer was formed on the surface of the dye-containing lens in the same manner as in Example 1 using the coating composition (C) prepared in Example.

The adhesion and the change in color tone were evaluated for the dye-containing lens in the same manner as in Example 9, and the results are shown in Table 4. Comparative Example 4—

The thiourethane resin lens having a refractive index of 1/60 used in Example 1 (or Comparative Example 1) was dyed with a dye in the same manner as in Example 9 to obtain a dye-containing lens. Using the coating composition (G) prepared in Comparative Example 1, a cured product layer was formed on the surface of the dye-containing lens in the same manner as in Example 1.

The dye-containing lens was evaluated for adhesion and change in color tone in the same manner as in Example 9, and the results are shown in Table 4. As can be seen from the results in Table 4, the laminates of the present invention (Examples 9 and 10) have good adhesion before and after the weather resistance test and little change in color tone. On the other hand, in the laminate of Comparative Example 4, when the weather resistance test was performed, the adhesion was reduced, and the color tone changed before and after the test.

Table 4

Coating composition Dyes ## EQU1

a * b * Visual color tone Adhesion a * b * Visual color tone Adhesion Example 9 A Sun ray -1.17 -5.34 Ray 100/100 -0.27 -5.12 Gray 100/100 Example 10 C ¾un ray -1.15 One 5.12 100 / 100 -0.23 -4.96 Gray 100/100 and Comparative Example 4 IG SunGray -1.17 -5.25 L Gray "100/100 -0.24 1.13 Yellow Grays 0/100

Claims

The scope of the claims

1. In a laminate in which a cured layer of a coating composition is formed on a resin substrate surface,

The coating composition comprises the following components (A) to (D):

(A) composite metal oxide fine particles obtained by coating a composite metal oxide composed of tin oxide and zirconium oxide with antimony pentoxide and silicon oxide;

(B) an epoxy group-containing gayne compound or a partial hydrolyzate thereof;

(C) an organic solvent;

(D) acetyl acetonate complex;

Containing, and

A laminate, wherein the resin substrate is a thiourethane resin substrate or an aryl resin substrate.

2. The coating composition contains 25 to 250 parts by mass of the composite metal oxide fine particles of the component (A) and 100 to 100 parts by mass of the organic solvent of the component (C) per 100 parts by mass of the component (B). 2. The laminate according to claim 1, wherein the laminate contains 2,500 parts by mass of the acetyl acetonate complex of the component (D) in an amount of 0.1 to 15 parts by mass.

3. The lanthanum body according to claim 1, wherein the thiourethane resin base material or the aryl resin base material has a refractive index of 1.55 or more.

4. The laminate according to claim 3, wherein the thiourethane resin base or the aryl resin base contains a dye.

5. A plastic lens comprising the laminate according to claim 3.

6. A plastic lens comprising the laminate according to claim 4.

7. The following (A) ~ on the surface of the polyurethane resin base or aryl resin base (D) Ingredient:

(A) composite metal oxide fine particles comprising a composite metal oxide composed of tin oxide and dinoreconium oxide, coated with hyantimon pentate and gay oxide;

(Β) an epoxy group-containing silicon compound or a partial hydrolyzate thereof;

(C) an organic solvent;

(D) acetyl acetate complex;

A method for producing a laminate, comprising: applying a coating composition containing the same; and heating the coating composition to a temperature of 80 ° C. or higher to cure the coating composition to form a cured product layer.