JPH11116843A - Coating composition and composite structure - Google Patents

Abstract

(57) [Summary] An object of the present invention is to dramatically improve the transparency and various durability (particularly, weather resistance) of a coating film having a refractive index of 1.52 or more. At the same time, the pot life of the coating solution at room temperature storage can be extended to 3 weeks or more. Kind Code: A1 A composite oxide fine particle comprising (A) tin oxide, titanium oxide and zirconium oxide; and (B)
(C) F as a curing catalyst for a specific organosilicon compound
e, at least one compound selected from the group consisting of acetylacetonate, perchloric acid, carboxylic acid or anhydride thereof having Al, Sn or Ti as a central metal, and a mixture thereof, and (D) Li, Cu Alternatively, a coating composition to which acetylacetonate having Mn as a central metal was added in combination was used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention forms a transparent film having excellent durability and dyeing properties such as abrasion resistance, chemical resistance, hot water resistance, heat resistance and weather resistance on the surface of a synthetic resin lens. And a coating composition for the same. Further, the present invention relates to a composite structure in which an antireflection film made of an inorganic substance (hereinafter, also referred to as “inorganic vapor-deposited film”) is provided on the transparent film.

[0002]

2. Description of the Related Art A lens made of a synthetic resin, particularly a diethylene glycol bisallyl carbonate (CR-39) resin lens, is superior to a glass lens in safety, workability and fashionability. Further, in recent years, due to the development of antireflection technology and hard coat technology, these synthetic resin lenses have rapidly spread.

As a hard coat composition, a method of providing a silicon-based hard coat film on the surface of a plastic lens is generally used. As hardening catalysts, JP-B-60-111727, JP-B-60-30350 and the like disclose a hard coat composition using acetylacetonate as an Al (III) central metal atom.

Japanese Patent Publication No. 33868/1986 discloses a hard coat composition containing an amine compound, a polycarboxylic acid, various acetylacetone metal salt compounds, a phenol compound, and a compound containing boron trifluoride. I have.

Further, Japanese Patent Publication No. 62-9266 discloses a hard coat composition using ammonium peroxy acid, and Japanese Patent Publication No. 4-59601 discloses a hard coat composition using magnesium peroxy acid. .

As a hard coat film having a high refractive index, Japanese Patent Publication No. Sho 61-54331 and Japanese Patent Publication No. Sho 63-37
No. 142 discloses Al, Ti, Zr having a high refractive index,
A coating technique using a colloidal dispersion of Sn and Sb oxide fine particles is disclosed. Further, Japanese Patent Laid-Open No.
No. 301517 discloses a method for producing a composite sol of titanium dioxide and cerium dioxide.
Japanese Patent Application Laid-Open No. 264902/1994 discloses a technique of using composite oxide fine particles of Ti and Ce in a coating composition, and Japanese Patent Application Laid-Open No. 3-68901 discloses a technique of using fine particles obtained by treating a composite oxide of Ti, Ce and Si with an organosilicon compound. I have.

[0007]

However, the hard coat composition using the above-mentioned curing catalyst has no problem in the basic properties of the coating film, but in order to extend the liquid life of the composition, It is not always satisfactory in that the control of the coating liquid becomes complicated such as the need to adjust the pH. In addition, in order to further extend the life of products coated with these hard coat compositions, it was a fact that it was desired to improve the level of weather resistance.

[0008]

The present inventors have conducted intensive studies to solve these problems. As a curing catalyst, acetylacetonate of Fe, Al, Sn or Ti or perchloric acid is used. Alternatively, it has been found that by using a carboxylic acid or an anhydride thereof and an acetylacetonate of Li, Cu or Mn together, both excellent productivity and basic characteristics can be harmonized. At the same time, among the numerous composite oxide fine particles, in particular, according to the composition mainly composed of the composite oxide fine particles composed of tin oxide, titanium oxide and zirconium oxide at a specific weight% ratio, the weather resistance is remarkably large. We also found that it was possible to level up.

The present inventors have further improved the transparency and curability of a coating film obtained by thermosetting by including a silane compound having a polymerizable reactive group and a polyfunctional epoxy compound in addition to the above components. The present invention has been found to improve the dyeing properties and the excellent performance in the adhesion (durability) with the inorganic vapor-deposited film, and at the same time, to extend the service life of the coating liquid.

That is, the coating composition of the present invention comprises the following components (A) and (B) as main components,
Further, it is characterized by containing the following components (C) and (D) as a curing catalyst.

(A) Composite oxide fine particles composed of tin oxide, titanium oxide and zirconium oxide.

(B) General formula

[0013]

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An organosilicon compound represented by the formula (wherein R ¹
Is an organic group having a polymerizable reactive group, R ² is a hydrocarbon group having 1 to 6 carbon atoms, X ¹ is a hydrolyzable group, and n is 0 or 1. ).

(C) (a) Fe (III), Al (III),
Acetylacetonate having Sn (IV) or Ti (IV) as a central metal, (ii) magnesium or ammonium perchlorate, (iii) an aliphatic saturated or unsaturated carboxylic acid or an aromatic carboxylic acid or an aromatic carboxylic acid thereof Anhydrous,
And one or more compounds selected from the group consisting of and mixtures thereof.

(D) Li (I), Cu (II), Mn (I
Acetyl acetonate containing I) or Mn (III) as a central metal atom.

In the present invention, the composite oxide fine particles of the component (A) preferably have a weight percentage of 60 to 85 tin oxide, 10 to 30 titanium oxide and 1 to 10 zirconium oxide. A composition.

As the polymerizable curable component as a main component constituting the coating composition, a conventionally known component can be used.

In particular, in the present invention, a coating composition containing the following components (E) and (F) and an antireflection film made of an inorganic substance are provided on the surface of the coating made of the coating composition. When it is configured as a composite structure, it exhibits its excellent effects.

(E) An organosilicon compound represented by the following formula:

[0021]

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(Wherein R ³ and R ⁴ are hydrocarbon groups having 1 to 6 carbon atoms, X ² and X ³ are hydrolyzable groups, and Y is an organic group containing a carbonate group or an epoxy group. And k and m are 0 or 1.) (F) Polyfunctional epoxy compound.

In the present invention, the combined use of the components (C) and (D) as the curing catalyst plays a very important role. That is, even when the component (C) is used alone, the effect as a curing catalyst is sufficient. However, by using these catalysts in combination with the component (D), various durability and productivity of the coating film are dramatically improved. Particularly, the combined use of the component (D) is excellent in improving the pot life of the composition (coating liquid).

Among these components (D), acetylacetonates of lithium and manganese are particularly preferred for exhibiting their effects.

The composite oxide fine particles composed of tin oxide, titanium oxide and zirconium oxide as the component (A) include those dispersed in a dispersion medium such as water, an alcohol or other organic solvent in a colloidal state. Can be
It is also possible to use those obtained by treating the surfaces of these fine particles with an organosilicon compound or an amine compound and / or a carboxylic acid in order to enhance the dispersion stability in these coating solutions. As the organosilicon compound used at this time, there are monofunctional silane, difunctional silane, trifunctional silane, tetrafunctional silane and the like. In the treatment, the hydrolyzable group may be untreated or hydrolyzed. Further, after the treatment, a state in which the hydrolyzable group has reacted with the —OH group of the fine particles is preferable, but there is no problem in stability even when a part remains. As the amine compound, ammonium or ethylamine,
There are alkylamines such as triethylamine, isopropylamine and n-propylamine, aralkylamines such as benzylamine, alicyclic amines such as piperidine, and alkanolamines such as monoethanolamine and triethanolamine. It is preferable to add the organic silicon compound and the amine compound in an amount of about 1 to 15% based on the weight of the fine particles. In all cases, the particle size is about 1 to 3
The thickness is preferably 10 nm to 50% by weight of the solid content, although the type and amount of application to the coating composition of the present invention are determined by the target film performance.
It is desirable that That is, if the amount is less than 10% by weight, the adhesiveness to the inorganic vapor-deposited film becomes insufficient, or the scratch resistance of the coating film tends to be insufficient. If it exceeds 50% by weight, cracks tend to occur in the coating film. In addition, the dyeability becomes insufficient.

In the component (B), R ¹ is an organic group having a polymerizable reactive group, preferably a vinyl group, an allyl group, an acryl group, a methacryl group, an epoxy group, a mercapto group, a cyano group, A silane compound having a polymerizable reactive group such as an isocyano group or an amino group;
² is a hydrocarbon group having 1 to 6 carbon atoms, and specific preferred examples thereof include a methyl group, an ethyl group, a butyl group, a vinyl group, and a phenyl group. X ¹ is a hydrolyzable functional group, and specific preferred examples thereof include an alkoxy group such as a methoxy group, an ethoxy group and a methoxyethoxy group, a halogen group such as a chloro group and a bromo group, and an acyloxy group. .

Preferred specific examples of the silane compound include vinyltrialkoxysilane, vinyltrichlorosilane, vinyltri (β-methoxy-ethoxy) silane,
Allyl trialkoxysilane, acryloxypropyl trialkoxysilane, methacryloxypropyl trialkoxysilane, methacryloxypropyl dialkoxymethylsilane, γ-glycidoxypropyl trialkoxysilane, β- (3,4-epoxycyclohexyl) -ethyltri Examples include alkoxysilane, mercaptopropyl trialkoxysilane, γ-aminopropyl trialkoxysilane, and N-β (aminoethyl) -γ-aminopropylmethyldialkoxysilane.

This component (B) may be used as a mixture of two or more kinds.

It is more effective to use either method after hydrolysis or use of an acid treatment on the cured film.

The amount of component (B) used is from 20 to
Desirably, it is 60% by weight. That is, if it is less than 20% by weight, the adhesion to the inorganic vapor deposition film tends to be insufficient. On the other hand, if it exceeds 60% by weight, cracks may occur in the cured film, which is not preferable.

Next, as for the component (E), in the general formula (E), R ³ and R ⁴ are a hydrocarbon group having 1 to 6 carbon atoms. , An ethyl group, a butyl group, a vinyl group, a phenyl group and the like. X ² and X ³ are hydrolyzable functional groups, and preferred specific examples thereof include alkoxy groups such as methoxy group, ethoxy group, and methoxyethoxy group, halogen groups such as chloro group and bromo group, and acyloxy groups. And the like. In addition, Y is an organic group containing a carbonate group or an epoxy group, and preferred specific examples include the following.

[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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These disilane compounds can be synthesized by various known methods.

For example, it can be obtained by subjecting diallyl carbonate and trichlorosilane or the like to an addition reaction, followed by alkoxylation. Alternatively, it can be obtained by adding trichlorosilane or the like to a compound having a functional group capable of being epoxidized therein, having a substitution machine capable of addition at both ends, and then performing alkoxylation.

It is more effective to use either component (E) after hydrolysis, or to apply an acid treatment to the cured film.

The amount used is desirably 3 to 40% by weight of the solid content. That is, if it is less than 3% by weight, it is not possible to simultaneously satisfy both the dyeability and the various durability of the inorganic vapor-deposited film. On the other hand, if it exceeds 40% by weight, the water resistance of the coating film deteriorates. Also, the pot life of the coating liquid is shortened.

The addition of the above-mentioned component (E) is preferable from the viewpoint of increasing the curing rate of the composition and improving the yield. In particular, an increase in the curing speed and a shortening of the curing time are excellent because the possibility of dust and impurities adhering to the coating surface in the coating film forming step is reduced.
Furthermore, since this component (E) also has an effect of improving the dyeability, it is advantageous in that the content of the component (F) described below can be reduced. Furthermore, the component (E) has an excellent effect in making the presence of defective portions such as scratches on the surface of the object to be coated less noticeable.

The polyfunctional epoxy compound of the component (F) is
It is widely used for paints, adhesives, casting, etc., for example, polyolefin epoxy resin synthesized by a peroxide method, cyclopentadiene oxide or cyclohexene oxide or polyglycidyl ester obtained from hexahydrophthalic acid and epichlorohydrin Such as alicyclic epoxy resins, polyphenols such as bisphenol A, catechol and resorcinol, or (poly) ethylene glycol, (poly) propylene glycol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerol, sorbitol, etc. Polyglycidyl ether obtained from polyhydric alcohol and epichlorohydrin, epoxidized vegetable oil,
Epoxy novolak obtained from novolak type phenol resin and epichlorohydrin, epoxy resin obtained from phenolphthalein and epichlorohydrin, copolymers of glycidyl methacrylate and methyl methacrylate acrylic monomers or styrene, and further containing the above epoxy compound and monocarboxylic acid ( Epoxy acrylates obtained by a glycidyl group ring-opening reaction with (meth) acrylic acid are exemplified.

Preferred examples of the polyfunctional epoxy compound include 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, Nonaethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl ether, nonapropylene glycol diglycidyl ether,
Neopentyl glycol diglycidyl ether, diglycidyl ether of neopentyl glycol hydroxyhyparate, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, diglycerol diglycidyl ether, Diglycerol triglycidyl ether, diglycerol tetraglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, dipentaerythritol tetraglycidyl ether, sorbitol tetraglycidyl ether, tris (2-hydroxyethyl) Diglyci of isocyanurate Aliphatic epoxy compounds such as triglycidyl ether of tris (2-hydroxyethyl) isocyanurate, alicyclic epoxy compounds such as isophoronediol diglycidyl ether, bis-2,2-hydroxycyclohexylpropane diglycidyl ether, resorcinol Examples thereof include aromatic epoxy compounds such as diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, diglycidyl orthophthalate, phenol novolak polyglycidyl ether, and cresol novolak polyglycidyl ether.

In the present invention, the component (F) is used to improve the water resistance and warm water resistance simultaneously with the role of the dyeing component. Therefore, among the above, 1,6-hexanediol diglycidyl ether, diethylene glycol diglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether,
Glycerol diglycidyl ether, glycerol triglycidyl ether, tris (2-hydroxyethyl)
Aliphatic epoxy compounds such as triglycidyl ether of isocyanurate are particularly preferred.

The amount of component (F) used is 5 to 4 of the total composition.
It must be 0% by weight. That is, if it is less than 5% by weight, the water resistance of the coating film becomes insufficient. On the other hand, if it exceeds 40% by weight, the adhesion to the inorganic vapor-deposited film tends to be insufficient, which is not preferable.

It is also useful to add a tetrafunctional silane compound represented by the general formula Si (OR) ₄ . Preferred specific examples include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetraacetoxysilane, tetraallyloxysilane, tetrakis (2-methoxyethoxy) silane,
Examples include tetrakis (2-ethylbutoxy) silane and tetrakis (2-ethylhexyloxy) silane. These may be used alone or as a mixture of two or more. Further, it is preferable to use them after hydrolysis in the absence of a solvent or in an organic solvent such as an alcohol in the presence of an acid.

The coating composition thus obtained can be used after being diluted with a solvent, if necessary. Solvents such as alcohols, esters, ketones, ethers, and aromatics can be used as the solvent.

The coating composition of the present invention may contain a small amount of a surfactant, an antistatic agent, an ultraviolet absorber, an antioxidant, a disperse dye, an oil-soluble dye,
By adding a fluorescent paint / pigment, a photochromic compound, a light- and heat-resistant stabilizer such as a hindered amine / hindered phenol compound, etc., the coating properties of the coating solution and the film performance after curing can also be improved.

Further, in applying the coating composition of the present invention, in order to improve the adhesion between the substrate lens and the film, the surface of the substrate is previously treated with an alkali, an acid, a surfactant, an inorganic or organic substance. It is effective to perform a polishing treatment, a primer treatment or a plasma treatment with fine particles.

Further, as a coating and curing method, a coating is formed by applying a coating liquid by a dipping method, a spinner method, a spray method or a flow method and then heating and drying at a temperature of 40 to 200 ° C. for several hours. be able to. In particular, for a substrate having a heat deformation temperature of less than 100 ° C., a spinner method that does not require fixing the lens substrate with a jig is preferable.

The thickness of the cured film is 0.05
It is preferably from 30 to 30 μm. That is, 0.05
If it is less than μm, basic performance is not obtained, and if it exceeds 30 μm, the surface smoothness is impaired and optical distortion occurs, which is not preferable.

The coating method includes a dipping method, a spray method, a roll coating method, a spin coating method, a flow coating method and the like.

As a method of forming an antireflection film made of an inorganic substance on the surface of the coating film thus obtained, a vacuum deposition method, an ion plating method, a sputtering method and the like can be mentioned. In the vacuum evaporation method, an ion beam assist method in which an ion beam is simultaneously irradiated during the evaporation may be used. Also, as the film configuration,
Either a single-layer antireflection film or a multilayer antireflection film may be used.

Preferred specific examples of the inorganic substance used include SiO ₂ , SiO, ZrO ₂ , TiO ₂ , TiO,
Ti ₂ O ₃ , Ti ₂ O ₅ , Al ₂ O ₃ , Ta ₂ O ₅ , C
eO ₂ , MgO, Y ₂ O ₃ , SnO ₂ , MgF ₂ , WO
_{3 and the} like. These inorganic substances are used alone or as a mixture of two or more.

In forming the antireflection film, it is desirable to perform a surface treatment on the hard coat film. Specific examples of the surface treatment include an acid treatment, an alkali treatment, an ultraviolet irradiation treatment, a plasma treatment by a high-frequency discharge in an argon or oxygen atmosphere, and an ion beam irradiation treatment with argon, oxygen, or nitrogen.

[0061]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 (1) Preparation of Coating Solution 1832 g of methyl cellosolve, 78 1,4-dioxane
5 g, sol of methanol-dispersed tin oxide-titanium oxide-zirconium oxide composite fine particles (weight ratio: 76.5 / 20.5)
/ 3, solid content concentration 20% by weight, Nissan Chemical Industry Co., Ltd. H
IT series) 5332 g, methanol-dispersed colloidal silica (manufactured by Kasei Kasei Kogyo Co., Ltd., trade name “Oscar 11
32 ", a solid content of 30% by weight) and 102 g of γ-glycidoxypropyltrimethoxysilane. 250 g of a 0.05N hydrochloric acid aqueous solution was added dropwise to the mixture with stirring, and the mixture was further stirred for 4 hours and then aged for 24 hours. After adding 762 g of 1,6-hexanediol diglycidyl ether (trade name “Denacol EX-212” manufactured by Nagase Kasei Kogyo Co., Ltd.) to this solution, Mg (Cl 2) was added.
37 g of O ₄ ) ₂ and 5.5 g of Li (C ₅ H ₇ O ₂ )
g, a silicon-based surfactant (manufactured by Nippon Unicar Co., Ltd., trade name “L-7001” 3 g) and a hindered amine light stabilizer (Sankyo KK, trade name “Sanol LS-77”)
0 "), and the mixture was stirred for 4 hours and then aged all day long to obtain a coating solution.

(2) Coating and Curing The coating liquid thus obtained was subjected to an alkali treatment with a refractive index of 1.60 spectacle lens (Seiko Epson Corporation)
Co., Ltd., lens fabric for Seiko Super Lucious). Lifting speed is 23cm / mi
n. After application, air-dry at 80 ° C for 20 minutes, then 130 ° C
For 60 minutes. The thickness of the cured film thus obtained was about 2 microns, and both the appearance and the dyeability were excellent.

Example 2 An antireflection coating thin film made of an inorganic substance was formed on each of the lenses obtained in Example 1 by the following method.

(1) Formation of Anti-Reflection Thin Film After the lens obtained by the above method is subjected to plasma treatment (argon plasma 400 W × 60 seconds), SiO ₂ , ZrO ₂ , SiO ₂ are sequentially taken from the substrate to the atmosphere. ₂ , Zr
An antireflection multilayer film composed of five layers of O ₂ and SiO ₂ was formed by a vacuum deposition method (BMC-1000 manufactured by Vacuum Instruments Co., Ltd.). The optical thickness of each layer is
₂ layers, next ZrO ₂ and SiO ₂ equivalent film layer and next Z
rO2 layers, the top layer of the SiO ₂ layer was formed as a lambda / 4, respectively. The design wavelength λ was 520 nm.

The resulting multilayer film had a reflection interference color of green and a total light transmittance of 98%.

(2) Test and Evaluation Results The lens obtained in Example 1 (hereinafter referred to as a hard coat lens) and the lens obtained in Example 2 (hereinafter referred to as a hard coat lens)
The test was performed by the following method, and the results are shown in Table 1.

(A) Abrasion resistance: 1 kg of Bonstar # 0000 steel wool (manufactured by Nippon Steel Wool Co., Ltd.)
Was applied and the surface was rubbed for 10 reciprocations, and the degree of damage was visually evaluated in the following stages.

A: There is no scratch in the area of 1 cm * 3 cm.

B: 1 to 10 scratches are made within the above range.

C: 10 to 100 scratches are made in the above range.

D: Although there are countless scratches, a smooth surface remains.

E: Due to scratches on the surface, no smooth surface remains.

(B) Water and chemical resistance: water, alcohol,
It was immersed in kerosene for 48 hours, and those having no change in the surface state were evaluated as good.

(C) Acid / detergent resistance: The product was immersed in an aqueous solution of 0.1N hydrochloric acid and 1% "Mama Lemon" (manufactured by Lion Oil & Fats Co., Ltd.) for 12 hours, and those having no change in surface condition were evaluated as good.

(D) Adhesion: The adhesion between the substrate and the hard coat film and between the hard coat film and the multi-coat film was determined by JI
A cross cut tape test was performed according to SD-0202. That is, cuts are made at 1 mm intervals on the base material surface using a knife, and 100 squares of 1 square mm are formed. Next, a cellophane adhesive tape (Nichiban Co., Ltd., product name "Cellotape") was strongly pressed onto the tape, and then it was suddenly pulled 90 degrees from the surface and peeled off. The index was used.

(E) Weather resistance: A sample having no change in surface state after being exposed to a sunshine weather meter using a xenon lamp for 400 hours was evaluated as good.

(F) Abrasion resistance after weather resistance: After exposure to a sunshine weather meter using a xenon lamp for 400 hours, the same test as in (a) was performed.

(G) Durability: The durability is considered to be essentially an adhesive connection, and the cross-cut tape test described above was performed on the test pieces (a) to (f), and the coating film was formed. Those without peeling were regarded as good.

(H) Dyeing property (hard coat lens only): 1 g of pure water at 92 ° C. was dispersed with 2 g of Amber D, a dye for Seiko Plux diamond coating, to prepare a dyeing solution. The dyeing solution was immersed in the dyeing solution for 5 minutes for dyeing, and a sample having no dyeing unevenness and having a total light transmittance of 20% or more between before dyeing and after dyeing was evaluated as good.

(I) Pot life of coating liquid: 2 after adjustment of coating liquid
After storing in an atmosphere at 0 ° C. for 3 weeks, coating and curing were performed in the same manner, and the durability and dyeability of the hard-coated lens were confirmed. Regarding the durability, a lens which did not decrease the durability of the lens applied after storage compared with the lens applied before storage was evaluated as good. Regarding the dyeability, a sample having no unevenness in dyeing and having a difference between the total light transmittance before storage and the total light transmittance after storage of 3% or less was defined as good.

Example-3 (1) Preparation of Coating Solution 383 g of butyl cellosolve and sol of methanol-dispersed tin oxide-titanium oxide-zirconium oxide composite (weight% ratio: 80/15/5, solid content concentration 20% by weight, Nissan Chemical Industries, Ltd.) 416 g of HIT series manufactured by Kogyo Co., Ltd.) and 95 g of γ-glycidoxypropyltrimethoxysilane were mixed. 27 g of a 0.1N aqueous hydrochloric acid solution was added dropwise to this mixed solution with stirring, and the mixture was stirred for 4 hours and then aged for 24 hours. Glycerol triglycidyl ether (trade name “Denacol EX-314”, manufactured by Nagase Kasei Kogyo Co., Ltd.) was added to the solution.
After adding ₇ g, ₂ g of Fe (C ₅ H ₇ O ₂ ) ₃ and 1.1 g of Mn (C ₅ H ₇ O ₂ ) ₂ , a silicon-based surfactant (trade name “FZ- 2110 "
0.3 g and phenolic antioxidant (trade name “Antage Crystal” manufactured by Kawaguchi Chemical Industry Co., Ltd.) 0.7 g
Was added and stirred for 4 hours, followed by aging for 24 hours to obtain a coating solution.

(2) Coating and Curing The coating liquid obtained as described above was coated on a spectacle lens having a refractive index of 1.66 (a lens fabric for Seiko Super Sovereign manufactured by Seiko Epson Corporation) by a spinner method. Was.

The coating conditions are as follows.

The coating liquid was applied at a rotation speed of 500 rpm for 10 seconds (the coating liquid was applied during this period). The rotation speed was set at 2,000 rpm for 1 second, and the rotation speed was set at 500 rpm for 5 seconds. The cured film thus obtained had a thickness of about 2.3 microns, and was excellent in both appearance and dyeability.

(3) Test and Evaluation Results The lenses thus obtained were tested in the same manner as in Example 1, and the results are shown in Table 1.

Example-4 (1) Formation of anti-reflection thin film After subjecting the lens obtained by the above method to plasma treatment (argon plasma 400 W × 60 seconds), ZrO ₂ , SiO ₂ , ZrO ₂ , S
An anti-reflection multilayer film composed of four layers of iO ₂ was formed by a vacuum deposition method (BMC-1000 manufactured by Vacuum Equipment Co., Ltd.). The optical film thickness of each layer is the first ZrO ₂ and SiO ₂
Was formed so that the equivalent film layer, the next ZrO ₂ layer, and the uppermost SiO ₂ layer each had λ / 4. The design wavelength λ was 520 nm.

The reflection interference color of the obtained multilayer film was green, and the total light transmittance was 98%.

(2) Test and Evaluation Results The lenses thus obtained were tested in the same manner as in Example 2, and the results are shown in Table 1.

Example 5 (1) Preparation of Coating Solution 385 g of isopropyl cellosolve, 112 g of pure water and a sol of methanol-dispersed tin oxide-titanium oxide-zirconium oxide composite fine particles (weight% ratio: 80/15/5, solid content concentration 30) (% By weight, HIT series manufactured by Nissan Chemical Industries, Ltd.)
After mixing 290 g, 97 g of γ-methacryloxypropyltrimethoxysilane, 51 g of γ-glycidoxypropyltrimethoxysilane and 16 g of tetramethoxysilane were mixed. 50 g of a 0.1N aqueous hydrochloric acid solution was added dropwise to this mixture with stirring, and after stirring for 5 hours, S
₂ g of nCl ₂ (C ₅ H ₇ O ₂ ) ₂ and Cu (C ₅ H
The ₇ O _{2) 2} was 0.8 g, a silicon surfactant (Nippon Unicar Co., Ltd., and trade name "L-7604") 0.3 g was then aged overnight after 4 hours with stirring added to the coating solution.

(2) Coating and Curing The thus obtained coating liquid was applied to a polycarbonate injection-molded spectacle lens having a refractive index of 1.58 by a spinner method. The coating conditions were the same as in Example-3.

After air-drying at 80 ° C. for 15 minutes after application, 13
Baking was performed at 0 ° C. for 60 minutes. The thickness of the cured film thus obtained was about 2.1 microns, and the appearance was excellent.

(3) Formation of anti-reflection thin film The lens obtained by the above-mentioned method was prepared by mixing ZrO ₂ of Example 4 with a mixture of ZrO ₂ and Ti oxide (ZrO ₂ / Ti oxide = 65/35 (weight ratio) An anti-reflection film was formed in the same manner except that the method was changed to)).

[0094] The reflection interference color of the obtained multilayer film was green, and the total light transmittance was 99%.

(4) Test and Evaluation Results The lenses thus obtained were tested in the same manner as in Example-2, and the results are shown in Table 1. The dyeability was evaluated in the state of a hard coat lens.

Example -6 (1) Preparation of coating liquid 390 g of methyl cellosolve, sol of methanol-dispersed tin oxide-titanium oxide-zirconium oxide composite fine particles (% by weight)
Ratio: 80/14/6, solid content concentration 30% by weight, Nissan Chemical Industry Co., Ltd. HIT series)
γ-glycidoxypropylmethyldimethoxysilane 69
g and 66 g of γ-glycidoxypropyltrimethoxysilane were mixed. 30 g of a 0.05N hydrochloric acid aqueous solution was added dropwise to this mixed solution with stirring, and the mixture was stirred for 4 hours and then aged for 24 hours. This solution was mixed with glycerol diglycidyl ether (trade name "Denacol EX-", manufactured by Nagase Kasei Kogyo Co., Ltd.).
313 ") after the addition of 73 g of maleic anhydride 8.5
g, and 1.9 g of Li (C ₅ H ₇ O ₂ ) and a silicon-based surfactant (manufactured by Big Chemie Co., Ltd .: trade name “BYK”).
-300 "), and the mixture was stirred for 4 hours and then aged all day and night to obtain a coating solution.

(2) Coating and Curing The coating liquid obtained as described above was used for a spectacle lens having a refractive index of 1.56 (Seiko Epson Corporation, Seiko Plux Co., Ltd.).
IIGX lens cloth) Coating was performed by a spray method.

Spraying was performed using Iwata Weider 61 (a nozzle having a diameter of 1 mm, manufactured by Iwata Coating Machine Co., Ltd.) at a spray pressure of 3 kg / square cm and a paint discharge rate of 100 ml / min.

After air-drying at 80 ° C. for 10 minutes after application, 130
Baking was performed at 60 ° C. for 60 minutes. The thickness of the cured film thus obtained was about 4 microns, and both the appearance and the dyeability were excellent.

(3) Test and Evaluation Results The lenses thus obtained were subjected to tests in the same manner as in Example 1, and the results are shown in Table 1.

Example -7 (1) Formation of anti-reflection thin film After subjecting the lens obtained in Example -6 to an ion beam irradiation treatment with oxygen gas (acceleration voltage 500 V × 60 seconds), the lens was exposed to the atmosphere. In order, SiO ₂ , Zr
An anti-reflection multilayer film composed of five layers of O ₂ , SiO ₂ , TiO ₂ , and SiO ₂ is vacuum-deposited (B: Vacuum Instruments Co., Ltd .: B
MC-1000). At that time, the fourth layer T
iO ₂ was formed by ion beam assisted deposition. The optical film thickness of each layer is as follows: first SiO ₂ , next Z
The equivalent film layer of rO ₂ and SiO ₂ is λ / 4, and the TiO ₂ layer is λ
/ 2, the uppermost SiO ₂ layer was formed to be λ / 4. The design wavelength λ was 520 nm.

The multilayer film thus obtained exhibited a reflection interference color of green and a total light transmittance of 99%.

(2) Test and Evaluation Results The lens thus obtained was subjected to a test in the same manner as in Example 2, and the results are shown in Table 1.

Example-8 (1) Preparation of coating liquid 1830 g of butyl cellosolve, tin oxide dispersed in methanol
Titanium oxide-zirconium oxide composite fine particle sol (wt%
Ratio: 76.5 / 20.5 / 3, solid content concentration 20% by weight,
5683 g) and γ-glycidoxypropyltrimethoxysilane 192
2 g were mixed. To this mixture, add 0.05N aqueous hydrochloric acid solution 5
28 g was added dropwise with stirring, and after stirring for 4 hours, aged for 24 hours, 36 g of Al (C ₅ H ₇ O ₂ ) ₃ and Li were added.
The _(C 5 _H 7 _{O 2)} was 5g, silicon-based surfactant (Nippon Unicar Co., Ltd., trade name "L-7001") was then aged overnight after 4 hours with stirring added 3g coating solution.

(2) Coating and Curing The coating liquid obtained in this manner was subjected to alkali treatment with a refractive index of 1.60 spectacle lens (Seiko Epson Corporation)
Co., Ltd., Seiko Super Luxurious Lens Fabric). The lifting speed is 18 cm / min
And After the application, it was air-dried at 80 ° C. for 20 minutes, and then baked at 130 ° C. for 120 minutes. The thickness of the cured film thus obtained was about 2 microns, and the appearance was excellent.

(3) Formation of antireflection thin film An antireflection film was formed on the lens obtained by the above method in the same manner as in Example-8.

The multilayer film thus obtained exhibited a green reflective interference color and a total light transmittance of 99%.

(4) Test and Evaluation Results The lenses thus obtained were tested in the same manner as in Example-2, and the results are shown in Table 1. The dyeability was evaluated in the state of a hard coat lens.

Comparative Example 1 A lens was coated in the same manner as in Example 1 except that Li (C ₅ H ₇ O ₂ ) was not added.

The lenses thus obtained were tested in the same manner, and the results are shown in Table 1.

Comparative Example 2 A lens was coated in the same manner as in Example 1, except that Mg (ClO ₄ ) ₂ was not added.

The lens obtained in this manner was used in Example-
The test was performed in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example-3 The same procedure as in Example-3 was carried out except that Fe (C ₅ H ₇ O ₂ ) ₃ was not added and the amount of Mn (C ₅ H ₇ O ₂ ) ₃ added was 3 g. Was applied to the lens in an appropriate manner.

The lens obtained in this manner was used in Example-
The test was performed in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 4 In Example 3, instead of the methanol-dispersed tin oxide-titanium oxide-zirconium oxide composite fine particle sol, a methyl cellosolve-dispersed cerium dioxide-titanium dioxide-silicon dioxide composite fine particle sol (Catalyst Chemical Industry Co., Ltd.) Coatings were applied to the lenses in the same manner, except that the trade name “OPTLAKE 1832” (solid content: 20 wt%) was used.

The lens obtained in this manner was used in Example-
The test was performed in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example-5 The procedure of Example 1 was repeated except that the methanol-dispersed tin oxide-titanium oxide-zirconium oxide composite microparticle sol was used instead of the methanol-dispersed tin oxide-tungsten oxide composite microparticle sol. Application was performed.

The lens obtained in this manner was used in Example-
The test was performed in the same manner as in Example 1, and the results are shown in Table 1.

[0119]

[Table 1]

[0120]

As described in detail above, according to the present invention,
The weather resistance of the high-refractive-index coating film is remarkably improved, and the pot life of the coating liquid can be significantly increased without requiring complicated management of the coating liquid. The present invention relates to a plastic lens material including (meth) acrylic resin, styrene resin, carbonate resin, allyl resin, allyl carbonate resin, vinyl resin, polyester resin, polyether resin, urethane resin, and a new monomer or comonomer. It can be applied to resins having various functions such as merging.

Plastic materials having both excellent productivity (no need for complicated coating liquid management and long coating liquid pot life) and various durability are used for plastic materials such as spectacle lenses, camera lenses, light beam fluorescent lenses and light beams. It can be widely applied to consumer or industrial use as a diffusion lens. Furthermore, the present invention can be applied or used in general for transparent glasses such as watch glasses and cover glasses for displays and transparent plastics for optical applications such as cover glasses, and is extremely useful in industry.

Claims (7)

[Claims] 1. A coating composition comprising the following components (A) and (B) as main components and a curing catalyst comprising the following components (C) and (D): . (A) Composite oxide fine particles composed of tin oxide, titanium oxide and zirconium oxide. (B) General formula Wherein R ¹ is an organic group having a polymerizable reactive group, R ² is a hydrocarbon group having 1 to 6 carbon atoms, and X ¹ is a hydrolyzable group. , N is 0 or 1.). (C) (A) acetylacetonate having Fe (III), Al (III), Sn (IV) or Ti (IV) as a central metal, (B) magnesium or ammonium perchlorate, (C) One or more compounds selected from the group consisting of aliphatic saturated or unsaturated carboxylic acids or aromatic carboxylic acids or anhydrides thereof, and mixtures thereof. (D) Li (I), Cu (II), Mn (II) or Mn
Acetyl acetonate having (III) as a central metal atom. 2. The composition according to claim 1, wherein the weight percentage of the composite oxide fine particles of the component (A) is 60 to 85 tin oxide, 10 to 30 titanium oxide, and 1 to 10 zirconium oxide. Composition for coating. 3. The coating composition according to claim 1, comprising an organosilicon compound represented by the following component (E). (E) An organosilicon compound represented by the following formula. Embedded image (Wherein, R ³ and R ⁴ are hydrocarbon groups having 1 to 6 carbon atoms, X ² and X ³ are hydrolyzable groups, Y is a carbonate group or an organic group containing an epoxy group,
k and m are 0 or 1. ) 4. The coating composition according to claim 1, which comprises a polyfunctional epoxy compound as the component (F). 5. A coating film comprising a cured product of the coating composition according to claim 1 is formed on a substrate, and an antireflection film comprising an inorganic substance is further provided on the surface of the coating film. Composite structure provided. 6. The composite structure according to claim 5, wherein said substrate is an optical article. 7. The composite structure according to claim 6, wherein said optical article is a spectacle lens.