JPH10292135A - Coating composition, method for producing the same, and laminate - Google Patents

Abstract

(57) [Problem] To provide a coating composition which satisfies both sufficient weather resistance of a coat film itself and durability when an antireflection film made of an inorganic substance is provided on the surface of the coat film. A specific composite oxide fine particle, a silane compound,
A coating composition containing a disilane compound and an epoxy compound as main components.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention
A transparent film having the same refractive index as the base material on the surface of the synthetic resin lens, and excellent in durability such as abrasion resistance, chemical resistance, warm water resistance, heat resistance, weather resistance and dyeing properties. Further, the present invention relates to a coating composition characterized in that an antireflection film (hereinafter referred to as an inorganic vapor deposition film) made of an inorganic substance can be provided on the coating.

[0002]

2. Description of the Related Art A lens made of a synthetic resin, particularly a diethylene glycol bisallyl carbonate resin (CR-39) lens, is superior to a glass lens in safety, workability, fashionability, and the like. With the development of technology, hard coat technology, and hard coat + anti-reflection technology, it has spread rapidly. But CR
Since the refractive index of -39 resin is 1.50, which is lower than that of a glass lens, the near vision lens has a disadvantage that the outer peripheral portion is thicker than the glass lens. For this reason, in the field of synthetic resin spectacle lenses, technology development for reducing the thickness by using a high-refractive-index resin material has been actively performed. As a technical proposal for that purpose, Japanese Patent Application Laid-Open No. 59-133211,
JP-A-63-46213, JP-A-2-27085
No. 9 proposes a high refractive index resin material having a refractive index of 1.60 or more.

On the other hand, plastic eyeglass lenses have a disadvantage that they are easily scratched, so that a method of providing a silicon-based hard coat film on the surface of a plastic lens is generally used. However, when the same method is applied to a high-refractive-index resin lens having a refractive index of 1.52 or more, interference fringes occur due to a difference in the refractive index between the resin lens and the coating film, which causes poor appearance. As a technical proposal for solving this problem, a colloidal dispersion of silicon dioxide fine particles used in a silicon-based coating composition as disclosed in JP-B-61-54331 and JP-B-63-37142 is highly refracted. Al, Ti, Zr, S
A coating technique has been disclosed in which a colloidal dispersion of oxide fine particles of n and Sb is used. Also,
JP-A-1-301517 discloses a method for producing a composite sol of titanium dioxide and cerium dioxide, and JP-A-2-264902 discloses a composite oxide fine particle of Ti and Ce, and JP-A-3-68901. In the gazette T
There is disclosed a technique in which fine particles obtained by treating a composite oxide of i, Ce and Si with an organosilicon compound are used in a coating composition.

[0004]

The high refractive index coating composition described above has a practically sufficient level of durability. However, in order to further extend the service life of products to which these coating compositions have been applied, it has actually been desired to improve the level of weather resistance.

[0005]

The present inventors have conducted intensive studies to solve these problems, and as a result, among various complex oxides, tin oxide, titanium oxide and zirconium oxide have been particularly developed. The coating composition obtained by containing the composite oxide fine particles constituted at a specific weight% ratio is excellent in transparency, curability, adhesion (durability) with an inorganic vapor-deposited film, and weather resistance. Has found it to be particularly good.

That is, the present invention is a coating composition comprising at least the following components (A) and (B) as main components.

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

[0008]

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An organosilicon compound represented by the formula:
¹ is an organic group having a polymerizable reactive group, and R ² is a hydrocarbon group having 1 to 6 carbon atoms. X ¹ is a hydrolyzable group, and n is 0 or 1. ) In addition, (A)
The weight% ratio of the composite oxide fine particles of tin oxide is 60 to 85,
It is characterized by titanium oxides 10 to 30 and zirconium oxides 1 to 10.

The coating composition of the present invention is useful even if it contains at least one of the following components (C), (D) and (E).

(C) General formula

[0012]

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An organosilicon compound represented by the formula (wherein R ³
, R ⁴ is a hydrocarbon group having 1 to 6 carbon atoms. X ² ,
X ³ is a hydrolyzable group. Y is an organic group containing a carbonate group or an epoxy group, and m is 0 or 1. (D). Polyfunctional epoxy compound (E) particle size 1 to 100 millimicrons silica fine particles and / or the general formula Si (OR ⁵⁾ a hydrolyzate of an organic silicon compound represented by the 4 and / or partial condensate. (Here, R ⁵ represents an alkyl group having 1 to 8 carbon atoms.) In the method for producing a coating composition of the present invention, the pH of a coating solution before the coating composition is thermally cured.
Is set to 4.5 to 7.5.

Further, the laminate of the present invention is characterized in that an antireflection film made of an inorganic substance is provided on the surface of a film produced using the coating composition.

The composite oxide fine particles composed of tin oxide, titanium oxide and zirconium oxide as the component (A) used in the present invention are colloidally dispersed in a dispersion medium such as water, an alcohol or another organic solvent. Things. It is also possible to use those obtained by treating the surfaces of these fine particles with an organosilicon compound, 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. These organosilicon compounds and amine compounds,
The amount of the carboxylic acid added is 1 to 15 based on the weight of the fine particles.
It is necessary to add within the range of about%. In any case, the particle diameter is preferably about 1 to 300 μm, and the kind and amount to be applied to the coating composition of the present invention are determined by the target film performance, but the amount to be used is 10 to 30% of the solid content. 5
It is desirably 0% by weight. That is, 10% by weight
If it is less than 30, the adhesion to the inorganic vapor-deposited film is insufficient, or the scratch resistance of the coating film is insufficient. If it exceeds 50% by weight, cracks occur in the coating film. In addition, the dyeability becomes insufficient.

Subsequently, in the component (B), R ¹ is an organic group having a polymerizable reactive group, and is a vinyl group, an allyl group, an acryl group, a methacryl group, an epoxy group, a mercapto group, a cyano group, an isocyano group. And a silane compound having a polymerizable reactive group such as an amino group, and R ² is a hydrocarbon group having 1 to 6 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a butyl group, and a vinyl group. Group, phenyl group and the like. X ¹ is a hydrolyzable functional group, and specific 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.

Specific examples of the silane compound include vinyltrialkoxysilane, vinyltrichlorosilane, vinyltri (β-methoxy-ethoxy) silane, allyltrialkoxysilane, acryloxypropyltrialkoxysilane, methacryloxypropyltrialkoxysilane, methacryl Oxypropyl dialkoxymethylsilane, γ-glycidoxypropyl trialkoxysilane, β- (3,4-epoxycyclohexyl) -ethyl trialkoxysilane, mercaptopropyl trialkoxysilane, γ-aminopropyl trialkoxysilane, N-β (Aminoethyl) -γ-aminopropylmethyldialkoxysilane and the like.

The component (B) may be used as a mixture of two or more kinds. Further, it is more effective to use after hydrolysis.

Component (B) is used in an amount of 20 to 20% of the total composition.
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, in the general formula of the component (C), R
³ , R ⁴ is a hydrocarbon group having 1 to 6 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a butyl group, a vinyl group, and a phenyl group. X ² , X
Reference numeral ³ denotes a hydrolyzable functional group, and specific examples 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. Further, Y is an organic group containing a carbonate group or an epoxy group.

[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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And the like.

These disilane compounds can be synthesized by various conventionally known methods. For example, it can be obtained by performing an addition reaction between diallyl carbonate and trichlorosilane or the like, followed by alkoxylation. Alternatively, the compound can be obtained by adding a trichlorosilane or the like to a compound having an addable substituent at both ends and further containing an epoxy group or an epoxidizable functional group therein, followed by alkoxylation.

It is more effective to use either the component (C) after hydrolysis or to subject the cured film to an acid treatment. 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 polyfunctional epoxy compound (D) is widely used for paints, adhesives, casting, and the like. For example, a polyolefin-based epoxy resin synthesized by a peroxide method, Alicyclic epoxy resins such as pentadiene oxide, cyclohexene oxide or polyglycidyl ester obtained from hexahydrophthalic acid and epichlorohydrin; polyhydric phenols such as bisphenol A, catechol and resorcinol; or (poly) ethylene glycol, (poly) propylene glycol; Polyglycidyl ether obtained from polyhydric alcohols such as neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerol, sorbitol and epichlorohydrin, epoxidized vegetable oil, novolak Epoxy novolac derived from phenol resin and epichlorohydrin, phenolphthalein and epoxy resins obtained from epichlorohydrin, copolymers of glycidyl methacrylate and methyl methacrylate acrylic monomer or styrene,
Further, an epoxy acrylate obtained by a glycidyl group ring-opening reaction between the above epoxy compound and a monocarboxylic acid-containing (meth) acrylic acid, and the like can be mentioned.

Specific 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 hydroxyhivalic acid ester, 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, Aliphatic epoxy compounds such as rubitol tetraglycidyl ether, diglycidyl ether of tris (2-hydroxyethyl) isocyanurate, triglycidyl ether of tris (2-hydroxyethyl) isocyanurate, isophorone diol diglycidyl ether, bis-2 Alicyclic epoxy compounds such as 1,2-hydroxycyclohexylpropane diglycidyl ether, resorcin diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, ortho phthalic acid diglycidyl ester, phenol novolak polyglycidyl And aromatic epoxy compounds such as ether and cresol novolak polyglycidyl ether.

In the present invention, if the component (D) alone is intended to ensure sufficient dyeing properties, the water resistance and warm water resistance are remarkably reduced. Used to improve warm water. Thus, 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-hydroxy Aliphatic epoxy compounds such as triglycidyl ether of ethyl) isocyanurate are particularly preferred.

The amount of component (D) 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 possible to include the component (E) in order to adjust the refractive index of the coating or to further improve the durability of the coating.

Effective examples of the silica fine particles having a particle diameter of 1 to 100 millimicrons of the component (E) include silica sol and silica fine particles. The silica sol is obtained by dispersing a high molecular weight silicic acid colloidally in a dispersion medium such as water, an alcohol or other organic solvent. The powdery silica fine particles are powders obtained by hydrophobizing the surface of colloidal silica, and all of them are commercially available. For the purpose of this invention, those having an average particle size of 1 to 100 millimicrons are used, but preferably those having a diameter of 5 to 30 millimicrons. If the particle diameter is less than 1 millimicron, fine silica particles do not exist stably, and constant quality cannot be obtained. Also 100
If it is more than milliminclone, there arises a problem that the coating film becomes cloudy.

The tetrafunctional silane compound represented by the general formula Si (OR ⁵ ) 4 includes tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane,
Tetraisopropoxysilane, tetrabutoxysilane,
Examples thereof include tetraphenoxysilane, tetraacetoxysilane, tetraallyloxysilane, tetrakis (2-methoxyethoxy) silane, 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. As the solvent, solvents such as alcohols, esters, ketones, ethers, and aromatics are used.

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,
Addition of a fluorescent dye / pigment, a photochromic compound, a light- and heat-resistant stabilizer such as a hindered amine / hindered phenol compound, and the like can also improve the coating properties of the coating solution and the film performance after curing.

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

As a coating and curing method, a coating film is formed by applying a coating solution by dipping, spinner, spraying or flow, 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. It is also useful to add a curing catalyst for silanol or an epoxy compound.

Preferred curing catalysts include perchloric acids such as perchloric acid, ammonium perchlorate and magnesium perchlorate, Cu (II), Zn (II), Co (II) and Ni (I
I), Be (II), Ce (III), Ta (III), Ti
(III), Mn (III), La (III), Cr (III)
), V (III), Co (III), Fe (III), Al
(III), amino acids such as acetylacetonate, amine, glycine and the like having a central metal atom of Ce (IV), Zr (IV), V (IV), etc .; Lewis acids; organic acid metal salts, and the like. Among these, the most preferred curing catalyst includes acetylacetonate of magnesium perchlorate, Al (III) and Fe (III). The addition amount is desirably within the range of 0.01 to 5.0% of the solid concentration.

The thickness of the cured film is 0.05
It is preferably about 30 μm. That is, 0.05μ
If it is less than 30, the basic performance is not obtained.
It is not preferable because surface smoothness is impaired and optical distortion occurs. The application method includes a dipping method and a spray method.
Method, roll coat method, spin coat method, flow coat method and the like.

In the present invention, the pH of the coating solution
Is an important factor in abrasion resistance, pot life of a coating solution, and the like. That is, when the pH is less than 4.5, the pot life of the coating liquid is shortened, and the productivity is reduced. On the other hand, if it exceeds 7.5, the abrasion resistance decreases.
In the present invention, the pH of the coating liquid is a measured value after diluting the coating liquid ten times with pure water.

As a method for forming an anti-reflection film made of an inorganic substance on the surface of the coat 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.

Specific examples of the inorganic substance used include Si
O2, SiO, ZrO2, TiO2, TiO, Ti2
O3, Ti2O5, Al2O3, Ta2O5, CeO2
, MgO, Y2O3, SnO2, MgF2, WO3
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. Hereinafter, the present invention will be described in more detail with reference to examples.

[0050]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

Example-1 (1) Preparation of coating liquid 1173 g of methanol and 502.7 of 1,4-dioxane
g, methanol-dispersed tin oxide-titanium oxide-zirconium oxide composite fine particle sol (weight% ratio: 76.5 / 20.5 /
3. Solid content concentration 20% by weight, HI manufactured by Nissan Chemical Industries, Ltd.
T series) 1853.4 g, methanol-dispersed colloidal silica (trade name “Oscar 1”, manufactured by Catalyst Chemical Industry Co., Ltd.)
132 ", solids concentration 30% by weight) and γ-glycidoxypropyltrimethoxysilane 39.
9 g and disilane (DS-1) 264.
8 g were mixed. To this mixture, add 0.05N aqueous hydrochloric acid solution 1
83 g was added dropwise with stirring, and after further stirring for 4 hours, the mixture was aged for 24 hours. 25 g of a 1% by weight aqueous sodium hydroxide solution and 1,6-hexanediol diglycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd., trade name "Denacol E")
X-212 ") after adding 388.7 g, magnesium perchlorate 10.5 g, a silicon-based surfactant (trade name" L-7001 ", manufactured by Nippon Unicar Co., Ltd.) 1.5 g and a hindered amine-based light stabilizer 5.3 g (manufactured by Sankyo Co., Ltd., trade name [Sanol LS-770]) was added, and the mixture was stirred for 4 hours and aged all day and night to obtain a coating solution. When the pH of this coating solution was measured, it was 4.82.

* Structural formula of DS-1

[0053]

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(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 High Road SMX). Lifting speed is 23cm / mi
n. After air-drying at 80 ° C for 20 minutes after application, 110 ° C
For 180 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 antireflection thin film After the lens obtained by the above method is subjected to plasma treatment (argon plasma 400 W × 60 seconds), SiO2, ZrO2, SiO2 are sequentially transferred from the substrate to the atmosphere.
, ZrO2, SiO2, an antireflection multilayer film composed of five layers was vacuum-deposited (manufactured by Vacuum Instruments Co., Ltd .; BMC-10).
00). The optical film thickness of each layer was formed such that the first SiO2 layer, the next ZrO2 and SiO2 equivalent film layer, the next ZrO2 layer, and the uppermost SiO2 layer were each λ / 4. The design wavelength λ is 52
It was set to 0 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 lens obtained in Example 1 (hereinafter referred to as a hard-coated lens) and the lens obtained in Example 2 (hereinafter referred to as a hard multi-coated lens) are respectively shown below. The test was performed in the manner described, 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: The area of 1 cm * 3 cm is not damaged at all. B: 1 to 10 scratches are made in the above range. C: 10 to 100 scratches are made in the above range. D: Countless scratches are present, but 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 and detergent resistance: 12% in 0.1N hydrochloric acid and 1% mama lemon (manufactured by Lion Oil & Fat Co., Ltd.) aqueous solution
It was immersed for a period of time, and those having no change in the surface state 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 is 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) Heat resistance (cooling cycle property): 70 ° C.
After storing in warm air for 1 hour, the surface condition was examined. Further-
A cycle at 5 ° C. for 15 minutes and at 60 ° C. for 15 minutes was repeated five times, and those having no change in the surface state were evaluated as good.

(H) Durability: It is considered that durability is essentially an adhesive connection, and the cross-cut tape test described above was carried out on those subjected to the tests (b) to (e) to obtain a coated film. Those without peeling were regarded as good.

(I) Dyeing ability (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. This dyeing solution was immersed in the dyeing solution for 5 minutes for dyeing, and a dye having no unevenness in dyeing and having a total light transmittance of 30% or more between before and after dyeing was evaluated as good.

Example-3 (1) Preparation of Coating Solution 475.5 g of butyl cellosolve and sol of fine particles of tin oxide-titanium oxide-zirconium oxide dispersed in methyl cellosolve (weight ratio: 76.5 / 20.5 / 3, solid content Concentration 20% by weight, HIT series manufactured by Nissan Chemical Industries, Ltd.) 3
After mixing 26.7 g, 78.7 g of γ-glycidoxypropyltrimethoxysilane was mixed. 28 g of a 0.05N 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. To this solution was added 2.5 g of aluminum acetylacetonate and a silicon-based surfactant (trade name "FZ-211" manufactured by Nippon Unicar Co., Ltd.).
0 ") was added, and the mixture was stirred for 4 hours and aged all day and night to obtain a coating solution. When the pH of this coating solution was measured, it was 5.26.
Met.

* Structural formula of DS-2

[0070]

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(2) Coating and Curing The coating liquid thus obtained was applied to a 1.66 spectacle lens (lens fabric for Seiko Super Sovereign manufactured by Seiko Epson Corporation) by a spinner method. Was. The coating conditions are as follows.

Rotation speed: 500 rpm for 10 seconds (coating liquid is applied during this period) Rotation speed: 2,000 rpm for 1 second Rotation speed: 500 rpm for 5 seconds After coating, air-dry at 80 ° C. for 20 minutes, then at 130 ° C. for 120 minutes
Baking was performed for minutes. The thickness of the cured film thus obtained was about 2.3 microns, and the appearance was excellent.

(3) Formation of Antireflection Thin Film After the lens obtained by the above method is subjected to plasma treatment (argon plasma 400 W × 60 seconds), ZrO 2, SiO 2, and ZrO 2 are sequentially transferred from the substrate to the atmosphere.
And an antireflection multilayer film composed of four layers of SiO2 were formed by a vacuum evaporation method (BMC-1000, manufactured by Vacuum Instruments Co., Ltd.). The optical thickness of each layer is the first ZrO2
, An equivalent film layer of SiO 2, the next ZrO 2 layer, and the uppermost SiO 2 layer were formed to have 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 98%.

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

Example-4 (1) Preparation of Coating Solution 408 g of isopropyl cellosolve, 102.2 g of pure water and a sol of methanol-dispersed tin oxide-titanium oxide-zirconium oxide composite fine particles (weight% ratio: 70/26/4, solid content After mixing 202.6 g of a 30% by weight concentration (HIT series manufactured by Nissan Chemical Industries, Ltd.), 45.7 g of γ-methacryloxypropyltrimethoxysilane, g of γ-glycidoxypropyltrimethoxysilane g and tetramethoxysilane 43 were mixed. .5 g and the aforementioned DS-186.6 g
Was mixed. 64 g of a 0.05N hydrochloric acid aqueous solution was added to this mixture.
Was added dropwise with stirring. After further stirring for 5 hours, the mixture was aged all day long. 18.8 g of trimethylolpropane diglycidyl ether (trade name "Denacol EX-321", manufactured by Nagase Kasei Kogyo Co., Ltd.), 1.2 g of Fe (III) acetylacetonate, and a silicon surfactant (Nihon Unicar) (Trade name "L-7604")
0.3 g was added, and the mixture was stirred for 4 hours and then aged for 24 hours to obtain a coating solution. When the pH of this coating solution was measured, it was 5.43.

(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,
The firing was performed at 0 ° C. for 2 hours. The thickness of the cured film thus obtained was about 2.1 microns, and both the appearance and the dyeability were excellent.

(3) Formation of Antireflection Thin Film The lens obtained by the above method was converted from the ZrO2 of Example-4 to a mixture of ZrO2 and Ti oxide (ZrO2 / Ti oxide = 65/35 (weight ratio)). Except for the change, an antireflection film was formed in the same manner. 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-5 (1) Preparation of Coating Solution 654 g of methyl cellosolve, sol of methanol-dispersed tin oxide-titanium oxide-zirconium oxide composite fine particles (% by weight)
Ratio: 80/15/5, solid content concentration 30% by weight, HIT series manufactured by Nissan Chemical Industry Co., Ltd.), 185.3 g, and then 21.2 g of γ-glycidoxypropylmethyldimethoxysilane and γ-glycide 50.5 g of xypropyltrimethoxysilane and the aforementioned DS-233.5 g 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. To this solution, a 1% by weight aqueous solution of sodium hydroxide 6.2 was added.
g, glycerol diglycidyl ether (trade name “Denacol EX-313”, manufactured by Nagase Kasei Kogyo Co., Ltd.) 2
After adding 6.2 g, stannous chloride 2.0 g, silicon-based surfactant (manufactured by Big Chemie Co., Ltd .; trade name "BYK-
300 "), and the mixture was stirred for 4 hours and aged all day and night to obtain a coating solution. The pH of this coating solution was measured.
96.

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

The spraying was performed using Iwata Weider 61 (manufactured by Iwata Coating Machine Co., Ltd .; nozzle diameter 1 mm) 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
Calcination was performed at 2 ° C. for 2 hours. The thickness of the cured film thus obtained was about 4 microns, and both the appearance and the dyeability were excellent.

(4) 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 -6 (1) Formation of antireflection thin film After subjecting the lens obtained in Example -5 to an ion beam irradiation treatment with an oxygen gas (acceleration voltage: 500 V × 60 seconds), the lens was exposed to the atmosphere. In order, SiO2, ZrO2
, SiO2, TiO2, and SiO2 antireflection multilayer film composed of five layers is vacuum-deposited (manufactured by Vacuum Instruments Co., Ltd .; B
MC-1000). At this time, a fourth layer of TiO2 was formed by ion beam assisted vapor deposition. The optical film thickness of each vapor deposition layer is λ / 4 for the first SiO 2, the next equivalent film layer of ZrO 2 and SiO 2, and TiO 2
The layer was formed so that the layer was λ / 2 and the uppermost SiO 2 layer was 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 99%.

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

Comparative Example-1 In Example-4, except that the methanol-dispersed tin oxide-tungsten oxide-zirconium oxide composite fine particle sol was used instead of the methanol-dispersed tin oxide-titanium oxide-zirconium oxide composite fine particle sol, the same method was used. Coating was performed on the lens.

The lens obtained in this manner was used in Example-
The test was carried out in the same manner as in Example 2, and the results are shown in Table 1.

Comparative Example-2 In Example-4, except that the sol of methyl cellosolve dispersed cerium oxide-titanium oxide-silicon oxide composite fine particles was used in place of the methanol-dispersed tin oxide-titanium oxide-zirconium oxide composite fine particles sol. The lens obtained by coating the lens in the same manner was tested in the same manner as in Example 2, and the results are shown in Table 1.

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[Table 1]

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As described in detail above, the present invention makes it possible to improve various durability (particularly, weather resistance) in a coat film having a refractive index of 1.52 or more. In addition, adhesion (durability) with an antireflection film made of an inorganic substance could be obtained at the same time. That is, plastic lens materials include (meth) acrylic resins, styrene resins, carbonate resins, allyl resins, allyl carbonate resins, vinyl resins, polyester resins, polyether resins, urethane resins, and polymers of new monomers and comonomers. It can be applied to functional resins.

A plastic material having both excellent weather resistance and good adhesion (durability) to an anti-reflection film made of an inorganic substance is used as a spectacle lens, a camera lens, a light beam focusing lens or a light diffusing lens for consumer use. Alternatively, it can be widely applied to industrial use. Further, the effects of the present invention can be applied to transparent glasses such as watch glasses and cover glasses for displays and transparent plastics for optical use such as cover glasses, and the effects obtained are enormous.

Claims (7)

[Claims] (1) At least the following components (A) and (B)
A coating composition comprising, as a main component: (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, and R ² has 1 to 6 carbon atoms.
Is a hydrocarbon group. X ¹ is a hydrolyzable group, and n
Is 0 or 1. ) 2. The coating according to claim 1, wherein the weight percentage of the composite oxide fine particles (A) is 60 to 85 tin oxide, 10 to 30 titanium oxide, and 1 to 10 zirconium oxide. Composition. 3. The coating composition according to claim 1, comprising the following component (C). (C) General formula Wherein R ³ and R ⁴ are a hydrocarbon group having 1 to 6 carbon atoms; X ² and X ³ are hydrolyzable groups; and Y is a carbonate group or an epoxy group. And m is 0 or 1.) 4. The coating composition according to claim 1, which comprises the following component (D). (D). Multifunctional epoxy compound 5. The coating composition according to claim 1, which comprises the following component (E). (E) Silica fine particles having a particle diameter of 1 to 100 mm and / or a hydrolyzate and / or partial condensate of an organosilicon compound represented by the general formula: Si (OR ⁵ ) 4. (Where R ⁵ represents an alkyl group having 1 to 8 carbon atoms) 6. A method for producing a coating composition according to any one of claims 1 to 5, wherein the pH of the composition for coating is 4.5 to 7.5. 7. A laminate comprising an antireflection film made of an inorganic substance provided on the surface of a coated film produced using the coating composition according to any one of claims 1 to 5.