JP2006057106A - Coating composition, method for producing the same and laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating composition satisfying both of sufficient weather resistance of the coated film itself and durability when formed with an inorganic antireflection film on the surface of the coated film. <P>SOLUTION: The coating composition is composed mainly of specific composite oxide particles, a silane compound, a disilane compound and an epoxy compound. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention has a refractive index comparable to that of the base material on the surface of a synthetic resin lens having a refractive index of 1.52 or more, such as wear resistance, chemical resistance, warm water resistance, heat resistance, weather resistance, etc. For coatings characterized by providing a transparent coating with excellent durability and dyeability, and further providing an antireflection coating (hereinafter referred to as an inorganic vapor deposition coating) made of an inorganic substance on the coating. It relates to a composition.

  Synthetic resin lenses, especially diethylene glycol bisallyl carbonate resin (CR-39) lenses, are superior to glass lenses in terms of safety, ease of processing, fashionability, etc. More recently, antireflection technology and hard coat technology With the development of hard coat + anti-reflection technology, it has spread rapidly. However, since the refractive index of CR-39 resin is 1.50, which is lower than that of a glass lens, the near vision lens has a drawback that the outer peripheral portion is thicker than that of the glass lens. For this reason, in the field of synthetic resin spectacle lenses, technological development for reducing the thickness by using a high refractive index resin material has been actively carried out. As a technical proposal for that purpose, Patent Documents 1 to 3 and the like propose a high refractive index resin material having a refractive index of 1.60 or higher.

  On the other hand, since plastic eyeglass lenses have the drawback of being easily damaged, a method of providing a silicon hard coat film on the surface of the plastic lens is generally performed. 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 are generated due to a difference in refractive index between the resin lens and the coating film, resulting in poor appearance. As technical proposals for solving this problem, as disclosed in Patent Documents 4 and 5, colloidal dispersions of silicon dioxide fine particles used in silicon-based coating compositions are made of Al, Ti, Zr, Sn having a high refractive index. And a coating technique of replacing with a colloidal dispersion of Sb oxide fine particles. Patent Document 6 discloses a method for producing a composite sol of titanium dioxide and cerium dioxide, Patent Document 7 discloses composite oxide fine particles of Ti and Ce, and Patent Document 8 discloses composite oxidation of Ti, Ce and Si. A technique using fine particles obtained by treating a product with an organosilicon compound in a coating composition is disclosed.

JP 59-133211 JP-A-63-46213 Japanese Patent Laid-Open No. 2-270859 Japanese Patent Publication No. 61-54331 Japanese Patent Publication No. 63-37142 JP-A-1-301517 JP-A-2-264902 Japanese Patent Laid-Open No. 3-68901

  The above-described high refractive index coating composition ensures a level of durability that is practically acceptable. However, in order to further extend the life of products to which these coating compositions are applied, it has been a reality to improve the weather resistance.

  As a result of intensive studies to solve these problems, the present inventors have constituted tin oxide, titanium oxide and zirconium oxide in a specific weight percentage ratio among various complex oxides. It has been found that the coating composition obtained by containing the composite oxide fine particles is excellent in transparency, curability and adhesion (durability) to the inorganic vapor-deposited film, and particularly excellent in weather resistance. .

  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

で表される有機ケイ素化合物 （式中、Ｒ¹は重合可能な反応基を有する有機基であり、Ｒ²は炭素数１〜６の炭化水素基である。Ｘ¹は加水分解性基であり、ｎは０または１である。）
また、前記（Ａ）の複合酸化物微粒子の重量％比が、酸化錫６０〜８５、酸化チタン１０〜３０、酸化ジルコニウム１〜１０であることを特徴とする。
また、本発明のコーティング用組成物は下記（Ｃ）、（Ｄ）、（Ｅ）成分のうち少なくとも１成分を含有させても有用である。 (B). General formula

(In the formula, 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.)
Further, the weight percentage ratio of the composite oxide fine particles (A) is tin oxide 60 to 85, titanium oxide 10 to 30, and zirconium oxide 1 to 10.
Further, the coating composition of the present invention is useful even if it contains at least one component among the following components (C), (D), and (E).

で表される有機ケイ素化合物（式中、Ｒ³、Ｒ⁴は炭素数１〜６の炭化水素基である。Ｘ²、Ｘ³は加水分解性基である。Ｙは、カーボネート基またはエポキシ基を含有する有機基であり、ｍは０または１である。） (C) General formula

(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 epoxy group.) And m is 0 or 1.)

(D). Multifunctional epoxy compound

(E) Silica fine particles having a particle diameter of 1 to 100 mm and / or the general formula is Si (OR ⁵ ) ₄
A hydrolyzate and / or partial condensate of an organosilicon compound represented by the formula: (Where R ⁵ represents an alkyl group having 1 to 8 carbon atoms)

  Moreover, the manufacturing method of the coating composition of this invention is characterized by making pH of a coating liquid 4.5-7.5 before thermosetting the coating composition.

  Furthermore, 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 the tin oxide, titanium oxide and zirconium oxide of the component (A) used in the present invention are colloidally dispersed in a dispersion medium such as water, alcohol or other organic solvent. . In order to enhance the dispersion stability in these coating liquids, it is also possible to use those obtained by treating the surface of these fine particles with an organosilicon compound, an amine compound and / or a carboxylic acid. Examples of the organosilicon compound used in this case include monofunctional silane, bifunctional silane, trifunctional silane, and tetrafunctional silane. In the treatment, the hydrolyzable group may be untreated or hydrolyzed. In addition, after the treatment, it is preferable that the hydrolyzable group reacts with the —OH group of the fine particles, but there is no problem in stability even if a part of the hydrolyzable group remains. Amine compounds include ammonium or alkylamines such as ethylamine, triethylamine, isopropylamine and n-propylamine, aralkylamines such as benzylamine, alicyclic amines such as piperidine, alkanolamines such as monoethanolamine and triethanolamine. There is. It is necessary to add these organosilicon compounds, amine compounds, and carboxylic acids within a range of about 1 to 15% with respect to the weight of the fine particles. In any case, the particle size is preferably about 1 to 300 mμ, and the type and amount used for the coating composition of the present invention are determined by the target film performance. 50% by weight is desirable. That is, if it is less than 10% by weight, the adhesion to the inorganic vapor-deposited film is insufficient, or the scratch resistance of the coating film is insufficient. On the other hand, if it exceeds 50% by weight, cracks occur in the coating film. In addition, the dyeability is insufficient.

Subsequently, in component (B), R ¹ is an organic group having a polymerizable reactive group, and is a vinyl group, allyl group, acrylic group, methacryl group, epoxy group, mercapto group, cyano group, isocyano group, amino group. A silane compound having a polymerizable reactive group such as 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, a vinyl group, and a phenyl group. Groups and the like. X ¹ is a hydrolyzable functional group, and 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.

  Specific examples of this silane compound include vinyltrialkoxysilane, vinyltrichlorosilane, vinyltri (β-methoxy-ethoxy) silane, allyltrialkoxysilane, acryloxypropyltrialkoxysilane, methacryloxypropyltrialkoxysilane, methacryloxypropyldisilane. Alkoxymethylsilane, γ-glycidoxypropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrialkoxysilane, mercaptopropyltrialkoxysilane, γ-aminopropyltrialkoxysilane, N-β (aminoethyl) ) -Γ-aminopropylmethyl dialkoxysilane.

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

  The amount of component (B) used is preferably 20 to 60% by weight of the total composition. 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, it causes a crack in the cured film, which is not preferable.

Next, in the general formula of the component (C), R ³ and R ⁴ are hydrocarbon groups having 1 to 6 carbon atoms. Specific examples thereof include methyl group, ethyl group, butyl group, vinyl group, phenyl group. Groups and the like. X ² and X ³ are hydrolyzable functional groups. Specific examples include alkoxy groups such as methoxy, ethoxy and methoxyethoxy, halogen groups such as chloro and bromo, acyloxy and the like. Is mentioned. Y is an organic group containing a carbonate group or an epoxy group. As a specific example,

Etc.

  These disilane compounds can be synthesized by various conventionally known methods.

For example, it can be obtained by subjecting diallyl carbonate and trichlorosilane to an addition reaction followed by alkoxylation. Alternatively, a compound having a substituent that can be added at both ends and further containing an epoxy group or a functional group that can be epoxidized therein is subjected to addition reaction of trichlorosilane or the like and then alkoxylated.
The component (C) is more effective if it is used after hydrolysis, or the film after curing is subjected to an acid treatment.

  The amount used is preferably 3 to 40% by weight of the solid content. That is, if it is less than 3% by weight, both the dyeability and various durability of the inorganic vapor deposition film cannot be satisfied at the same time. On the other hand, if it exceeds 40% by weight, the water resistance of the coating film becomes poor. In addition, the pot life of the coating liquid is shortened.

  Subsequently, the polyfunctional epoxy compound of component (D) is widely used for paints, adhesives, casting, and the like. For example, a polyolefin-based epoxy resin synthesized by a peroxide method, cyclopentadiene oxide, Cyclohexene oxide or cycloaliphatic epoxy resins such as polyglycidyl esters obtained from hexahydrophthalic acid and epichlorohydrin, polyhydric phenols such as bisphenol A, catechol, and resorcinol, or (poly) ethylene glycol, (poly) propylene glycol, neopentyl glycol , Glycerin, trimethylolpropane, pentaerythritol, diglycerol, polyglycidyl ether obtained from epichlorohydrin such as glycerol, epoxidized vegetable oil, novolac phenol Epoxy novolaks obtained from fat and epichlorohydrin, epoxy resins obtained from phenolphthalein and epichlorohydrin, copolymers of glycidyl methacrylate and methyl methacrylate acrylic monomers or styrene, and the above epoxy compounds and monocarboxylic acid-containing (meth) acrylic Examples thereof include epoxy acrylate obtained by a glycidyl group ring-opening reaction with an acid.

  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, and nonaethylene glycol diester. Glycidyl 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, neopentyl glycol hydroxyhyvalic acid Diglycidyl ether of ester, trimethylolpropa 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, triglycidyl ether of tris (2-hydroxyethyl) isocyanurate, triglycidyl ether of tris (2-hydroxyethyl) isocyanurate, etc. Group epoxy compounds, isophoronediol diglycy Ether, alicyclic epoxy compounds such as bis-2,2-hydroxycyclohexylpropane diglycidyl ether, resorcin diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, orthophthalic acid diglycidyl ester And aromatic epoxy compounds such as phenol novolac polyglycidyl ether and cresol novolac polyglycidyl ether.

In the present invention, when the component (D) is intended to ensure sufficient dyeability only with the component (C), the water resistance / warm water resistance is remarkably lowered. Use as an improvement. 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-hydroxy) Aliphatic epoxy compounds such as triglycidyl ether of ethyl) isocyanurate are particularly preferred.
(D) The usage-amount of a component needs to be 5 to 40 weight% of a whole composition. 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 with the inorganic deposited film tends to be insufficient, which is not preferable.

  It is also possible to contain a component (E) in order to further adjust the refractive index of the coating or 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. Silica sol is a colloidal dispersion of high molecular weight silicic acid in a dispersion medium such as water, alcohol or other organic solvent. The powdery silica fine particles are powders obtained by hydrophobizing the surface of colloidal silica, and are all commercially available. For the purposes of this invention, those having an average particle size of 1 to 100 millimicrons are used, preferably those having a diameter of 5 to 30 millimicrons. If the particle size is 1 millimicron or less, the particulate silica does not exist stably, and a constant quality cannot be obtained. Moreover, the problem that a coating film becomes cloudy arises that it is 100 millimincron or more.

The tetrafunctional silane compound represented by the general formula Si (OR ⁵ ) ₄ is tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetraacetoxysilane. Tetraallyloxysilane, tetrakis (2-methoxyethoxy) silane, tetrakis (2-ethylbutoxy) silane, tetrakis (2-ethylhexyloxy) silane, and the like. These may be used alone or in combination of two or more. These are preferably used after being hydrolyzed in the presence of an acid in the absence of a solvent or in an organic solvent such as alcohol.

  The coating composition thus obtained can be diluted with a solvent and used as necessary. As the solvent, solvents such as alcohols, esters, ketones, ethers and aromatics are used.

  In addition to the above components, 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 / oil-soluble dye / fluorescent dye / pigment, photochromic. A compound, a light and heat resistant stabilizer such as a hindered amine / hindered phenol, and the like can be added to improve the coating property of the coating liquid 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 alkali, acid, surfactant, and polishing with inorganic or organic fine particles for the purpose of improving the adhesion between the substrate lens and the coating. It is effective to perform treatment, primer treatment or plasma treatment.

  In addition, as a coating / curing method, a coating film can be formed by applying a coating solution by dipping, spinner, spraying, or flow method, followed by heating and drying at a temperature of 40 to 200 ° C. for several hours. . In particular, a spinner method that does not require the lens substrate to be fixed with a jig is suitable for a substrate having a heat distortion temperature of less than 100 ° C.

  It is also useful to add a silanol or an epoxy compound curing catalyst.

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

  Moreover, as a film thickness of a cured film, it is preferable that it is 0.05-30 micrometers. That is, if it is less than 0.05 μm, the basic performance does not appear, and if it exceeds 30 μm, the smoothness of the surface is impaired or optical distortion occurs, which is not preferable.

  Examples of the coating method include an immersion method, a spray method, a roll coat method, a spin coat method, a flow coat method and the like.

  In the present invention, the pH of the coating liquid is an important factor in the scratch resistance, the pot life of the coating liquid, and the like. That is, when the pH is less than 4.5, the pot life of the coating solution is shortened and the productivity is lowered. On the other hand, if it exceeds 7.5, the scratch resistance is lowered. In the present invention, the pH of the coating solution is a measured value after the coating solution is diluted 10 times with pure water.

  Examples of a coating method for forming an antireflection film made of an inorganic substance on the surface of the coating film thus obtained include a vacuum deposition method, an ion plating method, and a sputtering method. In the vacuum vapor deposition method, an ion beam assist method in which an ion beam is simultaneously irradiated during vapor deposition may be used. As the film configuration, either a single-layer antireflection film or a multilayer antireflection film may be used.

Specific examples of the inorganic material 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 , CeO ₂ , MgO, and Y _2. Examples thereof include O ₃ , SnO ₂ , MgF ₂ , and WO ₃ . These inorganic substances are used alone or in a mixture of two or more.

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

  According to the present invention, various durability (particularly weather resistance) can be improved in a coat film having a refractive index of 1.52 or more. Moreover, adhesiveness (durability) with the antireflection film made of an inorganic material could be obtained at the same time. In other words, plastic lens materials such as (meth) acrylic resin, styrene resin, carbonate resin, allyl resin, allyl carbonate resin, vinyl resin, polyester resin, polyether resin, urethane resin, and other monomers and comonomer polymers It can be applied to functional resin.

  Plastic materials that combine excellent weather resistance and adhesion (durability) with a good antireflective coating made of inorganic materials are used for consumer or industrial use as spectacle lenses, camera lenses, light beam condensing lenses, and light diffusion lenses. It can be widely applied to. Furthermore, the effects of the present invention can be applied and applied to all transparent plastics for optical applications such as transparent glass such as watch glass and cover glass for displays, and cover glass, and the obtained effect is great.

  The present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

(1) Preparation of coating solution 1173 g of methanol, 502.7 g of 1,4-dioxane, 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, 1853.4 g of Nissan Chemical Industries, Ltd. HIT series), and 225 g of methanol-dispersed colloidal silica (manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name “Oscar 1132”, solid content concentration 30% by weight) were mixed. Thereafter, 399 g of γ-glycidoxypropyltrimethoxysilane and 264.8 g of disilane (DS-1) having the following structural formula were mixed. To this mixed solution, 183 g of 0.05N hydrochloric acid aqueous solution was added dropwise with stirring, and the mixture was further stirred for 4 hours and then aged overnight. To this solution was added 25 g of a 1% by weight aqueous sodium hydroxide solution and 388.7 g of 1,6-hexanediol diglycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd., trade name “Denacol EX-212”), and then magnesium perchlorate. 10.5 g, 1.5 g of silicon surfactant (manufactured by Nihon Unicar Co., Ltd., trade name “L-7001”) and hindered amine light stabilizer (manufactured by Sankyo Co., Ltd., trade name “Sanol LS-770”) 5.3 g was added, stirred for 4 hours, and then aged overnight to prepare a coating solution. The pH of this coating solution was measured and found to be 4.82.
* DS-1 structural formula

(2) Application and curing The coating solution thus obtained is immersed in an alkali-treated refractive index 1.60 spectacle lens (Seiko Epson Co., Ltd. Seiko High Road SMX lens fabric). Application was performed. The pulling rate was 23 cm / min. After the coating, it was air-dried at 80 ° C. for 20 minutes and then baked at 110 ° C. for 180 minutes. The thickness of the cured film thus obtained was about 2 microns, and both the appearance and dyeability were excellent.

An antireflection coating thin film made of an inorganic substance was formed on the lens obtained in Example-1 by the following method.
(1) Formation of antireflection thin film The lens obtained by the above method is subjected to plasma treatment (argon plasma 400 W × 60 seconds), and then sequentially from the substrate to the atmosphere, SiO ₂ , ZrO ₂ , SiO ₂ , ZrO _{2. An} antireflection multilayer film composed of 5 layers of SiO ₂ was formed by a vacuum deposition method (manufactured by Vacuum Instrument Industry Co., Ltd .; BMC-1000). The optical film thickness of each layer was formed such that the first SiO ₂ layer, the next ZrO ₂ and SiO ₂ equivalent film layer, the next ZrO ₂ layer, and the uppermost SiO ₂ layer were 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 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 described by the following methods. Tests were conducted and the results are shown in Table 1.

(A) Abrasion resistance: A load of 1 kg was applied with Bonstar # 0000 steel wool (manufactured by Nippon Steel Wool Co., Ltd.), and the surface was rubbed for 10 reciprocations. .
A: No scratches in the range of 1 cm * 3 cm B: 1-10 scratches in the above range C: 10-100 scratches in the above range D: Innumerable scratches 、 Smooth surface remains E ： Smooth surface does not remain due to scratches on the surface

(B) Water resistance / chemical resistance: Dipped for 48 hours in water, alcohol, or kerosene, and the surface state was not changed.

(C) Acid resistance / detergent resistance: Immersion 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 considered good.

(D) Adhesiveness: Adhesiveness between the base material and the hard coat film and between the hard coat film and the multicoat film was determined by a cross-cut tape test in accordance with JISD-0202. That is, using a knife, cuts are made on the substrate surface at intervals of 1 mm to form 100 squares of 1 mm square. Next, after strongly pressing cellophane adhesive tape (product name “Cellotape” manufactured by Nichiban Co., Ltd.) onto it, it was pulled and peeled away 90 degrees from the surface, and then the adhesiveness was maintained with the grids remaining on the coating film. It was used as an index.

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

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

(G) Heat resistance (cooling cycle property): After storing for 1 hour in warm air at 70 ° C., the surface condition was examined. Further, a cycle of 15 minutes at −5 ° C. and 15 minutes at 60 ° C. was repeated 5 times, and those having no change in the surface state were evaluated as good.

(H) Durability: Durability is considered to be essentially an adhesive connection, and the above-mentioned cross-cut tape test was performed on the ones subjected to the tests (b) to (e), and the coating film was not peeled off. Things were good.

(I) Dyeability (hard coat lens only): 2 g of a dye D amber D for Seiko Plax diamond coat was dispersed in 1 liter of pure water at 92 ° C. to prepare a dye solution.
The dyeing solution was immersed in this dyeing solution for 5 minutes and dyeing was performed. The material having no dyeing unevenness and having a total light transmittance of 30% or more before and after dyeing was evaluated as good.

(1) Preparation of coating liquid 475.5 g of butyl cellosolve and methyl cellosolve dispersed tin oxide-titanium oxide-zirconium oxide composite fine particle sol (weight ratio: 76.5 / 20.5 / 3, solid content concentration 20% by weight, Nissan Chemical Co., Ltd.) After mixing 326.7 g of HIT series manufactured by Kogyo Co., Ltd., 78.7 g of γ-glycidoxypropyltrimethoxysilane was mixed. To this mixed solution, 28 g of 0.05N hydrochloric acid aqueous solution was added dropwise with stirring, and the mixture was stirred for 4 hours and then aged overnight. To this solution was added 2.5 g of aluminum acetylacetonate and 0.3 g of a silicon surfactant (manufactured by Nippon Unicar Co., Ltd., trade name “FZ-2110”). The mixture was stirred for 4 hours and then aged overnight to prepare a coating solution. .
The pH of this coating solution was measured and found to be 5.26.
* DS-2 structural formula

(2) Application and curing The coating solution thus obtained was applied to a refractive index 1.66 spectacle lens (manufactured by Seiko Epson Corporation, lens fabric for Seiko Super Sovereign) by the spinner method.
The coating conditions are as follows.
10 seconds at 500 rpm (coating solution is applied during this time)
Rotational speed: 2000 rpm for 1 second Rotational speed: 500 rpm for 5 seconds After application, the coating was air-dried at 80 ° C. for 20 minutes and then fired at 130 ° C. for 120 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 The lens obtained by the above method is subjected to plasma treatment (argon plasma 400 W × 60 seconds), and then in order from the substrate to the atmosphere, ZrO ₂ , SiO ₂ , ZrO ₂ , SiO _{2 An} antireflection multilayer film composed of _two layers of ₂ was formed by a vacuum deposition method (manufactured by Vacuum Instrument Industry Co., Ltd .; BMC-1000). The optical film thickness of each layer was formed such that the first ZrO ₂ and SiO ₂ equivalent film layer, the next ZrO ₂ layer, and the uppermost SiO ₂ layer were 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%.

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

(1) Preparation of coating solution 408 g of isopropyl cellosolve, 102.2 g of pure water and methanol-dispersed tin oxide-titanium oxide-zirconium oxide composite fine particle sol (weight ratio: 70/26/4, solid content concentration 30% by weight, Nissan Chemical Co., Ltd.) HIT series manufactured by Kogyo Co., Ltd.) After mixing 202.6 g, 45.7 g of γ-methacryloxypropyltrimethoxysilane, 43.5 g of γ-glycidoxypropyltrimethoxysilane and 43.5 g of tetramethoxysilane and the above-mentioned DS- 186.6 g was mixed. To this mixed solution, 64 g of 0.05N aqueous hydrochloric acid was added dropwise with stirring. The mixture was further stirred for 5 hours and then aged overnight. To this solution, 18.8 g of trimethylolpropane diglycidyl ether (manufactured by Nagase Chemical Industries, Ltd., trade name “Denacol EX-321”) and 1.2 g of Fe (III) acetylacetonate, silicon surfactant (Nihon Unicar) Co., Ltd., trade name “L-7604”) 0.3 g was added, stirred for 4 hours, and then aged overnight to prepare a coating solution.
The pH of this coating solution was measured and found to be 5.43.

(2) Application and curing The coating solution thus obtained was applied to a polycarbonate injection-molded spectacle lens having a refractive index of 1.58 by the spinner method. The coating conditions were the same as in Example-3.
After the coating, it was air-dried at 80 ° C. for 15 minutes and then baked at 130 ° C. for 2 hours. The thickness of the cured film thus obtained was about 2.1 microns, and both the appearance and dyeability were excellent.

(3) Formation of antireflection thin film For the lens obtained by the above method, ZrO ₂ of Example 4 was changed to a mixture of ZrO ₂ and Ti oxide (ZrO ₂ / Ti oxide = 65/35 (weight ratio)). An antireflection film was formed in the same manner except that it was changed.
The reflection interference color of the obtained multilayer film was green, and the total light transmittance was 99%.

(4) Test and Evaluation Results The lens thus obtained was 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.

(1) Preparation of coating liquid Methyl cellosolve 654 g, methanol-dispersed tin oxide-titanium oxide-zirconium oxide composite fine particle sol (weight% ratio: 80/15/5, solid content concentration 30 wt%, manufactured by Nissan Chemical Industries, Ltd. HIT Series) After mixing 185.3 g, 21.2 g of γ-glycidoxypropylmethyldimethoxysilane, 50.5 g of γ-glycidoxypropyltrimethoxysilane, and the aforementioned DS-233.5 g were mixed. To this mixed liquid, 30 g of 0.05N hydrochloric acid aqueous solution was added dropwise with stirring, and the mixture was stirred for 4 hours and then aged overnight. After adding 6.2 g of 1 wt% aqueous sodium hydroxide and 26.2 g of glycerol diglycidyl ether (manufactured by Nagase Kasei Kogyo Co., Ltd., trade name “Denacol EX-313”) to this solution, 2.0 g of stannous chloride was added. Then, 0.2 g of a silicon-based surfactant (manufactured by Big Chemie Co., Ltd .; trade name “BYK-300”) was added, and the mixture was stirred for 4 hours and then aged overnight to prepare a coating solution.
The pH of this coating solution was measured and found to be 4.96.

(3) Application and curing The coating solution thus obtained was applied by a spray method with a refractive index of 1.56 spectacle lens (manufactured by Seiko Epson Corporation, lens fabric for Seiko Plax IIGX).
Spraying was performed using an Iwata Weider 61 (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 the coating, it was air-dried at 80 ° C. for 10 minutes and then baked at 130 ° C. for 2 hours. The thickness of the cured film thus obtained was about 4 microns, and the appearance and dyeability were excellent.

(4) Test and Evaluation Results The lens thus obtained was tested in the same manner as in Example 1, and the results are shown in Table 1.

(1) Formation of antireflection thin film The lens obtained in Example-5 was subjected to ion beam irradiation treatment with oxygen gas (acceleration voltage: 500 V × 60 seconds), and then in order from the substrate to the atmosphere, SiO ₂ , ZrO ₂ , an antireflection multilayer film composed of 5 layers of SiO ₂ , TiO ₂ , and SiO ₂ was formed by a vacuum deposition method (manufactured by Vacuum Instrument Industry Co., Ltd .; BMC-1000). At that time, a fourth layer of TiO ₂ was formed by ion beam assisted deposition. The optical thickness of each deposited layer is λ / 4 for the first SiO ₂ , the equivalent film layer for the next ZrO ₂ and SiO ₂ , λ / 2 for the TiO ₂ layer, and λ / 4 for the uppermost SiO ₂ layer. Formed. 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 lens thus obtained was tested in the same manner as in Example-2, and the results are shown in Table 1.

[Comparative Example 1]
In Example-4, the coating was applied to the lens in the same manner except that methanol-dispersed tin oxide-tungsten oxide composite fine particle sol was used instead of methanol-dispersed tin oxide-titanium oxide-zirconium oxide composite fine particle sol.
The lens thus obtained was tested in the same manner as in Example-2, and the results are shown in Table 1.

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

Claims (7)

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

(In the formula, 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.)   The coating composition according to claim 1, wherein the weight percentage ratio of the composite oxide fine particles (A) is tin oxide 60 to 85, titanium oxide 10 to 30, and zirconium oxide 1 to 10. The coating composition according to claim 1 or 2, comprising the following component (C).
(C) General formula

(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 epoxy group.) And m is 0 or 1.) The coating composition according to any one of claims 1 to 3, comprising the following component (D).
(D). Multifunctional epoxy compound The coating composition according to any one of claims 1 to 4, further comprising the following component (E):
(E) Silica fine particles having a particle diameter of 1 to 100 mm and / or the general formula is Si (OR ⁵ ) ₄
A hydrolyzate and / or partial condensate of an organosilicon compound represented by the formula: (Where R ⁵ represents an alkyl group having 1 to 8 carbon atoms)   A method for producing a coating composition, wherein the coating composition according to any one of claims 1 to 5 has a pH of 4.5 to 7.5.   A laminate comprising an antireflective film made of an inorganic substance on the surface of a coat film produced using the coating composition according to any one of claims 1 to 5.