JP4586391B2 - Coating composition and plastic lens - Google Patents

Description

  The present invention provides a transparent film having a refractive index comparable to that of a base material on the surface of a plastic lens and excellent in durability such as wear resistance, chemical resistance, hot water resistance, heat resistance, and weather resistance. . The present invention also relates to a coating composition characterized in that an antireflection film made of an inorganic substance can be provided on the film.

  Synthetic resin lenses, especially diethylene glycol bisallyl carbonate resin lenses (CR-39), are superior to glass lenses in terms of safety, ease of processing, fashionability, etc., and more recently, hard coat technology and antireflection technology. With the development of, has been rapidly spread.

  As a hard coat composition, a method of providing a silicon hard coat film on the surface of a plastic lens is generally performed. For example, Patent Document 1 and Patent Document 2 disclose hard coat compositions using acetylacetonate having an Al (III) central metal atom.

  Patent Document 3 discloses a hard coat composition to which an amine compound, a polyvalent carboxylic acid, a number of acetylacetone metal salt compounds, a phenol compound, a boron trifluoride-containing compound, and the like are added.

  Patent Document 4 discloses a hard coat composition using ammonium perchlorate, and Patent Document 5 discloses a hard coat composition using magnesium perchlorate.

  In addition, 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, which causes poor appearance. In order to solve this problem, a colloidal dispersion of silicon dioxide fine particles used in silicon-based coating compositions as in Patent Document 6 and Patent Document 7 is made of Al, Ti, Zr, Sn having a high refractive index. , Coating techniques such as replacement with a colloidal dispersion of Sb inorganic oxide fine particles are disclosed. Patent Document 8 discloses a method for producing a composite sol of titanium dioxide and cerium dioxide, Patent Document 9 discloses composite inorganic oxide fine particles of Ti and Ce, and Patent Document 10 discloses a composite of Ti, Ce, and Si. A technique using fine particles obtained by treating an inorganic oxide with an organosilicon compound for a coating composition is disclosed. Further, in Patent Document 11, composite oxide fine particles in which a coating layer is formed of a composite oxide of silicon oxide and zirconium and / or aluminum oxide with core particles of titanium and tin oxide are used as a coating composition. The technique used is disclosed.

Japanese Patent Publication No. 60-11727 Japanese Patent Publication No. 60-30350 Japanese Patent Publication No.61-33868 Japanese Patent Publication No.62-9266 Japanese Examined Patent Publication No. 4-59601 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 JP 2000-204301 A

  Compared with the coating film performance by the coating technology disclosed in Patent Documents 1 to 10, the coating film performance by the coating technology disclosed in Patent Document 11 is excellent in quality balance and has a remarkable weather resistance. To improve. However, there has been a drawback in that it develops color by receiving light such as sunlight and exhibits a blue color. In particular, when an antireflection film is disposed on the surface of the coating film, a color that has developed color remains, thereby impairing visibility and causing a problem that the color tone changes in a dyed lens.

  As a result of intensive studies to solve the above problems, the present inventors have found that the core particles are composed of oxides of titanium and tin, and are composed of a complex solid solution oxide having a rutile structure, and silicon oxide is used as a coating layer. Compound containing Fe atom and / or vanadium atom in coating composition mainly composed of composite oxide fine particles composed of oxide of zirconium and / or aluminum and silane compound having polymerizable reactive group It has been found that a stable hard coat film can be formed without doping with light such as sunlight, and has excellent coating film performance such as durability and scratch resistance by doping. It came to.

  That is, in the first invention, at least the following components (A) and (B) are the main components and the following component (C) is doped, and the (C) component is in a weight ratio with respect to the (A) component. (C) / (A) = 0.004 to 0.06 is provided.

(A) Composite oxide fine particles composed of a solid solution oxide in which the core particles are composed of an oxide of titanium and tin and have a rutile structure, and which is composed of a silicon oxide and an oxide of zirconium and / or aluminum as a coating layer.

(B) An organosilicon compound represented by the following 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, X is a hydrolyzable group, and n is 0 or 1.)

  (C) Fe (III) acetylacetonate and / or vanadium (IV) oxyacetylacetonate and / or vanadium (III) acetylacetonate.

  According to the first invention, it is possible to suppress the property of the hard coat film that develops color upon receiving light such as sunlight. In addition, stable dispersibility in the coating composition can be obtained, and stable characteristics in the coating composition can be obtained. In addition, it is easy to handle because of its high safety. Furthermore, the appearance quality can be maintained without causing blue discoloration, and various durability can be obtained.

  In the second invention, a hard coat film formed from the coating composition is provided on the surface of a plastic lens having a refractive index of 1.60 or more, and an antireflection film made of an inorganic substance is laminated on the hard coat film surface. A plastic lens is provided.

  According to the fourth invention, it is possible to obtain sufficient adhesion between the plastic lens as the base material and sufficient anti-reflection film made of an inorganic substance.

  The component (A) used in the present invention is composed of a composite solid solution oxide in which the core particles are composed of titanium and tin oxides and has a rutile structure, and a silicon oxide and zirconium and / or aluminum are oxidized as a coating layer. This is a composite oxide fine particle made of a material.

As a specific example, a composite oxide fine particle having a particle diameter of 1 to 100 millimicrons and in which an inorganic oxide of SnO ₂ and TiO ₂ is coated with an inorganic oxide of SiO ₂ and ZrO ₂ is used as a dispersion medium such as water. , Colloidally dispersed in an alcohol or other organic solvent.

  Further, in order to enhance the dispersion stability in the coating liquid, it is also possible to use those obtained by treating the surface of these fine particles with an organosilicon compound or an amine compound. 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 and amine compounds 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. 70% 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 70% by weight, cracks occur in the coating film.
Next, in component (B), R ¹ is an organic group having a polymerizable reactive group, such as vinyl group, allyl group, acrylic group, methacryl group, epoxy group, mercapto group, cyano group, isocyano group, amino group, etc. 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, a vinyl group, and a phenyl group. Etc.

  X 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, etc., which may be used alone or in admixture of two or more.

  The amount of component (B) used is desirably 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.

  Subsequently, the compound (C) containing a Fe atom and / or a compound containing a vanadium atom includes iron dioxide, iron trioxide, iron chloride, Fe (III) acetylacetonate, vanadium oxide, vanadium (IV) oxy. Known compounds such as acetylacetonate and vanadium (III) acetylacetonate can be used.

  Among these, Fe (III) acetylacetonate, vanadium (IV) oxyacetylacetonate, vanadium (in terms of stability in coating composition and hard coat film, effect on doping amount, handleability, etc. III) Acetylacetonate is preferred. The acetylacetonate compound part alone has the effect of stabilizing the component (A) against external light such as sunlight, and at the same time, promotes the curing of silanol groups and epoxy groups as a curing catalyst. In addition, a cured film having excellent transparency and durability can be formed. On the other hand, a form using the acetylacetonate compound as a light stabilizer and another compound as a curing catalyst is also possible.

Curing catalysts include amines such as n-butylamine, triethylamine and guanidine, amino acids such as glycine, metal acetylacetonates such as aluminum acetylacetonate and cobalt acetylacetonate, sodium acetate, zinc naphthenate, zinc octylate , Metal salts of organic acids such as tin octylate, perchloric acids such as perchloric acid, ammonium perchlorate, magnesium perchlorate and salts thereof, acids such as hydrochloric acid, phosphoric acid, nitric acid, SnCl ₂ , AlCl ₃ , Examples thereof include metal chlorides which are Lewis acids such as TiCl ₄ , ZnCl ₂ and SbCl ₃ , and may be used alone or in combination of two or more.

  In the present invention, it is also useful to add a polyfunctional epoxy compound. Polyfunctional epoxy compounds are widely used for paints, adhesives, casting, etc., for example, polyolefin epoxy resins synthesized by peroxidation methods, cyclopentadiene oxide, cyclohexene oxide or hexahydrophthalic acid. And alicyclic epoxy resin such as polyglycidyl ester obtained from epichlorohydrin, polyphenols such as bisphenol A, catechol, and resorcinol, or (poly) ethylene glycol, (poly) propylene glycol, neopentyl glycol, glycerin, trimethylolpropane, Polyglycidyl ether, epoxidized vegetable oil, novolak type phenolic resin and epichlorohid obtained from polyhydric alcohols such as pentaerythritol, diglycerol, sorbitol and epichlorohydrin Epoxy novolak obtained from phosphorus, epoxy resin obtained from phenolphthalein and epichlorohydrin, glycidyl methacrylate and methyl methacrylate acrylic monomer or copolymer such as styrene, and the above epoxy compound and monocarboxylic acid-containing (meth) acrylic acid And epoxy acrylate obtained by the ring opening reaction of glycidyl group.

  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.

  The polyfunctional epoxy compound is used to improve water resistance / warm water resistance simultaneously with the role of the dye 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-hydroxy) Aliphatic epoxy compounds such as triglycidyl ether of ethyl) isocyanurate are particularly preferred.

In addition, when the refractive index needs to be adjusted, the tetrafunctional silane compound represented by the general formula Si (OR) ₄ and / or the SiO ₂ fine particles are colloidally formed in water, alcohol-based or other organic solvents. It is also useful to add a dispersed one. Specific examples of tetrafunctional silane compounds include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetraacetoxysilane, tetraallyloxysilane, tetrakis (2-methoxyethoxy) Examples thereof include 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 is optionally provided with a surfactant, an antistatic agent, an ultraviolet absorber, an antioxidant, a disperse dye / oil-soluble dye / fluorescent dye / pigment, a photochromic compound, Light-resistant heat-resistant stabilizers such as hindered amines and hindered phenols can be added to improve the coating properties of the coating liquid and the coating 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.

  As a coating / curing method, a coating solution is applied by dipping method, spin method, spray method, roll coating method, flow coating method, etc., and then heated and dried at a temperature of 40 to 200 ° C. for several hours to form a coating film. Can be formed. In addition, 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 surface smoothness is impaired and optical distortion occurs, which is not preferable.

  An antireflection film made of an inorganic substance is formed on the surface of the coating film thus obtained. Examples of the film forming method 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, but a multilayer antireflection film is preferably used in order to suppress the reflectance as much as possible.

Specific examples of the inorganic substance to be _{used, 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, Y 2 O ₃ , SnO ₂ , MgF ₂ , WO _{3 and the} like can be mentioned. 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, the coating film obtained by applying and curing on the surface of a substrate has a refractive index comparable to that of a synthetic resin lens having a refractive index of 1.60 or more, and has a scratch resistance, a weather resistance, and a water resistance. It is excellent in durability such as heat resistance and heat resistance and transparency, and at the same time, adhesion to an antireflection film made of an inorganic material and various durability can be obtained at the same time. In particular, coloring against light such as outside light can be suppressed, and the stability can be dramatically improved.

[Example 1]
(1) Preparation of coating composition 1000.3 g of 2-n-butoxyethanol and 1553.7 g of γ-glycidoxypropyltrimethoxysilane were mixed. To this mixture, 427.0 g of a 0.1N hydrochloric acid aqueous solution was added dropwise with stirring, and the mixture was further stirred for 2 hours and then aged overnight. Next, 6981.6 g of methanol-dispersed titanium dioxide-tin dioxide-silicon dioxide-zirconium oxide composite oxide fine particle sol (manufactured by Catalyst Kasei Kogyo Co., Ltd., solid content concentration: 20 wt%) was mixed, and then Fe (III) acetylacetonate. 29.4 g and 3.0 g of a silicon-based surfactant (trade name “L-7604” manufactured by Nihon Unicar Co., Ltd.) were added, and the mixture was stirred for 4 hours and then aged overnight to obtain a coating composition.

(2) Application and curing Using the coating composition, a pulling speed by a dipping method on a plastic spectacle lens having a refractive index of 1.67 (Seiko Epson Co., Ltd., Seiko Super Sovereign lens fabric) that has been subjected to alkali treatment in advance. Application was at 250 mm / min. After the coating, it was air-dried at 70 ° C. for 40 minutes and then baked at 120 ° C. for 120 minutes. The cured coating thus obtained had a thickness of 1.9 microns.

(3) Formation of antireflection thin film The lens obtained by the above method was subjected to plasma treatment (argon plasma 400 W × 60 seconds), and then in order from the substrate toward the atmosphere, SiO ₂ , ZrO ₂ , SiO ₂ , ZrO ₂ A multilayer antireflection film composed of 5 layers of SiO ₂ was formed by a vacuum vapor deposition machine (manufactured by Shincron; CES-21). The optical film thickness of each layer is λ / 4 for 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 with a design wavelength λ of 520 nm. It was formed to become. The reflection interference color of the obtained multilayer film was green, and the total light transmittance was 98%.
The obtained lenses were evaluated according to the following test methods, and the results are shown in Table 1.

(4) Test and Evaluation Results The obtained lens was evaluated for coating film performance by the following test method, and the evaluation results are shown in Table 1.

(A) Scratch resistance: The surface of 10 reciprocating surfaces rubbed with a bonster # 0000 steel wool (manufactured by Nippon Steel Wool Co., Ltd.) under a load of 1 kg was visually observed to the extent that it was damaged within a range of 1 cm × 3 cm. The evaluation was divided into the following stages.
A: Not scratched at all.
B: 10 to 10 scratches.
C: 10 to 100 scratches are attached.
D: There are countless scratches, but a smooth surface remains.
E: A smooth surface does not remain because of scratches on the surface.

(B) Acid resistance / detergent resistance: The sample was immersed in an aqueous solution of 0.1N hydrochloric acid and 1% Mama lemon (manufactured by Lion Corporation) for 12 hours, and the surface state was not changed.

(C) Initial adhesion: Adhesion between the base material and the hard coat film and between the hard coat film and the multi-coat film is a cross-cut tape according to JIS K5400 8.5.1-2 cross cut method / cross cut tape method Performed by testing. That is, using a cutter knife, the substrate surface is cut at intervals of 1 mm to form 100 squares of 1 mm square. Next, after strongly pressing a cellophane adhesive tape (trade name “Cellotape” manufactured by Nichiban Co., Ltd.) onto it, it was pulled and peeled away from the surface in a direction of 90 degrees, and the remaining number of the coating film was as follows: Classified.
A: No film peeling (remaining cell number 100)
B: Almost no peeling (remaining grid number 99.9 to 95)
C: Some peeling (remaining cell number 94.9-80)
D: Peeled (remaining cell number: 79.9-30)
E: Peeling of almost entire surface (remaining cell number: 29.9 to 0)

(D) Weather resistance: After being exposed to a sunshine weather meter with carbon arc for 300 hours, the cross-cut tape test described in (c) was performed, and the number of remaining squares of the coat film was used as a durability index.

(E) Moisture resistance: after standing for 10 days in a constant temperature and humidity chamber maintained at a temperature of 60 ° C. and a relative humidity of 98%, the cross-cut tape test described in the above (c) is performed, and the remaining squares of the coating film Was used as a durability index.

(F) Hot water resistance: After being immersed in a warm bath maintained at a temperature of 80 ° C. for 1 hour, the cross-cut tape test described in the above (c) was performed, and the residual cell number of the coat film was used as a durability index.

(G) Color developability: In a thermostatic chamber maintained at a temperature of 25 ° C., it was allowed to stand under an artificial sun lamp for 20 hours and then classified as follows.
A: No change B: Some color development is observed, but there is no problem in use. C: Color development is observed and visibility is impaired [Example 2]

In Example 1, a hard coat film and an antireflection film were formed in the same manner as in Example 1 except that 7.4 g of vanadium (IV) oxyacetylacetonate was used instead of Fe (III) acetylacetonate. The reflection interference color of the obtained multilayer film was green, and the total light transmittance was 98%. Table 1 shows the evaluation results of the coating film performance.
Example 3

In Example 1, instead of using Fe (III) acetylacetonate alone, 22.1 g of Fe (III) acetylacetonate and 6.8 g of vanadium (III) acetylacetonate were used in the same manner as in Example 1. A hard coat film and an antireflection film were formed. The reflection interference color of the obtained multilayer film was green, and the total light transmittance was 98%. Table 1 shows the evaluation results of the coating film performance.
Example 4

After mixing 1243.4 g of propylene glycol monomethyl ether and 6860.0 g of methanol-dispersed titanium dioxide-tin dioxide-silicon dioxide-zirconium oxide composite fine particle sol (manufactured by Catalyst Chemical Industry Co., Ltd., solid content concentration 20 wt%), γ- 1249.1 g of glycidoxypropyltrimethoxysilane was mixed. To this mixed solution, 343.3 g of 0.1N hydrochloric acid aqueous solution was added dropwise with stirring, and after stirring for 4 hours, 239.9 g of EX-313 (trade name EX-313, manufactured by Nagase Kasei Kogyo Co., Ltd.) was added and 2 After stirring for a period of time, the mixture was aged overnight. In this solution, 25.6 g of Fe (III) acetylacetonate and 7.8 g of aluminum acetylacetonate, 2.2 g of silicon surfactant (manufactured by Nihon Unicar Co., Ltd., trade name “L-7604”) and phenolic oxidation 18.0 g of an inhibitor (manufactured by Kawaguchi Chemical Industry Co., Ltd., trade name “ANTAGE CRYSTAL”) was added, stirred for 4 hours, and then aged overnight to obtain a coating composition. When a hard coat film was formed using the coating composition and then an antireflection film was provided in the same manner as in Example 1, the reflection interference color of the obtained multilayer film was green, and the total light transmittance was 98. %Met. Table 1 shows the evaluation results of the coating film performance.
[Comparative Example 1]

In Example 1, a hard coat film and an antireflection film were formed in the same manner as in Example 1 except that 20.3 g of aluminum acetylacetonate was used instead of Fe (III) acetylacetonate. The reflection interference color of the obtained multilayer film was green, and the total light transmittance was 98%. Table 1 shows the evaluation results of the coating film performance.
[Comparative Example 2]

In Example 1, a hard coat film and an antireflection film were formed in the same manner as in Example 1 except that 4.4 g of Fe (III) acetylacetonate was used. The reflection interference color of the obtained multilayer film was green, and the total light transmittance was 98%. Table 1 shows the evaluation results of the coating film performance.
[Comparative Example 3]

In Example 1, a hard coat film and an antireflection film were formed in the same manner as in Example 1 except that 100.0 g of Fe (III) acetylacetonate was used. The reflection interference color of the obtained multilayer film was green, and the total light transmittance was 98%. Table 1 shows the evaluation results of the coating film performance.
[Comparative Example 4]

In Example 1, instead of methanol-dispersed titanium dioxide-tin dioxide-silicon dioxide-zirconium oxide composite fine particle sol (manufactured by Catalyst Kasei Kogyo Co., Ltd., solid content concentration 20% by weight), methanol-dispersed titanium dioxide-zirconium oxide-silicon dioxide A hard coat film and an antireflection film were formed in the same manner as in Example 1 except that composite fine particle sol (manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name: 1120Z S · 7-G, solid content concentration: 20 wt%) was used. The reflection interference color of the obtained multilayer film was green, and the total light transmittance was 98%. Table 1 shows the evaluation results of the coating film performance.
[Comparative Example 5]

  In Example 4, a hard coat film and an antireflection film were formed in the same manner as in Example 2 except that 23.5 g of aluminum acetylacetonate was used instead of using both Fe (III) acetylacetonate and aluminum acetylacetonate. . The reflection interference color of the obtained multilayer film was green, and the total light transmittance was 98%. Table 1 shows the evaluation results of the coating film performance.

Plastic materials with excellent optical properties, scratch resistance and durability, and adhesion to inorganic anti-reflective coatings are used for consumer or industrial purposes as spectacle lenses, camera lenses, light beam condensing lenses and light diffusion lenses. Can be widely applied for use. 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.

Claims (1)

At least the following components (A) and (B) are the main components and the following component (C) is doped, and the (C) component is (C) / (A ) = 0.004 to 0.06 An antireflection film comprising a hard coat film formed using a coating composition on the surface of a plastic lens and comprising an inorganic substance on the hard coat film surface A plastic lens characterized by laminating.
(A) Composite oxide fine particles comprising a solid solution acid oxide in which the core particles are composed of oxides of titanium and tin and having a rutile structure, and comprising a silicon oxide and an oxide of zirconium and / or aluminum as a coating layer.
(B) An organosilicon compound represented by the following 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, X is a hydrolyzable group, and _n is 0 or 1.)

(C) Fe (III) acetylacetonate and / or vanadium (IV) oxyacetylacetonate and / or vanadium (III) acetylacetonate.