JPH0444241B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is made of synthetic resin that has excellent surface properties such as dimming performance, scratch resistance, light resistance, and chemical resistance by applying a highly hard coating film containing silver halide to the surface of the synthetic resin lens. Regarding photochromic lenses. With the establishment of FDA standards in the United States in 1972, the safety of eyeglass lenses was reviewed, and safer synthetic resins began to be used as lens materials instead of inorganic glass. In Japan, the share of synthetic resin lenses is increasing year by year. On the other hand, diethylene glycol bisallyl carbonate (hereinafter referred to as
The ratio of lenses made of resin (abbreviated as CR-39) is said to be approximately 50% in the United States, and it is said that the ratio has almost stopped increasing after reaching 50%. This is because CR-39 resin is more easily scratched compared to glass, and the other reason is that
It is speculated that this is because the CR-39 lens does not have a photochromic lens that exhibits excellent light control performance. This is the only lens on the market that exhibits blue photochromism. The dimming performance of this lens is not satisfactory compared to that of glass lenses in terms of light attenuation rate, coloring speed, and fading speed. Almost the same thing can be said about photochromic lenses made of thermoplastic resin. On the other hand, consumer demands regarding the coloring of Photochromic lenses are
The mainstream is to change color from colorless to brown or gray due to absorption of light. In other words, it is no exaggeration to say that there are no satisfactory photochromic lenses made of synthetic resin lenses. In view of the above points, the present inventors conducted extensive research in order to complete a synthetic resin photochromic lens that has excellent dimming performance, scratch resistance, solvent resistance, light resistance, and impact resistance. We have arrived at the invention described below. That is, the present invention is a synthetic resin photochromic lens characterized by containing silver halide in a coating composition containing the following A and B. A General formula

[Formula] (where R ¹ is an organic group containing at least one selected from vinyl, propyl, butyl, amino, imino, glycidoxy, methacryloxy, phenyl, and SH group, R ² is hydrogen, carbonized carbon having 1 to 6 carbon atoms) Hydrogen group or vinyl group, R ³ has 1 or more carbon atoms
5 hydrocarbon group, alkoxyalkyl group or acyl group having 1 to 4 carbon atoms, a is 1 or 2, b
is 0 or 1, and is a hydrolyzate of one or more silicon compounds represented by a+b≦2). B General formula R ⁴ c-Si-(OR ⁵ ) ₄ -c (wherein R ⁴ is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, R ⁵ is a hydrocarbon group having 1 to 5 carbon atoms, alkoxyalkyl group, or an acyl group having 1 to 4 carbon atoms, c is 0 to
One or more hydrolysates selected from the silicon compounds represented by (which is an integer of 2). Specific examples of the silicon compound as component A used in the present invention include vinyltrimethoxysilane, vinyltriethoxysilane, ethylenediaminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β-glycidoxyethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-(3,
Examples include 4-epoxycyclohexyl)propyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, phenyltrimethoxysilane, and γ-mercaptopropyltrimethoxysilane. Specific examples of the silicon compound of component B include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, and ethyl Examples include triethoxysilane, propyltriethoxysilane, and butyltriethoxysilane. As is well known, the above-mentioned silane compound can be easily hydrolyzed by using water or an aqueous solution of hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid, etc. in the presence or absence of a solvent such as alcohol. can. In addition, each of the silane compounds A and B is 1
A species or a mixture of two or more species may be used, and those in which the corresponding alkoxy group has been previously hydrolyzed or partially dehydrated and condensed are essentially equivalent, and even if they contain these, they are equivalent. Effects can be obtained. Examples of solvents that may be included in the coating composition include alcohols, ketones, esters, ethers, cellosolves, halides, carboxylic acids, aromatic compounds, etc.; Alternatively, it can be used as a mixed solvent of two or more kinds. Furthermore, if necessary, organic polymers, curing catalysts, and surfactants that are compatible with these materials can be added to impart leveling properties, viscosity, drying properties, etc. necessary for the paint. In addition, silver halides include silver bromide, silver chloride,
Silver iodide can be used; silver bromide is preferred. The coating liquid made of the above-mentioned liquid mixture is applied by a commonly used method such as dipping, spraying, spin coating, flow coating, etc., and is then heated and dried to form a cured film. The heating temperature and heating time are determined depending on the properties of the base material. The thickness of the obtained cured film is preferably 1 to 30μ; if it is less than 1μ, satisfactory scratch resistance cannot be obtained and it is difficult to fully demonstrate the performance of the film. Even if the film thickness is increased, the effect of increasing the film thickness cannot be expected. The coating composition obtained in this way can be applied to polycarbonate resin, acrylic resin, CR
-39 It is coated on the lens surface made of transparent resin such as resin or polystyrene, and has excellent transparency and dimming performance, and also has the practically necessary scratch resistance, chemical resistance, light resistance, and hot water resistance. A synthetic resin photochromic lens can be obtained. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. Note that parts in the examples indicate parts by weight. Also,
The coating was evaluated using the method shown below. Dimming performance: Photochromic Lens Dimming Lens Tester HE-223 (manufactured by Hasegawa Picault)
was used, and those with an average attenuation rate of 30% or more in the visible range in one test were considered good. Scratch resistance: A load of 1 kg was applied with #0000 steel wool, the surface was rubbed back and forth 10 times, and the degree of scratching was divided into the following grades and evaluated. A: No scratches at all within a 1cm x 3cm area. B: 1 to 10 scratches within the above range. C: 10 to 100 scratches are made within the above range. D: There are countless scratches, but a smooth surface remains. E: No smooth surface remained due to scratches on the surface. Adhesion of coating film: Based on cross-cut tape test. In other words, cross-cut with a knife on the surface of the film and make a 1 mm x 1 mm square.
After making 100 squares and adhering cellophane adhesive tape to them, the tape was peeled off and the number of squares that did not peel out of the 100 squares was displayed. Hot water resistance: The state of the film was examined after being immersed in boiling water for 1 hour. Heat resistance: The state of the film was examined after being stored in a hot air drying oven at 130°C for 2 hours. Chemical resistance: The state of the film was examined after 48 hours of immersion in 95% ethanol, acetone, 3% sulfuric acid aqueous solution, and 1% sodium hydroxide aqueous solution. Example 1 (1) Preparation of hydrolyzate of γ-glycidoxypropyltrimethoxysilane and tetramethoxysilane In a reactor equipped with a stirring device, 67 parts of γ-glycidoxypropyltrimethoxysilane and tetramethoxysilane were added. 101 parts and 135 parts of isopropyl alcohol were charged, and while stirring vigorously, 77 parts of a 0.05N aqueous hydrochloric acid solution was added at room temperature to perform hydrolysis, and stirring was continued for an additional 1 hour at room temperature. Thereafter, stirring was stopped and the mixture was aged at room temperature for one day and night. (2) Preparation and painting of paint Add 0.3 parts of stannous chloride to the hydrolyzate obtained in (1).
Add 0.2 parts of silicone surfactant, stir at room temperature for 30 minutes, add 9 parts of silver bromide with an average particle size of 100 mμ, stir for 1 hour at 20,000 rpm with a homogenizer,
A mixed dispersion was obtained and used as a paint. This paint,
It was applied to SEIKO Plax (CR-39 lens) by the dipping method (pulling speed 20 cm/min), heated and cured in a hot air dryer at 80°C for 30 minutes, and then at 120°C for 90 minutes.
The thickness of the film after curing was 3 μm, and the film had a pale yellow tinge but was transparent. Table 1 shows the characteristics of the lens. Example 2 γ-glycidoxypropyltrimethoxysilane
γ-Glycidoxypropyltrimethoxysilane and tetramethoxysilane were prepared in the same manner as in Example 1, except that 142 parts of 0.01N hydrochloric acid aqueous solution was added to 141 parts of γ-glycidoxypropyltrimethoxysilane, 61 parts of tetramethoxysilane, and 180 parts of methyl cellosolve while stirring at room temperature. A hydrolyzate of methoxysilane was obtained. To this solution, 1 part of lead chloride and 0.4 part of a silicone surfactant were added, and the mixture was stirred at room temperature for 1 hour to disperse silver iodide having an average particle size of 50 mμ, and the mixture was stirred for 30 minutes to obtain a coating liquid. The obtained coating liquid was immersed in a polycarbonate resin under the same conditions as in Example 1, and was then dried and cured. The obtained lens is a transparent lens with a slight yellowish tinge, and the thickness of the film is
It was 3.3μ. Table 1 shows the characteristics of the lens. Example 3 Methyl cellosorg was added to a reaction vessel equipped with a stirring device.
190 parts, B-(3,4-epoxycyclohexyl)
97 parts of ethyltrimethoxysilane, 13 parts of methyltrimethoxysilane, 15 parts of Aerosil (manufactured by Nippon Aerosil Co., Ltd.) of approximately 50 mμ, and 4.5 parts of tetrabutoxytitanium were added, and after stirring at room temperature for 4 hours, 4.5 parts of water was added. was added dropwise over 10 minutes with strong stirring, and then left to ripen at room temperature for 24 hours. Add 7 parts of silver bromide (approximately 50 mμ) to the solution obtained in this way, and use a homogenizer at room temperature to
Stir at 20,000 rpm for 30 minutes to form a coating solution, apply it to sunglasses obtained by injection molding polymethyl methacrylate using the dipping method (pulling speed 10 cm/min), dry and cure at 60°C for 1 hour, and at 80°C for 3 hours. did. The obtained lens was a transparent lens with a slight yellowish tint, and the thickness of the coating was 2.5 μm. Table 1 shows the characteristics of the lens. Example 4 149 parts of γ-methacryloxypropyltrimethoxysilane, 83 parts of tetraethoxysilane, 155 parts of isopropyl alcohol, and 0.7 parts of silicone surfactant were charged into a reaction vessel equipped with a stirrer, and at room temperature, while stirring, 0.05 parts of 80 parts of N hydrochloric acid aqueous solution was added all at once, and the mixture was further stirred for 1 hour. This liquid was aged at room temperature for 24 hours, 12 parts of silver bromide of about 50 mμ was added, and the mixture was stirred at room temperature for 1 hour to obtain a dispersion mixture. The coating solution obtained in this way was applied to SEIKO Highroad lenses by dipping method (pulling speed 5 cm/min), dried and cured under the same conditions as in Example 1, and a high refractive index photochromic lens was obtained. Obtained. The obtained lens had a slightly yellowish, transparent coating, and the coating had a thickness of 2.5 μm. Table 1 shows the characteristics of the lens.

【table】

Claims (1)

[Scope of Claims] 1. A photochromic lens made of synthetic resin, characterized in that a coating composition containing the following A and B contains silver halide. A General formula [Formula] (where R ¹ is an organic group containing at least one selected from vinyl, propyl, butyl, amino, imino, glycidoxy, methacryloxy, phenyl, and SH group, R ² is hydrogen, and has 1 to 1 carbon atoms) 6 hydrocarbon group or vinyl group, R ³ has 1 to 1 carbon atoms
5 hydrocarbon group, alkoxyalkyl group or acyl group having 1 to 4 carbon atoms, a is 1 or 2, b
is 0 or 1, and is a hydrolyzate of one or more silicon compounds represented by a+b≦2). B General formula R ⁴ c-Si-(OR ⁵ ) ₄ -c (wherein R ⁴ is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, R ⁵ is a hydrocarbon group having 1 to 5 carbon atoms, alkoxyalkyl group or acyl group having 1 to 4 carbon atoms, c is 0 to 2
One or more hydrolysates selected from the silicon compounds represented by (which is an integer of ).