JPH0443242B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides excellent surface properties such as dimming performance, scratch resistance, light resistance, chemical resistance, and dyeability with disperse dyes by applying a highly hard coating film containing silver halide to the surface of a synthetic resin lens. This invention relates to a synthetic resin photochromic lens having the following features. With the enactment of FDA standards in the United States in 1972, the safety of eyeglass lenses was reviewed, and safer plastics began to be used as lens materials instead of inorganic glass. In Japan, the market for plastic cleansing is expanding year by year. On the other hand, the market share of diethylene glycol bisallyl carbonate (hereinafter referred to as CR-39) resin lenses, which are the mainstream of plastic lenses, is said to be 50% in the United States;
It is said that growth has almost stopped after reaching 20%. This is because CR-39 resin is more easily scratched compared to glass, and the other is CR-39 resin glass.
It is speculated that this is because there is no photochromic lens that exhibits excellent light control performance. Currently, there is only one 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, the mainstream consumer's request for the coloring of photochromic lenses is that they change 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 synthetic resin photochromic lenses. In view of the above points, the present inventors have worked diligently to complete a synthetic resin photochromic lens that has excellent dimming performance, scratch resistance, solvent resistance, light resistance, impact resistance, and dyeability with disperse dyes. As a result of research, we have arrived at the present 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, B, and C. A General formula

[Formula] (where R' is an organic group containing at least one selected from vinyl, amino, imino, epoxy, methacryloxy, phenyl, and SH group,
R ² is hydrogen, a hydrocarbon group having 1 to 6 carbon atoms or a vinyl group, R ³ is a hydrocarbon group having 1 to 5 carbon atoms,
Hydrolyzate of one or more silicon compounds represented by an alkoxyalkyl group or an acyl group having 1 to 4 carbon atoms, a is 0 or 1 or 2, b is 0 or 1, and a+b≦2) . B At least one type selected from epoxy compounds. C Curing Catalyst Specific examples of the silicon compound as component A used in the present invention include vinyltrimethoxysilane, vinyltriethoxysilane, ethylenediaminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane. Methoxysilane, γ-glycidoxypropyltriethoxysilane, γ-crisidoxypropylmethyldimethoxysilane, β-glycidoxyethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ- (3,
4-epoxycyclohexyl)propyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, phenyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, Examples include tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltriethoxysilane, and butyltoluethoxysilane. As is well known, the above-mentioned silane compound can be easily hydrolyzed by using water or an aqueous solution of nitric 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 of A may be used alone or in a mixture of two or more, and those in which the corresponding alkoxy group has been previously hydrolyzed or partially dehydrated and condensed are essentially equivalent. ,
Even if these ingredients are included, the same effect can be obtained. As the epoxy compound of component B, (poly)ethylene glycol, (poly)propylene glycol, glycerol, neopentyl glycol,
1,6-hexanediol, trimethylolpropane, pentaerythritol, diglycerol,
Mono-, di-, tri-, and tetraglycidyl ethers of polyhydric alcohols such as sorbitol and bisphenol A (OH groups may remain) and part or all of the double bonds of unsaturated fatty acids such as oleic acid are epoxied. The converted version is used. Various epoxy curing agents can be used as the curing catalyst for component C. For example, BF ₃ , SnCl ₄ ,
SnCl ₂ , ZnCl ₂ , FeCl ₃ , aluminum chelate compound, and HBr, HNO ₃ , H ₃ PO ₄ , carboxylic acid,
Such as sulfonic acid. Examples of solvents that may be included in the coating composition include alcohols, ketones, esters, ethers, cellosolves, halides, carboxylic acids, aromatic compounds, etc., and one or two of these may be mentioned. It can be used as a mixed solvent of more than one species. Also, if necessary, use a surfactant or
It is also possible to add thixotropic agents, organic polymers, inorganic silica fine particles, etc. to impart properties necessary as a paint. Examples of the silver halide include silver bromide, silver chloride, silver iodide, and mixtures thereof, with silver bromide being preferred. In addition to the above components, Cu ⁺ and monovalent or divalent metal ions may also be added. The coating liquid made of the above-mentioned mixture is applied by a commonly used method such as a dipping method, a spray method, a spin coating method, a flow coating method, etc., and the layers are laminated and dried by heating 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 thus obtained is made of polycarbonate resin, acrylic resin, CR-39
It is applied to the lens surface made of transparent resin such as resin or polystyrene, and has excellent transparency and light control performance.
Furthermore, it is possible to obtain a synthetic resin photochromic lens having practically necessary scratch resistance, chemical resistance, light resistance, and hot water resistance. The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.
Note that parts in the examples indicate parts by weight, and the coatings were evaluated using the method shown below. Dimming performance: Using a photochromic lens photochromic lens tester HE-223 (manufactured by Hasegawa Picault Co., Ltd.), those with an average dimming rate of 30% or more in the visible range in one test were considered good. Scratch resistance: The surface was rubbed 10 times with #0000 steel wool under a 1 kg load, and the degree of scratching was evaluated by dividing the lower stairs. 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 coatings: Based on cross-cut tape test. In other words, cross-cut the coating surface with a knife to make 100 squares of 1 mm x 1 mm, adhere cellophane adhesive tape on top of it, peel off the tape, and select the squares that will not peel out of the 100 squares. Displayed with number. 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, and 1% sodium hydroxide aqueous solution. Dyeability with disperse dye: Terrasil Black B
(manufactured by Ciba Kaigy) was dispersed in 85° C. hot water, and a lens was immersed in this solution for 5 minutes, and those with an average luminous index in the visible range of 25% or more were evaluated as good. Example 1 (1) Preparation of hydrolyzate of γ-glycidoxypropyltrimethoxysilane and tetramethoxysilane In a reaction vessel equipped with a stirring device and a cooling tube, 110 parts of γ-glycidoxypropyltrimethoxysilane, 80 parts of tetramethoxysilane and 230 parts of isopropyl alcohol were charged, and while stirring vigorously, 76 parts of a 0.05 N nitric acid aqueous solution was added at room temperature, and stirring was further continued at room temperature for 1 hour to effect hydrolysis. Thereafter, stirring was stopped and the mixture was aged at room temperature overnight. (2) Preparation and coating of paint For the hydrolysis obtained in (1), 115 parts of 1.6-hexanediol dixidyl ether (Epolite 1600 manufactured by Kyoeisha Yushi Co., Ltd.), 1.2 parts of stannous chloride, and 0.2 parts of silicone surfactant were added. The mixture was stirred at room temperature for 30 minutes, and 45 parts of silver bromide having an average particle size of 50 mμ was added and stirred for 1 hour to obtain a mixed dispersion, which was used as a paint. Apply this paint to SEIKO Platz (CR-39).
It was applied to the lens made by the manufacturer using the dipping method at a pulling speed of 20 cm/mm, then dried in a hot air dryer at 80°C for 30 minutes, and then dried at 120°C.
It was heated and cured for 90 minutes. The thickness of the film after curing is
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 vinyltrimethoxysilane were prepared in the same manner as in Example 1 except that 60 parts of a 0.01N nitric acid aqueous solution at room temperature was added to 100 parts of vinyltrimethoxysilane, 60 parts of vinyltrimethoxysilane, and 200 parts of ethyl cellosolve. A hydrolyzate was obtained. To this solution, 80 parts by weight of ethylene glycol diglycidyl ether (Epolite 40E, manufactured by Kyoeisha Yushigakusha Co., Ltd.) and 1 part of BF ₃ O (C ₂ H ₅ ) ₂ were added and stirred for 1 hour.
Disperse 20 parts of silver iodide and 10 parts of silver bromide of 100 mμ,
Flow control agent “Disparon AQ4200−”
10N" (Kusumoto Kasei Co., Ltd.) was added and mixed with a homogenizer at 20,000 rpm for 1 hour to form a paint. The resulting coating liquid was immersed in polycarbonate sunglasses under the same conditions as Example 1, and allowed to dry and harden. I went.
The obtained lens was a transparent lens with a slight yellow tinge, and the thickness of the film was 5.0 μm. Table 1 shows the characteristics of the lens. Example 3 100 parts of β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 35 parts of methyltrimethoxysilane, 15 parts of Aerosil (manufactured by Nippon Aerosil Co., Ltd.) of approximately 10 to 50 mμ, isopropyl alcohol
44 parts of 005N sulfuric acid aqueous solution was added to 180 parts with stirring, and hydrolysis was carried out in the same manner as in Example 1. Add trimethylolpropane triglycidyl ether (Epolite) to the solution thus obtained.
100MF, Kyoeisha Yushi Kagaku) 80 parts, tin tetrachloride
After adding 1.5 parts and stirring at room temperature for 30 minutes, 25 parts of silver bromide of about 50 mμ was added and vigorously stirred at room temperature to obtain a mixed dispersion, which was used as a paint. The above coating liquid was applied to sunglasses obtained by injection molding of polymethyl methacrylate by the dipping method (pulling speed 10 cm/mm), and then heated at 60°C for 1 hour and at 80°C for 3 hours.
Dry and cure for an hour. The obtained lens is a transparent lens with a slight yellowish tinge, and the thickness of the coating film is
It was 2.5μ. Table 1 shows various properties of the lens. Example 4 149 parts of γ-methacryloxypropyltrimethoxysilane, 93 parts of tetraethoxysilane, 110 parts of isopropylcol, and 0.7 parts of a silicone surfactant were charged into a reaction vessel equipped with a stirrer and a cooler, and stirred at room temperature. At the same time, 80 parts of a 0.05N nitric 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. Sorbitol polyglycidyl ether (Denacol) is added to the liquid thus obtained.
EX-614, Nagase Sangyo) 90 parts, zinc chloride 1.8 parts, approx.
45 parts of silver bromide of 50 mμ was added and stirred vigorously at room temperature for 1 hour to obtain a dispersion mixture. The obtained coating liquid
Immersion method in SEIKO High Road (pulling speed 5cm/
mm), dried and cured under the same conditions as in Example 1 to obtain a high refractive index photochromic lens. The obtained lens had a slightly yellowish, transparent coating and 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, B, and C contains silver halide. A General formula [Formula] (where R' is an organic group containing at least one selected from vinyl, amino, imino, epoxy, methacryloxy, phenyl, and SH group,
R ² is hydrogen, a hydrocarbon group having 1 to 6 carbon atoms or a vinyl group, R ³ is a hydrocarbon group having 1 to 5 carbon atoms,
an alkoxyalkyl group or an acyl group having 1 to 4 carbon atoms, a is D or 1 or 2, b is 0 or 1, and a hydrolyzate of one or more silicon compounds represented by a+b≦2) . B At least one type selected from epoxy compounds C Curing catalyst