JPS6045224A - Photochromic plastic lens - Google Patents

Abstract

PURPOSE:To obtain a lens having superior surface hardness, wear resistance, durability and photochromic performance by coating a lens with a composition contg. silver halide, colloidal silica and the hydrolyzate of a silicon compound and by hardening the composition. CONSTITUTION:A lens is coated with a coating composition contg. silver halide except silver fluoride, colloidal silica of 1-100mmu particle size and the hydrolyzate of one or more kinds of silicon compounds represented by the general formula as principal components, and the composition is hardened. In the formula R<1> is vinyl, amino, imino, epoxy, (meth)acryloxy, phenyl or SH; R<2> is H, 1-6C (halogenated) hydrocarbon; R<3> is 1-5C hydrocarbon, alkoxyalkyl or 1-4C acyl; each of a and b is 0, 1 or 2; and a+b<=2. The silicon compounds include vinyltrimethoxysilane.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention complies with the 1972 U.S. FDA standard (Standard for eye safety) regarding a photochromic lens made of synthetic resin that has excellent surface hardness, abrasion resistance, durability, and photochromic performance. Due to the enactment, the safety of eyeglass lenses has been reviewed, and safer synthetic resin materials have come to be used instead of inorganic glass as lens materials. In Japan, the share of plastic lenses is increasing year by year, and has already reached 6.
It is said to have exceeded 0%. In addition to the safety, lightness, fusion properties, and ease of processing that plastic materials have, we also offer anti-reflection coatings and hard coatings.

It is thought that this is because many manufacturers have conducted research and commercialized products one after another to provide functions such as hard anti-reflection coating, anti-fog properties, high refractive index resin, etc. On the other hand, diethylene glycol bisallyl carbonate (hereinafter referred to as 0R), which is the mainstream of diblastic lenses, -39) The market share of resin lenses in the United States is said to be approximately 50%, with a share of 5Qr.
It is said that growth has slowed down since reaching the new cent.
It is speculated that this is because the 0R-19 lens is more easily scratched compared to the glass, and the other reason is that the 0R-59 lens does not have an excellent photochromic lens. Currently, the only photochromic lens that changes color to blue is on the market, but there are problems with its functionality (light attenuation rate: speed of coloring, speed of fading). On the other hand, the overwhelming majority of consumer requests for coloring of photochromic lenses are for a change from colorless to brown or gray due to light absorption.In other words, there are no satisfactory synthetic resin photochromic lenses. It is no exaggeration to say that the abrasion resistance of plastic materials is technically important.

Research to improve durability and research on materials that exhibit photochromic performance have been conducted individually and many proposals have been made, but no research that comprehensively considers both has been conducted. sex.

A photochromic lens made of synthetic resin that simultaneously satisfies the 7 otochromic properties has not yet been established.

Typical examples of techniques for improving the wear resistance of plastic materials are JP-A-50-48674 and JP-A-51-427.
52, JP 52-112698, JP 53-111
33 (S, JP-A-56-99266, USP-3,98
On the other hand, the technology related to 7 odochromic materials (lenses) is disclosed in 6,997, etc.
12716-1971, 28893-28893, 1106-1106, 89179-1989, 45541-1971, 152887-1972, 152887-1972, 955-955, 152887-1970 110854, Japanese Patent Publication No. 55
-12141'・Special Publication 57-39214・Special Publication 1977
-55, ;l'.

747, Japanese Patent Application Laid-Open No. 57-156645, and the like. It is difficult to infer photochromic performance to plastic resin materials using these technologies.

Molecules that exhibit photochromic properties made of organic or inorganic compounds are added to plastic materials, bonded to polymer chains, brought into contact and transferred thermally, or included in resin and laminated. However, in either case, the abrasion resistance is poor and the material is unsatisfactory as a lens material.Additionally, the method of adding a photochromic material to the resin is preferable for the appearance of the lens. This is because spectacle lenses that are not 0 generally have different thicknesses between the center and the outer periphery, so if 7 otochromic molecules are uniformly distributed in the lens material, there will always be a concentration gradient in the light attenuation rate due to color development.

Furthermore, when a casting method such as 0R-39 is employed, most of the photochromic molecules are deactivated by a commonly used peroxide such as diisopropyl monooxydicarbonate. The method in which photochromic molecules are moved by contact is difficult to achieve uniform transfer, tends to cause unevenness, and tends to cause defects on the lens surface.

Japanese Patent Laid-Open No. 58-34437 describes a method of imparting photochromic functions by dispersing and dissolving 7 otochromic substances in a solvent and impregnating the treated plastic substrate with Sin, Sin.

, *i,o, , A method for depositing ZvO2 is disclosed. Although this technology is excellent in improving the various drawbacks mentioned above, problems remain in terms of wear resistance and heat resistance. In other words, in terms of improving heat resistance, abrasion resistance, and S impact resistance, silicon It is a well-known technology in the eyeglass lens industry that the performance is better when only an antireflection layer made of an inorganic material is deposited on top of a silicone hard foot or silicone hard coat. .

In addition, the present inventors have previously proposed a photochromic lens made of synthetic resin that uses tetraalkyl silicate or the like instead of the B component in the present invention (Patent Application No. 1996/1993).
8' r 2 ) was found to have a shortcoming in terms of pot life.

In view of the above points, the present inventors developed a material that has a photochromic function that develops a brown color upon irradiation with light and reversibly returns to colorless in the dark, and has surface hardness and abrasion resistance.

As a result of research to obtain a synthetic resin photochromic lens with excellent durability, the invention described below was achieved.In other words, the present invention involves coating and curing a coating composition containing the following A, B, and O as main components. O A1 silver halide (halogen is halogen excluding fluorine) BN particle size 1 to 100 mm colloidal LR
1 is vinyl, amino, imino, and epoxy.

(meth)acryloxy, phenyl, and an organic group containing at least one selected from SH group, R2 is hydrogen, carbon Wi
1-6 (halogenated) hydrocarbon group, R3 has 1-6 carbon atoms
5 hydrocarbon group, alkoxyalkyl group, or acyl group having 1 to 4 carbon atoms・a is 0.1 or 2, b is 0,1 or 2, and one type of silicon compound represented by α+b≦2) or two or more types of hydrolyzate 0 Next, each component constituting the coating composition of the present invention will be described.

Examples of the silver halide of component A include silver bromide, silver iodide, silver chloride, and mixtures of two or more of these. The colloidal silica with a particle size of 1 to 100 millimicrons, which is suitable for combination with OB component, refers to a product obtained by dispersing a high molecular weight anhydrous silica in a dispersion medium such as water, alcohol, or cellosolve, and is well known. It is manufactured by this method and is commercially available.

Particle sizes of 5 to 40 tnμ are particularly useful in the practice of the present invention.

Component B is a silicon compound wire that is important for improving the abrasion resistance and durability of the coating, and is an essential component for improving the adhesion, flexibility, and abrasion resistance of the coating. Toquinsilane, vinyltriethoxysilane, vinyltriacetoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ
-Glycidoxypropylmethyldimethoxysilane.

β-glycidoxyethyltrimethoxysilane, β-(3
, 4-epoxycyclohexyl)ethyltrimethoxysilane, r-(3,4-epoxycyclohexyl)ethyltriethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxydilobylmethyldimethyldimethylsilane Methginsilane, phenyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, β-cyanoethyltriethoxysilane, tetramethoxysilane, tetraethquinsilane, tetrapropoxysilane .

Tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriprogoxysilane, methyltriplox, disilane, ethyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, dimethyljethoxysilane, phenylmethyljethoxysilane, etc. There is. Hydrolysis of these silane compounds is carried out by a well-known method, for example, in a mixed solvent of water and alcohol in the presence of an acid. When the compound of component C is used without being hydrolyzed, the wear resistance is insufficient. Furthermore, when two or more types of silicon compounds are hydrolyzed and used, better results are often obtained by mixing them and simultaneously co-hydrolyzing them than by hydrolyzing them separately and then mixing them. Further, although hydroxyl groups generated by hydrolysis exist in a partially condensed form, this does not affect the effects of the present invention.

In order to more effectively exhibit the 7 otochromic properties of the present invention, it is preferable to add a trace amount of oxidized steel, or a metal oxide such as antimony oxide or iron oxide.

If necessary, an alkali metal salt of a carboxylic acid such as sodium acetate + an amine carboxylate such as ethanolamine + a quaternary ammonium salt such as tetramethylammonium/l/boxylate and triethylamine, Condensation catalysts such as glycine, pyridine, alkali hydroxide, BF, 5nOn, 5nOj2
2. It is effective to use a Lewis acid such as ARO13, or a Bränsted's acid, an aluminum chelate compound, other metal chelate compounds, or an epoxy curing catalyst such as ammonium perchlorate.□ Improvement of painting work, as a paint Various solvents, surfactants, thixotropic agents, ultraviolet absorbers, antioxidants, and various polymers can be added for the purpose of imparting the necessary properties. As the solvent or diluent, various solvents such as alcohol, ketone, ester, cellosolve, halogenated hydrocarbon, carboxylic acid, aromatic compound, etc. can be used, and one or more of these solvents can be used as a mixed solvent. It is also possible.

The composition of the present invention can be applied to a synthetic resin lens by a well-known method such as a dipping method, a spray method, a spin coating method, or a flow coating method. The synthetic resin lens coated in this manner is heated and dried to obtain a hardened coating.

Conditions such as heating temperature and heating time are determined in consideration of the characteristics of the resin, but a temperature of 60 to 150°C is usually applied.

The thickness of the resulting cured film is preferably 1 to 30μ; if it is less than 1μ, satisfactory wear resistance cannot be obtained, and in order to maintain the required properties,
It is necessary to limit the amount of photochromic substances. On the other hand, even if the thickness is 60 μm or more, no effect can be expected from increasing the film thickness, and cranks are likely to occur.

In order to improve the adhesion between the synthetic resin lens and the coating composition, the lens surface is pretreated with various primers, activated gas treatment, acid, alkali, etc. in advance, 1.1. Useful in practicing the invention.

The coating composition thus obtained is applied to the surface of a lens made of a transparent resin such as polycarbonate resin, acrylic resin, 0R-69 resin, polystyrene, etc.
Transparency 9 A synthetic resin photochromic lens with excellent surface hardness, abrasion resistance, durability, and photochromic performance can be provided.

The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.

Note that parts in the examples indicate parts by weight. The coating was evaluated using the method shown below. Photochromic performance: 7 Otochromic lens photochromic lens tester HE-223 (manufactured by Hasegawa Wabiko Co., Ltd.) was used to evaluate the average light attenuation rate in the visible range in one test. Those with 30% or more were considered good.

- Abrasion resistance: A load of IK71 was applied with 5oooo steel wool, and the surface was rubbed 10 times back and forth, and the degree of scratching was divided into the following grades and evaluated.

A: There are almost no scratches.

B: Some damage will occur.

C: Significant damage will occur.

Adhesion of the coating film: In the so-called cross-cut tape test, 10 parallel lines were drawn vertically and horizontally at one-word intervals on the coating surface using a knife, 100 squares were cross-cut, and cellophane adhesive tape was applied on top of the cross-cuts. After adhesion, the tape was peeled off and the number of squares that did not peel off among 100 squares was expressed.

Hot water resistance: The state of the coating was visually examined after being immersed in boiling water for 1 hour.

Heat resistance: The state of the film was visually inspected after being stored in a hot air drying oven at 120°C for 2 hours.

Chemical resistance: ethanol, acetone, 1% sulfuric acid aqueous solution, 0
．． After being immersed in an aqueous solution of 5% hydroxide for 24 hours, the condition of the film was visually examined.

Example 1 (1) Preparation of hydrolyzate of r-glycidoxypropyltrimethoxysilane In a reactor equipped with a stirring device, 30% of isopropyl alcohol was added.
59 parts, 200 parts of isopropyl alcohol-dispersed Coro 1 Dal silica (Catalyst Chemical Industry Co., Ltd. "Oscar 1452" solid content concentration 60%), 266 parts of γ-glycythoxypropyltrimethoxine oran.

After charging 0.3 parts of a silicone surfactant and adding 81 parts of a 0.05 N nitric acid aqueous solution at room temperature while stirring,
Stirring was continued for 1 hour. Thereafter, stirring was stopped, and the mixture was aged at room temperature overnight.

(2) Preparation and coating of paint Add 30 parts of silver bromide with an average particle size of 50μ to the hydrolyzate obtained in (1), and mix with a homogenizer at 20,000 rpm.
This paint was stirred for 1 meter to disperse and form a paint.
Immersion method (pulling speed 23 cm /
m), and was heated and cured in a hot air drying oven at 80°C for 30 minutes and then at 120°C for 120 minutes. The thickness of the coating after curing was 5 microns.

The initial viscosity of the coating liquid according to type B viscosity was 52 centimeters, and the viscosity after one month was 58 centimeters, and the liquid life was good.

The properties of the obtained lens are shown in the table.

Example 2 160 parts of methyl cellosolve, 118 parts of γ-glycidoxyprobyltrimethoxysilane, 23 parts of methyltrimethoxysilane, 200 parts of methanol-dispersed colloidal silica (
Nissan Chemical Co., Ltd. 6 methanol silica sol “solid content concentration 30”
%) into a reactor equipped with a rotor, and while stirring vigorously using a magnetic stirrer, the mixture was heated to 0.05% at room temperature.
Aqueous N acetic acid solution was added all at once and stirring continued for 1 hour. Stirring was stopped and the solution was aged at 10°C for a day and night. To this solution was added 1 part of silicone surfactant and 40% silver bromide with an average particle size of 50rnμ.
1 part and 4 parts of acetylacetone zirconium were added, and the mixture was stirred using a homogenizer at 2000 rpm for 1 hour to disperse the mixture, thereby preparing a paint. The obtained coating liquid was applied to sunglasses made of polymethyl methacrylate using the immersion method (pulling speed 20 cm/t).
The thickness of the O coating was 65μ after being dried and cured at 60°C for 1 hour and 80°C for 5 hours. The liquid life of the paint was good for one month. The properties of the obtained lens are shown in the table.

Example 3 Isopropyl alcohol .;i in a reactor equipped with a rotor
・280 parts of methanol-dispersed colloidal silica
0 parts (Catalyst Chemical Industry Co., Ltd. Oscar 1162 Solid content concentration 3
0%), 165 parts of γ-glyndoxybrobylmethyldiethoxysilane, and 0.6 part of a silicone surfactant were added in this order and stirred. Next, 31 parts of 005N acetic acid aqueous solution was added while stirring at room temperature, and stirring was continued for 1 hour.Afterwards, stirring was stopped and the mixture was aged at room temperature overnight.

To the solution obtained in this way, 60 parts of silver bromide and 10 parts of silver iodide with an average particle size of 50 μm were added, and 20 parts of silver
The mixture was stirred at 0.000 rpm for 1 hour to disperse and form a paint.

This paint was applied to polycarbonate sunglasses by the dipping method (pulling speed: 20 cm/ttis) and cured by heating in the same manner as in Example 1. The thickness of the film after O-curing was 5 μm. The properties of the obtained lens are shown in the table.

The life of the paint was good even after one month.

Example 4 24 hours of isopropyl alcohol in a reactor equipped with a rotor
0 parts, 600 parts of water-dispersed colloidal silica (catalyst chemical industry flavor, α1oidsN on Ca, solid content concentration 20%), γ
- 142 parts of glycidoxypropyltrimethoxysilane + 41 parts of γ-methacryloxypropyltrimethoxysilane
1 part and 0.5 parts of silicone surfactant were added in this order while stirring with a magnetic stirrer, and stirring was continued for 2 hours. After stopping stirring, the mixture was aged at room temperature day and night.

Add 40 parts of silver bromide having an average particle size of 50 mμ to the above solution.

Add 2 parts of stannous chloride and use a homogenizer to
The resulting paint was stirred for 30 minutes at 0.00 rpm and dispersed to form a paint. ■ Using the resulting paint, it was applied to a -6,00D lens with the trade name of Seiko SE Ko Hiroad in the same manner as in Example 1. Hardened. The film thickness was 7 μm, and a high A index photochromic lens was obtained. The properties of the obtained lens are shown in the table.The pot life of the paint was good for one month.

Claims (1)

[Claims] (1) A synthetic resin photochromic lens characterized by being coated and cured with a coating composition containing the following A, B, and O as main components. A1 Silver halide (2) (excluding fluorine <halogen) B1 Colloidal silica with a grain size of 1 to 100 millimicrons (R1 is vinyl, amino, imino, epoxy, (
an organic group containing at least one selected from meta)acryloxy, phenyl, and SH group, R2 hydrogen, carbon number 1-
6 ()・Rogenich) hydrocarbon group, R3 has 1 carbon number
-5 hydrocarbon group, alkoxyalkyl group, or acyl group having 1 to 4 carbon atoms, a is 0,1 or 2, b is 0.1
or 2, and one or more hydrolysates of silicon compounds represented by α1≦2).