JPS6046528A - Plastic photochromic lens - Google Patents

Abstract

PURPOSE:To obtain a plastic photochromic lens having excellent surface hardness, wear resistance, durability and photochromic performance by coating a coating compsn. of prescribed composition on a plastic lens and curing the same. CONSTITUTION:The compsn. consisting of the following A, B, C is coated on a plastic lens and is cured: A: Colloidal silica having 1-100mmu grain size. B: the hydrolyzate of a silicon compd. expressed by R<1>a-Si (-R<2>b side chain)-(OR<3>)4-a-b, where R<1> is an org. group contg. at least one kind selected from vinyl, amino, imino, epoxy, (meth)acryloxy, phenyl and SH groups, R<2> is hydrogen, (halogenated) hydrocarbon group of 1-6C, R<3> is a hydrocarbon group and alkoxyl alkyl group of 1-5C or an acyl group of 1-4C, a, b=0.1 or 2 and a+b<=2. C: the benzopyrilosprane expressed by the formula. The plastic photochromic lens having excellent surface hardness, wear resistance, durability and photochromic performance is thus obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a synthetic resin photochromic lens having excellent surface hardness, abrasion resistance, durability, and photochromic performance.

The safety of eyeglass lenses was reviewed in 1972 with the enactment of the US FDA Standards (Standards for Eyeglass Safety), and safer synthetic resin materials were used instead of inorganic glass as lens materials. It has become. In Japan, the share of plastic lenses is increasing year by year, and has already reached 3.
It is said to have exceeded 0%. In addition to the safety, lightness, fashionability, and ease of processing that plastic materials have, there are many other functions that can be added such as anti-reflection coating, hard coating, hard anti-reflection coating, anti-fog properties, and high refractive index resin. This is thought to be due to manufacturers conducting extensive research and commercializing products one after another. On the other hand, diethylene glycol bisallyl carbonate (
The market share of resin lenses (hereinafter referred to as 1!R-39) in the United States is said to be approximately 5%, with a market share of 50%.
It is said that growth has slowed down since reaching 200%.

This is thought to be due to the fact that CR-39 lenses are more easily scratched compared to the glass, and the other reason is that (!) R-39 lenses do not have excellent photochromic lenses.

Currently, photochromic lenses that change color to dark blue are commercially available, but they have problems in terms of functionality (light attenuation rate, coloring speed, and fading speed). On the other hand, the overwhelming majority of consumer requests for coloring of photochromic lenses are for the lens to change from colorless to brown or gray due to absorption of light. It is no exaggeration to say that there are no synthetic resin photochromic lenses that are completely satisfactory. Technically, research on improving the abrasion resistance and durability of plastic materials and research on materials that exhibit photoclock performance have been conducted individually and many proposals have been made, but both can be considered comprehensively. No research has been conducted, and a synthetic resin photochromic lens that satisfies wear resistance, durability, and photochromic performance at the same time has not yet been established.

Typical examples of techniques for improving the wear resistance of plastic materials are JP-A-50-40674 and JP-A-51-427.
52, JP 52-112698, JP 53-111
336, JP-A-56-99263, USF-39869
97, etc.

On the other hand, the technology related to photochromic materials (lenses) is disclosed in Japanese Patent Publication No. 12716/1971, Japanese Patent Publication No. 28893/1973, Japanese Patent Publication No. 1106/1976, and Japanese Patent Publication No. 89179/1989. @ JP 51-45541, JP 52-152887, JP 54-955, JP 54-110854, JP 55
-121412, Special Publication No. 57-39244, Special Publication No. 5.
7-55747° JP-A No. 57-136645, etc., and many others. To impart photochromic properties to plastic resin materials using these technologies, molecules that exhibit photochromic properties made of organic or inorganic compounds are added to the plastic material, or they are bonded to polymer chains, or they are brought into contact with the plastic material and thermally applied. Methods have been taken to either move the material or to laminate it in a resin, but in either case, it is inferior in terms of wear resistance and is not satisfactory as a lens material. Further, the method of adding a photochromic material to the resin is not preferable in terms of the appearance of the lens. This is because eyeglass lenses 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 using a casting method such as 0R-39, most of the photochromic molecules are deactivated by the commonly used peroxides such as diisopropylebaroxydicarbonate, and the photochromic molecules are inactivated by contact. With the moving method, it is difficult to achieve uniform transfer, and unevenness tends to occur (and defects on the lens surface are also likely to occur).

1985-54457 describes a method for imparting photochromic functions by dispersing and dissolving an odochromic substance in a solvent and impregnating it, and the treated plastic substrate is coated with sio, SiO2, At2o, .

A method of depositing ZrO□ is disclosed. Although this technology is excellent in improving the above-mentioned drawbacks, problems remain in terms of wear resistance and heat resistance. In other words, in terms of improving heat resistance, abrasion resistance, and impact resistance, silicon-based materials are more effective than when inorganic materials are deposited due to the large difference in thermal expansion coefficient between the plastic base material and the vapor-deposited material, problems with adhesion, etc. It is a well-known technique in the eyeglass lens industry that a hard coat or a silicone hard coat is applied and then an antireflection layer made of an inorganic material is deposited on top of it.

Further, the present inventors proposed a synthetic resin photochromic lens using tetraalkyl silicate or the like in place of Aljy in the present invention, but a drawback was found in terms of pot life.

In view of the above-mentioned points, the present inventors have developed a photochromic function that develops a dark brown color upon irradiation with light and reversibly returns to a colorless or pale color in a dark place, and has a material that is hard-wearing, wear-resistant, and durable. To obtain a synthetic resin photochromic lens with excellent properties
As a result of my research, I came up with the invention described below.

That is, the present invention is 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.

L Colloidal silica 2b with a particle size of 1 to 100 mμ B, General formula R1α-s'j-(OR3), -a-b
(However, R1 is vinyl, amine, imino, epoxy, (
(meta) 7 An organic group containing at least one selected from cryloxy, phenyl, and SH group, hydrogen, carbon number 1 to 6
(halogenated) hydrocarbon group, R3 is a hydrocarbon group having 1 to 5 carbon atoms, an alkoxyalkyl group, or a carbon number 1 to 4
acyl group, α is 0.1 or 2, b is 0.1 or 2
A hydrolyzate of one or more silicon compounds represented by α+b≦2).

Next, the coating of the present invention is a penzobilirosbin compound represented by Each component constituting the composition will be described.

The colloidal silica having a particle size of 1 to 100 millimicrons as component A refers to a product in which a high molecular weight anhydrous silica is dispersed in a dispersion medium such as water, alcohol, or cellosolve, and is produced by a well-known method and commercially available. It is something that exists.

Particles having a particle size of 5 to 40 mμ are particularly useful in the practice of the present invention. Ingredient A is an important component for improving the abrasion resistance and durability of the coating.Iron-forming compounds are essential components for improving the adhesion, removability, and abrasion resistance of the coating. Methoxysilane, vinyltriethoxysilane,
Vinyltriacetoxysilane, r-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, r-glycidoxyfuropylmethyldimethoxysilane, β-glycidoxy Ethyltrimethoxysilane, β-(
3,4-Epoxycyclohexyl)ethyltrimethoxysilane, r-(3,a-epoxycyclohexyl)ethyltrimethoxysilane, r-(meth)acryloxyfurobyltrimethoxysilane, r-(ip)acryloxypropylmethyl dimethoxine, phenyltrimethoxysilane, r-mercaptopropyltrimethoxysilane,
Phenyltriacetoxysilane, r-chloropropyltrimethoxysilane, β-cyanoethyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, detraproboxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltrimethoxysilane, methyltrimethoxysilane propoxysilane, methyltriptoxysilane,
Examples include ethyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, dimethyljethoxysilane, and phenylmethyljethoxysilane. 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 compound B is used without hydrolysis, the abrasion resistance is insufficient.Also, when two or more silicon compounds are used without hydrolysis, they must be hydrolyzed separately and mixed. In many cases, better results are obtained by mixing and co-hydrolyzing at the same time than by co-hydrolyzing.Additionally, some of the hydroxyl groups produced by hydrolysis exist in a condensed form, but this does not affect the effects of the present invention. .

A specific example of the C component exhibiting photochromic properties is as follows.

1.3.3-) dimethylindolino-6-ditropenzopyrillospirane, 1,3.3-) rifthylindolino-5-chloro-6'-nitropenzopyrillospirane, 1
,5.3-trimethylindolino-6'-nitro8'
-methoxybenzobilirosvirane, 1,3,3-trimethylindolino-7'-nitropenzobilirospiran,
1,3.3-trimethylindolino-8-bromobenzopyrillospirane, 1,3.3-trimethylindolino-6'-totro 8'-fluorobenzopyrillospirane, 1°3.3-) samethylindolino-6-promo 8'-nitropenzopyryloshirane, j, 3,5-) dimethylindolino-5-nitro-8'-methoxybenzobilirosbilane, 1,3,3-trimethylindolino-8 Examples include benzobirilosvirane i such as -methoxybenzobilirosvirane.

These photochromic compositions exhibit remarkable improvement in deterioration resistance in coating compositions consisting of the above-mentioned components A and B.

In the present invention, it was possible to obtain gray, brown, and various other colors that could not be obtained with organic 11S compounds, which were a matter of the degree of photochromism.

This problem can be solved by dissolving one or more components C in a coating composition consisting of components A and B in an arbitrary ratio.

For example, to obtain a dark brown color, use 1,3,3-trimethylindolino 8-bromo-b'--j lomobenzopyrylosvira, 1,3,3-)limethylidolino 7'-nitrobenpyrylosviran , 1,3,3-drimethylindolinoda-12tro-8'methoxybenzopyrylosbilane in a weight ratio of 3:1:2. In addition, colors that could not be obtained by a single method, in addition to claim 1 (C), include G, H, Bro.
It can be obtained by optionally mixing photo-colored spiropyrans described in "Wnr Photochromi-8m". Furthermore, by dyeing the lens base material, a desired color can be obtained even before irradiation with light.

In addition, if necessary, alkali metal salts of carboxylic acids such as sodium acetate, amine carboxylates such as acetic acid, nolamine, quaternary ammonium carboxylates such as tetramethylammonium acetate, and triethylamine, glycine pyridine, alkali hydroxide, etc. Honorarium catalyst and BF3゜BnCj14. EJnO12kl
Lewis acids such as ot, or Plainstead acids,
Aluminum chelate compound.

It is effective to use other metal chelate compounds and epoxy curing catalysts such as ammonium perchlorate.

Various solvents, surfactants, thixotropic agents, ultraviolet absorbers, antioxidants, and various polymers can be added to improve coating work and impart necessary properties as a paint. 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 a mixed solvent of two or more of these solvents can be used. It is also possible to use it as

The composition of the present invention can be applied to a synthetic resin lens by any of the well-known methods such as a dipping method, a spray method, a nuvin method, a coating method, and a flow coating method. The synthetic resin lens coated in this manner becomes a cured film by heating and drying.

Conditions such as heating temperature and heating time are determined based on the characteristics of #-t#J fat, but a temperature of 60 to 150° C. is usually applied.

It is preferable that the resulting cured film has a thickness Fi of 1 to 60 μm; if it is less than 1 μm, satisfactory abrasion resistance cannot be obtained, and in order to maintain the required properties, the thickness of the photochromic material must be I have no choice but to limit the amount. On the contrary, it is more than 30μ! ! Even if the film is thickened, no effect can be expected from increasing the film thickness, and cracks are likely to occur.

In order to improve the adhesion between the synthetic resin lens and the coating composition, the lens surface may be pretreated with various primers, activated gas treatment, acid, alkali, etc. in the practice of the present invention. Useful.

The coating composition thus obtained is applied to the lens surface of a transparent resin such as polycarbonate resin, acrylic resin, 0R-39 resin, polystyrene, etc.
Transparency 0 surface hardness, wear resistance.

It is possible to provide a synthetic resin photochromic lens with excellent durability, photochromic properties, and photochromic properties.

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

The coating was evaluated using the method shown below.

Photochromic performance by visually inspecting the lens surface: Photochromic lens dimming, lens tester HE-223 (manufactured by Hasegawa Wabiko Co., Ltd.) was used, and the average light attenuation rate in the visible range was 60 coefficients or higher in one test. I thought it was good.

Abrasion resistance: A load of IK9 was applied with #0000 Nutile wool, and 9 surfaces were rubbed in 10 reciprocations, and the degree of scratches was divided into the following grades: A: Almost no scratches B: Some scratches or The eyes were cross-carmeted, a cellophane adhesive tape was attached thereon, 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 100°C.

Chemical resistance: Equinol, acetone, 1% sulfur, acid aqueous solution,
After being immersed in an aqueous IJ solution for 244 hours, the state of the coating was visually inspected.

Example 1 (1) Preparation and application of paint r-glycidoxyprobyltrimethoxysilane 57Nf
Part k, ethanol-dispersed colloidal silica medium Kasei Kogyo 08CAL-1232' solid content concentration 30%)
10 parts by weight of 0.05N acetic acid was added dropwise at once to a solution consisting of 40 parts by weight of 112 Chungei xy-2-methylglobanol, and the mixture was stirred at room temperature for 1 hour. This solution niflow control agent (Nippon Unicar eηg)"L-7001
') was added in an amount of 0.03 part by weight. Further, as a light modulating component, 1,3,3-)11methylindolino-8-promo-6'-furomobenzovirirosvirane 18x parts, 1,
3.3-trimethyl'indolino 7'-nitrobenzopyrillosbin 0.6 p part, 1.3.3-'l-limethylindolino 5'-nitro8'-methoxybenzopyrylospirane 1.2 parts by weight was added and stirred at room temperature for 1 hour to form a coating solution. This coating liquid was applied to a lens made of (!R-39) by a dipping method at a speed of 15 CIrVrnin,
It was cured by heating in a 707G hot air dryer for 1 hour and then at 90°C for 2 hours. The thickness of the obtained film was 2.3 μm. The characteristics of the lens are shown in Table 1.

Example 2 51 parts by weight of vinyltrimethoxysilane, colloidal silica dispersed in inpropyl alcohol (manufactured by Catalysts & Chemicals Co., Ltd.)
8OAL-1432' solid content concentration 50m) 86 parts by weight,
0.05M in a solution of 90 parts by weight of methyl sexolp
Hydrochloric acid was gradually added dropwise, and the mixture was stirred at room temperature for 1 hour. Add a flow control agent (“I” manufactured by Nippon Unicar ■) to this solution.
, -7604') and add 0.06 parts by weight. In addition, the light modulating component and 1,3゜3-trimethylindolino-6
'-Nitropensobi+70subin 2-3 parts by weight, 1,3.
3-1 Limethylindolino-5'-nitro 81-methoxybenzopyry 0262215 was added and stirred at room temperature for 1 hour. This coating liquid was applied to polycarbonate sunglasses using the dipping method at a speed of 20 LyrVrn, in, and dried in a hot air dryer at 70°C for 30 minutes, and then at 100°C for 1 hour.
It was heated and cured for 30 minutes. The thickness of the obtained film is 1d3
It was μm. Characteristics 1' of the lens are shown in Table 1.

Comparative Examples 3 and 4 Comparative Examples 3 and 4 were conducted under the same conditions except for the dimming component of Example 1.2.

Claims (1)

[Claims] (1) Synthetic resin photochromic lens vinyl, amine, imino, characterized by being coated and cured with a coating composition containing the following A, B, and O as main components.
Epoxy, (meth)7cryloxy, phenyl and 8H
R2 is hydrogen, a (halogenated) hydrocarbon group having 1 to 6 carbon atoms, R is a hydrocarbon group having 1 to 5 carbon atoms, an alkoxyalkyl group, or an organic group containing at least one selected from the group consisting of 1 to 6 carbon atoms; 4 acyl group, α is 0.1 and Vi2,
bha, 1 or Tri2, and a hydrolyzate of one or more silicon compounds represented by a+b≦2). A benzopyrillospyran compound represented by the general formula C1 (wherein R' is hydrogen, fluorine, chlorine, and bromine; R11B represents at least one selected from hydrogen, fluorine, chlorine, bromine, a nitro group, and a methoxy group).