JPS6053938A - Photochromic plastic lens - Google Patents

Abstract

PURPOSE:To provide high surface hardness, wear resistance and durability to a lens and to produce a significant antireflection effect while maintaining the superior photochromism by coating the surface of the lens with a specified coating composition, curing the composition, and forming a single-layered or multilayered antireflection film on the lens. CONSTITUTION:The surface 10 of a lens is coated with a coating composition 11 consisting essentially of colloidal silica of 1-100mmu particle size, a compound represented by formula I (where R<1> is vinyl, amino, imino, epoxy, (meth)acryloxy, phenyl, SH or the like, R<2> is H, 1-6C hydrocarbon or the like, and R3 is 1- 5C hydrocarbon, alkoxyalkyl or 1-4C acyl) and a compound represented by formula II (where each of R<4> and R<5> is H-, F-, Br-, NO2- or the like). After curing the composition, a single-layered or multilayered antireflection film 12, 13, 14 is formed on the lens. It is preferable that the lens is treated with a primer before coating with the coating composition. On the thin antireflection film is formed on the composition, so superior water resistance, hot water resistance and shock resistance are provided, and the film has high adhesive strength.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photochromic lens made of a synthetic resin lid, which has a monolayer or multilayer antireflection coating on a coated Bu layer that has 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 5.
It is said that it has exceeded aLf6. In addition to the advantages of plastic materials such as safety, lightness, fashionability, and ease of processing, anti-reflective coating, hard coating,
This is thought to be because many manufacturers have researched and commercialized all types of products one after another to add functions such as hard anti-reflection coatings, waterproof properties, and high refractive index resins. On the other hand, lenses made from diethylene glycol bisallyl carbonate (hereinafter referred to as 0R-39), the mainstream plastic lens, have a market share of approximately 50% in the United States.
%, the growth slows down and is said to be in mourning. This is thought to be due to the ease of scratching compared to the glass of the R-69 lens, and the lack of an excellent photochromic lens in the 0R-39 lens. Currently, this is the only photochromic lens that changes color to blue. are commercially available, but there are problems with their functionality (light attenuation rate, coloring speed, and fading speed.) - Consumers' desire for coloring of photochromic lenses changes from colorless to brown or gray due to light absorption. The changes are overwhelming.It would be an exaggeration to say that there are no synthetic resin photochromic lenses that can handle 9A.

Also, from a technical point of view, the wear resistance and durability of plastic materials
Research on improving photochromic performance and materials that exhibit photochromic performance have been conducted individually and many proposals have been made, but no research has been conducted that comprehensively considers both.
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 abrasion resistance (IE) of plastic materials are JP-A-50-40674, JP-A-51-42752, JP-A-52-1126.98, and JP-A-53-11ff. RoS6, JP 56-99263, U
It is disclosed in SF-3,986,997 and the like.

-Technology related to photochromic materials (lenses) is
JP 45-12716, JP 45-28B95, JP 46-1106, JP 48-89179, JP 51-45541, JP 52-152887, JP 54-955, JP 54- 1108'54, Japanese Patent Publication No. 5
5-1214'12, Tokuko Sho 57-39244, Tokuko Sho! 57-55747, Japanese Patent Application Laid-Open No. 57-36645, and the like. In order to impart photochromic properties to plastic resin materials using these technologies, molecules that exhibit photochromic properties consisting of organic or inorganic compounds are added to plastic materials, or they are bonded to polymer chains, or they are thermally brought into contact with them. Methods have been taken to either move the material or to laminate it in a resin, but in either case the wear resistance is poor and it 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 photochromic molecules are uniformly distributed in the lens material, a concentration gradient will necessarily occur in the light attenuation rate due to color development.

In addition, when a casting method such as 0R-39 is used, most of the 7-otochromic molecules are deactivated by peroxides such as diisopropyl peroxydicarbonate, which is commonly used. In this method, it is difficult to achieve a uniform transition, and unevenness tends to occur, and defects are also likely to occur on the lens surface.

Japanese Patent Laid-Open No. 58-34457 describes a method of imparting a photochromic function by dissolving the entire photochromic substance in a solvent and impregnating it, and SiO, 5i02 is applied to the treated plastic substrate.

All! 203, a method for depositing ZrO2f is disclosed.

This technology is an excellent technology that improves the various drawbacks mentioned above, but in order to improve wear resistance, it is necessary to provide a thick inorganic hard coat film, which results in poor heat resistance and
There are problems with hot water resistance, impact resistance, etc. Furthermore, in terms of improving heat resistance, etc., due to the large difference in thermal expansion coefficient between the plastic base material and the vapor deposition material, and problems with adhesion, etc.
It is well known in the eyewear industry that it is better to apply an anti-reflection layer made of an inorganic material on top of a silicone hard coat than to deposit only an inorganic material. be.

In addition, the present inventors, in place of the A component in the present invention,
A photochromic lens made of synthetic resin using tetraalkyl silicate was proposed, but a drawback was found in terms of pot life.

In view of the above, the present inventors have developed a material that has a photochromic function that develops a brown color when exposed to light and becomes colorless or light-colored reversibly in the dark, and has a high surface hardness, abrasion resistance, durability, and reflectivity. As a result of research to obtain a photochromic lens made of synthetic resin with excellent prevention effects, the invention described below was achieved.

That is, the present invention provides a photochromic lens made of synthetic resin, characterized in that a single-layer or multi-layer antireflection film is provided on the lens surface completely coated and cured with a coating composition containing the following A, B, and C as main components. It is related to.

A1 A hydrolyzate of one or more silicon compounds consisting of colloidal silica having a particle size of 1 to 100 mμ. (However, R1 is vinyl, amine, or imino.

Organic groups comprising at least species among epoxy, (meth)acryloxy, phenyl and BH groups. R2 is hydrogen or a ()/logenated) hydrocarbon group having 1 to 6 carbon atoms. R3
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 0, 1 or 2°, b is 0, 1 or 2, and a + b≦2.

C3 general formula A benzopyrillospyran compound represented by

(In the formula, R4 is hydrogen, fluorine, chlorine, and bromine.

R6 represents at least one type selected from hydrogen, fluorine, chlorine, bromine, nitro group and methoxy group. ) Next, each component constituting the coating composition of the present invention will be described.

Component A, colloidal silica with a particle size of 1 to 100 millimeters, is a product in which a high molecular weight anhydrous silica is dispersed in a dispersion medium such as water, alcohol, or selonlube, and is manufactured 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.

Component A is a silicon compound that is important for improving the abrasion resistance and durability of the coating.A silicon compound is an essential component for improving the adhesion, flexibility, and abrasion resistance of the coating.A specific example is vinyltrimethoxysilane. , vinyltriethoxysilane, vinyltriacetoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ
-Glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropyltrimethoxysilane, β-(6゜4-epoxycyclohexyl)ethyltrimethoxysilane, γ-
(3,4-epoxycyclohexyl)ethyl trime 1-
i-disilane, γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, phenyltrimethoxysilane,
γ-mercaptopropyltrimethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, β-cyanoethyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyl Triethoxysilane, methyltripropoxy 7rane.

Examples include methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, dimethyljethoxysilane, and phenylmethyljethoxysilane. Hydrolysis of these silane compounds is carried out by a well-known method in a mixed solvent such as water and alcohol in the presence of an acid. When compound B is used without water decomposition at the cutting edge, the wear resistance is insufficient. In addition, when using two or more types of silicon compounds after total hydrolysis, rather than hydrolyzing them separately and mixing them,
Is it better to mix and co-hydrolyze at the same time? There is a lot to gain. Further, although hydroxyl groups generated by hydrolysis exist in a partially condensed form, this does not affect the effects of the present invention.

Specific examples of the C component exhibiting photochromic properties are 1.3.
3-trimethylindolino-6'-nitrobenzopyrillospiran, 1,3.3-trimethylindolino-5-chloro-6-nitropenzopyrrillospiran, 1,3.3
-) dimethylindolino-6'-2) o -8' -
) Toxybenzopyrillospirane, 1,3.3-1-limethylindolino-7'-nitrobenzopyrillospirane, i
, 3.3-trimethylindolino-8-bromobenzopyrylospirane l'13+3-trimethylindolino-6
'-nitro8'-fluorobenzopyrylospirane, 1
゜6.3-trimethylindolino-6'-bromo8'
-Nitrobenzopyrillospiran, 1',3,3-trimethylindolino-5'-nitro81-methoxybenzopyrrillospiran, 1.3,3-1su,methy/l'indolino-8'-methoxybenzo Examples include benzopyrillospirans such as pyrillosvirane.

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

With the present invention, we were able to obtain grays, browns, and various other colors that could not be obtained with organic compounds due to the problem of photochromism. C
This problem can be solved by dissolving one or more components in a desired ratio in a coating composition consisting of components A and B.

For example, to obtain a dark brown color, 1,3,3-trimethylindolino 8-bromo-6'-bromobenzopyrylosvira, 1,3,3-)limethylindolino 7'-nitrobenvirillospirane , 1.3.3-trimethylindolino-5'-nitro-8'-methoxybenzobilillospirane are mixed in a weight ratio of 3:1:2.

In addition, colors that could not be obtained by a single method can be obtained by using [Ph
It can be obtained by arbitrarily mixing all of the photo-colored spiropyrans described in otochr-onoismJ. 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 ethanolamine acetate, quaternary ammonium carboxylates such as tetramethylammonium acetate, and triethylamine, glycine pyridine, alkali hydroxide, etc. condensation catalysts, BF3, SnO/, 5nOJ,
It is effective to use a Lewis acid such as .

Various solvents, surfactants, chirotroping agents, ultraviolet absorbers, antioxidants and various polymers can be added to improve the coating process and provide all the 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 more of these solvents can be used as a mixed solvent. It is also possible to use

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 form a cured film.

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 30 microns. If it is less than 1μ, satisfactory wear resistance cannot be obtained, and in order to maintain all the required characteristics,
There is no choice but to limit the amount of photochromic substances. On the other hand, even if the thickness is 30 μm or more, no effect can be expected from increasing the film thickness, and cracks are likely to occur.

In order to improve the density between the synthetic resin lens and the coating composition, the lens surface 1) is treated with various primers, activated gas treatment, acid, alkali, etc.
Pre-caking treatments are useful in the practice of this 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 + OR39 resin, or polystyrene.
Transparency 9 surface hardness, wear resistance.

A synthetic resin photochromic lens with excellent durability and photochromic performance can be provided.

In the present invention, an antireflection film is provided on the coating film thus obtained. Part 1: To take advantage of the above-mentioned characteristics of the coating film, and to further reduce reflection on the lens surface, metal oxides, metal nitrides, metal oxynitrides, metal carbides, metal fluorides, etc. are added to the coating film to further reduce reflection on the lens surface. A single-layer or multi-layer antireflection coating consisting of a transparent inorganic dielectric layer was provided.

The coating film of the present invention is an organic material, and only a thin anti-reflection film is provided on it, so the drawbacks of conventional products such as poor heat resistance, hot water resistance, impact resistance, etc. are improved. There is. Furthermore, if the density between the coating film and the anti-reflection film is not good, it is not possible to improve the scratch resistance, etc., and problems such as cracks occur during the etching process. By selecting all the antireflection film materials on the coating film according to the components of the coating film of the present invention, an antireflection film with good adhesion can be obtained.

The antireflection layer uses silicon dioxide, magnesium fluoride, etc. as a low refractive index material, and metal oxides such as titanium oxide, zirconium oxide, tantalium pentoxide, etc., or silicon nitride as a high refractive index material.

A nitride such as aluminum nitride may be used, and an oxide or oxynitride such as yttrium oxide, ytterium oxide, or aluminum oxide may be used as the intermediate refractive index material. The antireflection film can be formed by vacuum evaporation, sputtering, ion blasting, or the like.

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

The coating was evaluated using the method shown below.

Photochromic performance: Using a photochromic lens dimming lens tester HE7223 (manufactured by Hasegawa Picor Co., Ltd.), those with an average light attenuation factor of 60 or more in the visible range in one test were considered to be good.

Abrasion resistance: +oooo A load of 1 kg was applied with steel wool, the surface was rubbed 10 times, and the degree of scratching was divided into the following grades and evaluated.

A: Almost no scratches B: Some scratches C: Severe scratches Adhesion of the coating film: In the so-called cross-cut tape test, the surface of the coating film was tested with a knife at 1-meg interval in vertical and horizontal directions. Insert the parallel lines of the book, cross-cut 100 squares, apply cellophane adhesive tape on top of it, peel off the tape completely, and display the number of squares that do not peel out of the 100 squares. .

Hot water resistance Visually check the condition of the coated film after immersing it in hot water at 280℃ for 1 hour! I looked into it.

Heat Resistance: The state of the film was visually inspected after being stored in a hot air drying oven at 90° C. for 1 hour.

Rigid chemicals: ethanol, acetone, 1% sulfuric acid bath solution, 0
．． After being immersed in a 5% sodium hydroxide water bath for 24 hours, the condition of the film was visually examined.

Example 1 (1) Preparation and application of paint 37 parts by weight of γ-glycidoxyprobyltrimethoxysilane, ethanol-dispersed colloidal silica (catalyst chemical industry)
Manufactured by "08OAL-1232" solid content concentration 30%) 112
A total of 10 parts by weight of OO5N acetic acid was added dropwise at once to a solution consisting of 40 parts by weight of 2-methylpropanol, and the mixture was stirred at room temperature for 1 hour. A flow control agent ("L-7001" manufactured by Nippon Unicar ■) ff was added to this solution.

003 heavy plan Shigekane Naeta. Furthermore, as a dimming component, 1.3
．． 3-) Limethylindolino-8-glomo-6'-!
1.8 parts by weight of lomobenzopyrylohyran.

1,3.3-trimethylindolino-7'-ditrobenzopyrylospirane 0.6 weight m+ 1', s, s=
1.2 parts by weight of nitrimethylindolino-57-nitro-8'-methoxybenzopyrrillospiran was added and stirred at room temperature for 1 hour to obtain a coating solution. This coated giOR-39 lens was coated by dipping at a pulling rate of 15 tm/IE+I+, and heated and cured in a hot air dryer at 70°C for 1 hour and then at 90°C for 2 hours. The thickness of the resulting coating was 2.6 μm.

On the coating film obtained as above, Yb, 0
．． 'i optical film thickness n a= ”/a + T &-2o
, k n d =”/2 r8i0. to na-re4
The entire structure was coated with an anti-reflection film by sequential vacuum deposition. The overall membrane structure is shown in FIG.

The spectral reflectance characteristics of one surface of this lens are shown in FIG. 21. 20 in FIG. 2 is the spectral reflectance characteristic when no antireflection film is provided. The properties of the obtained lens are shown in the table.

Example 2 51 parts by weight of vinyltrimethoxysilane, isopropyl alcohol-dispersed colloidal silica (manufactured by Catalysts & Chemicals Industry Co., Ltd.)
0EICAD-1432” solid content concentration 60%) 86
0.05N hydrochloric acid was gradually added dropwise to a solution consisting of 1 part by weight + 9.0 parts by weight of methylseron rub, and the mixture was stirred at room temperature for 1 hour. To this solution, 0.06 parts by weight of a flow control agent ("L 7604" manufactured by Nippon Unicar) was added. In addition, as a light modulating component, 1.5.3-) rimetherindolino 67-nitrobenzopyrillospiran hexafold i part, 1,3.3-trimethylindolino-5'-nitro-
1.5 parts by weight of 87-medoxybenzobilillospiran was stirred at room temperature for 1 hour. This coating liquid was applied to polycarbonate sunglasses by the dipping method at a pulling rate of 20α/opening, and heated and cured in a hot air dryer at 70° C. for 30 minutes and then at 10° C. for 1 hour and 60 minutes. The thickness of the obtained film was 3
Friends who meet in μm.

A603 was applied as an anti-reflection film on the coating film obtained as described above, with an optical thickness of n d = ”/a *Ion blating was performed in argon plasma to give a thickness of 1 cm. Chrome '1n
A layer of d=0.01 was sequentially vacuum-deposited, and 1% Mg was applied thereon at na=λ/4. Ion silating was performed in argon plasma. Based on this film structure, Figure 5 shows the spectral reflectance %.
Notes are shown in Figure 661. The properties of the obtained lens are shown in the table.

Comparative Examples 3 and 4 Except for the dimming component of Examples 1 and 2, the other conditions were the same. Comparative Example 3.4 was used.

Table a) Shows the results of shore abrasion resistance after testing (hot water resistance, heat resistance).

[Brief explanation of drawings]

FIG. 1 shows the membrane structure of Example 1. 10 is 0R-39
Made of lens, 11 is photochromic, Tsuku coating film, 121'1Y1) to 3.13 is Ta206+14
Fs, S10. and 12 forces λ et 1475Z anti-reflection IIu. FIG. 2 shows the spectral reflection custom made 21 of one surface of the example lunches, and 20 is the spectral reflectance % when no antireflection film is provided. Similarly, the horizontal @ represents the wavelength of light, and the vertical axis represents the reflectance. FIG. 6 shows the membrane structure of Example 2. 3D
I': I polycarbonate lens, 31 is photochromic coated IL 32 is I'JJrzOB
HS 5idZrO,, S 4 is Or, 55 fl
MgF2f is shown, and 32 to 35 are antireflection films. FIG. 4 shows the spectral reflectance customization 41 of one surface of the implementation v12 lens. Applicant: Suwa Kozue Kosha Co., Ltd. Agent Patent Attorney No. 11 Tono V Moxibustion (nm) No. 31 Tono + (nm)

Claims (1)

[Scope of Claim] A synthetic resin photochromic lens containing all of the following components A, B, and C. A. A hydrolyzate of one or more colloidal silicon compounds having a particle size of 1 to 100 mμ. (However, R1 is vinyl, amine, imino. Ephoxy, (meth)acryloxy, phenyl and FIH
An organic group containing at least one type of group. R2 is hydrogen or a (halogenated) hydrocarbon group having 1 to 6 carbon atoms. R3
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 0,1 or 2; b is Q, 1 or 2, and a is ≦2) A benzobyrillospyran compound represented by the general formula C1. (In the formula, R4 represents hydrogen, fluorine, chlorine, and bromine, and R5 represents at least one metal selected from hydrogen, fluorine, chlorine, bromine, nitro group, and metquine group.)