JPS59214002A - Synthetic resin photochromic lens - Google Patents

Abstract

PURPOSE:To enhance abrasion resistance, chemical resistance, weather resistance, dimming performance, etc. by forming a coating layer having dimming function and high hardness. CONSTITUTION:A 1-30mum thick hardened film is formed by coating a lens with a compsn. consisting of (A) a hydrolyzate of a silicon compd. represented by formula I (R<1> is an org. group having at least one of vinyl, epoxy, etc.; R<2> is H, 1-6C hydrocarbon group, or vinyl R<3> is 1-5 hydrocarbon group, alkoxylalkyl, or the like; and (a) is 0-2, (b) is 0 or 1, and a+b<=2), (B) a hydrolyzate of a silicon compd. represented by formula II (R<6> is a 1-5C hydrocarbon group or alkoxyalkyl; R<7> is H or 1-5C hydrocarbon group; and (c) is 0-3, (d) is 0-2, and c+d=3), (C) silver halide, such as silver bromide, and (D) a hardening catalyst, such as ammonium perchlorate.

Description

[Detailed description of the invention] The present invention has a synthetic resin lens surface (modeled with light control function).
Concerning light control lenses made of synthetic resin that have excellent surface properties such as abrasion resistance, chemical resistance, hot water resistance, heat resistance, weather resistance, dyeability, and light control properties by applying a high-hardness coating film. It is something.

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 in place of inorganic glass. In our country, the share of plastic lenses is increasing year by year, and 3
It is also said to be 0chi. In addition to the safety, lightness, and fashionability (dyeability) of a commercial product, many manufacturers are conducting research to add functions such as anti-reflective coating, hard coating, and anti-reflective coating. This is thought to be due to the fact that they were commercialized one after another. On the other hand, the market share of lenses made of dielene glycol bisallyl carbonate (CR-a 9) resin, which is the mainstream of plastic lenses, is said to be 50 inches in the United States, and after reaching 50%, growth has almost stopped. It is said. This is thought to be due to the fact that the CR-39 lens is more easily scratched compared to the glass, and also because the CR-39 lens does not have a photochromic lens with an excellent dimming function. 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 can be said for photochromic lenses made of thermoplastic resin. On the other hand, the main consumer demand for coloring photochromic lenses is to change from colorless to dark 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 invention has excellent wear resistance, chemical resistance,
The present invention was achieved as a result of repeated research in order to obtain a synthetic resin photochromic lens having excellent surface properties such as hot water resistance, heat resistance, weather resistance, dyeability, and light control properties.

That is, the present invention relates to a synthetic resin photochromic lens coated with a coating composition composed of the following components A, B, C, and D.

A, at least one type selected from one or more hydrolyzed silicon compounds represented by the general formula (Tassoshi R1 is vinyl, amine, imi-4-), epoxy, methacryloxy, phenyl, and SH group; Contains organic groups.

R1 is hydrogen, a hydrocarbon group having 1 to 6 carbon atoms, or a vinyl group; Ha is a hydrocarbon group having 1 to 5 carbon atoms, an alkoxyalkyl group, or an acyl group having 1 to 4 carbon atoms; α is 0.1 or 2. b is O or 1, and α+b≦2).

B, a hydrolyzate of one or more silicon compounds represented by the general formula (wherein R1 is a hydrocarbon group having 1 to 5 carbon atoms or an alkoxyalkyl group; R1 is hydrogen or a hydrocarbon group having 1 to 5 carbon atoms); group, C is an integer of 0 to 3, d is an integer of 0 to 2, and 2 is C+
d=3).

C, silver halide, curing catalyst In the present invention, the above-mentioned A, B, C, and D are essential components, and if any of the above components is missing, the object of the present invention cannot be achieved.

Next, each component constituting the coating composition of the present invention will be described.

The silicon compound of component A is an important component for improving wear resistance, strong chemical resistance, hot water resistance, and weather resistance. Methoxysion,
γ-Aminebrobyltrimethoxysilone, γ-glycidoxybrobyltrimethoxysilane, r-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β-glycidoxyethyltrimethoxysilane , β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane, γ-
Methacryloxybrobyltrimethoxysilone, r-methacryloxybrobylmethyldimethoxysilone, phenyltrimethoxysilone, γ-methylcaptopropyltrimethoxysilane, tetramethoxysilane, tetho6-ethoxysilane, tethobroboxyone, tethobutoxysilane , methyltrimethoxysilone.

Methyltriethoxysilone, methyltribroboxylon, methyltributoxysilone, ethyltrimethoxysilane, ethyltriethoxysilane.

Propyltriethoxysilone, butyltriethoxysilone, etc. can be used.

The silicon compound of component B is an important component for improving dyeability, weather resistance, hot water resistance, and chemical resistance. In many cases, molecules with long molecular chains are introduced into the hard coat layer to widen the intermolecular distance of the hard coat layer, to provide dispersibility and dyeability of component C, which will be described later, and to add hydrolyzed silanol at the end of the molecule. When the group is dehydrated and condensed with the hydrolyzed silanol of the silane compound of component A, it is stably fixed in the hard coat layer, resulting in a coating film with excellent durability.

Specific examples of component B include bis(trimethoxysilylpropyl)epoxysuccinate, bis(triethoxysilylpropyl)epoxysuccinate, bis(tripropoxysilylpropyl)e7-boxysuccinate, bis(methyldimethoxysilyl) Pyrfeboxysuccinate, bis(methyljethoxysilylpropyl)epoxysuccinate, bis(methyldipropoxysilylpropyl)epoxysuccinate, bis(ethyljethoxysilylpropyl)epoxysuccinate, bis(ethyljethoxysilylpropyl)epoxysuccinate, bis(methyljethoxysilylpropyl)epoxysuccinate, bis(ethyljethoxysilylpropyl)epoxysuccinate, Toxysilylprovir)
Epoxysuccinate, Bis(propyldimethoxysilylpropyl)epoxysuccinate, Bis(dimethylmethoxysilylpropyl)epoxysuccinate, His(
Examples include dimethylethoxysilylprobyl) epoxysuccinate, bis(diethylmethoxysilylprobyl)epoxysuccinate, and the like.

As is well known, the above-mentioned silane compounds A and B can be 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 be obtained easily. In addition, the silane compounds A and B may each be used in the form of 1s or a mixture of two or more types, or those in which the corresponding alkoxy group has been hydrolyzed in advance,
Or -8 partially dehydrated and condensed are essentially equivalent, and even if they are included, the same effect can be obtained.

Examples of the silver halide for C include silver bromide, silver chloride, silver iodide, and mixtures of two or more thereof, with silver bromide being preferred.

In addition to the above components, monovalent or divalent metal ions can also be added.

The curing catalyst for component D is hydrochloric acid, sulfuric acid, phosphoric acid, sulfonic acid, perchloric acid, ammonium perchlorate. , Lewis acids and their complexes such as antimony pentachloride and titanium tetrachloride, sodium acetate, zinc nanthenate,
Organic metal salts such as tin octylate, metal borofluorides such as zinc borofluoride, boric acid esters such as ethyl borate, titanate esters, aluminum chelate compounds such as aluminum acetylacetonate, metals such as titanium, cobalt, zirconium, etc.* (2) compounds, oxygenated metal halides, n-butylamine, and amines such as imidazole.

9- Examples of solvents that may be included in the coating composition include alcohols, ketones, esters, ethers, selonlubes, halides, carboxylic acids, and aromatic compounds, and one or more of these may be used. It can be used as a mixed solvent of two or more types. Also, if necessary,
These are compatible organic polymers and ultraviolet absorbers,
By adding surfactants and flow control agents, it is possible to impart leveling properties, viscosity, coating properties, light resistance, etc. necessary for paints.

The coating solution consisting of components A, B, C:, D, solvents, and other additives can be applied to synthetic resin lenses by dipping, spraying, spin coating, and 7-day coating. Laminated using the method used,
It becomes a hardened film by heating and curing. The heating temperature and heating time are determined by the characteristics of the base lens and the coating liquid. The thickness of the cured film obtained is preferably 1 to 30μ, and 1
If the thickness is less than 3lO-0μ, satisfactory abrasion resistance cannot be obtained and it is difficult to fully demonstrate the performance of the coating. I can't wait.

The thus obtained coating composition 1d is coated on the lens surface made of transparent resin such as polycarbonate resin, acrylic resin, CR-39 resin, polystyrene, etc., and has excellent transparency and light control performance, and is useful for practical use. It is possible to obtain a synthetic resin photochromic lens having the necessary scratch resistance, durability, and dyeability with disperse dyes.

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. Furthermore, the following method was used to evaluate the film.

The surface of the silens was inspected by visual inspection.

Lightfastness: 50 on Canon Long Wife Fade Meter
The state of the film after 0 hours of exposure was examined.

Light control performance: Photochromic lens light control lens f
1-HH-223 ()-manufactured by Segawa Picault Co., Ltd.) was used, 1
Those with an average light attenuation rate of 30 or more in the visible range in multiple tests were considered good.

Abrasion resistance: A load of 1 fly was applied with Su0000 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: No burns occur within the area of 1 m x 3 crn.

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 remains due to scratches on the surface.

Adhesion of coating film: Based on cross-cut tape test.

That is, cross-cut with a knife on the surface of the coating, and
1.Draw 100 squares of 1 piece of paper, attach adhesive tape on top of it, peel off the tape, and make 100 squares.
The number of squares that did not peel off among the squares was shown.

Hot water resistance: The appearance of the coating after immersion in boiling water for 1 hour was inspected, and an abrasion resistance test was conducted.

Chemical resistance: The state of the film was examined after being immersed in 95% ethanol for 24 hours.

Dyeability with disperse dyes: Tetowo Silk Works B (manufactured by Ciba Geigy) 2F with 85℃ warm water 1! The lens was immersed in this solution for 5 minutes, and the average light attenuation rate in the visible range was 2.
5% or more was considered good.

Example 1 (1) Hydrolysis of γ-glycidoxypropyltrimethoxysilone, tethomethoxysilone, bis(methyldimethoxysilylprobyl)epoxysuccinate.

Tethomethoxysilone 62 was added in a reactor equipped with a stirring device.
Part, γ-glycidoxypropyltrimethoxysion 41
1 part, 21 parts of bis(methyldimethoxysilylprobyl) epoxy succinate, 103 parts of isopropyl alcohol, and 0.1 part of silicone surfactant, and with vigorous stirring, 52 parts of 0.05N hydrochloric acid aqueous solution was added at room temperature to add water. After decomposition, stirring was continued for an additional hour at room temperature. Thereafter, stirring was stopped and the mixture was aged at room temperature overnight.

[2] Preparation of paint and application Add ammonia perchlorate 13 to the hydrolyzate obtained in (1).
- 40.08 parts were added and stirred at room temperature for 30 minutes, and further 70 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. This coating liquid was applied to a CR-39 lens by a dipping method at a pulling rate of 20 cm/sin, and heated and cured in a hot air dryer at 80°C for 30 minutes and then at 120°C for 90 minutes. After curing, the film had a pale yellow tinge, but was transparent and had a thickness of 7.5 μm. Table 1 shows the characteristics of the obtained lens.

Example 2 148 parts of γ-glycidoxypropyltrimethoxysilone, 76 parts of bis(triethoxysilylpropyl)epoxysuccinate, 200 parts of ethyl cellosolve, 0.2 parts of silicone surfactant at room temperature, 0.0 IN Nitric acid aqueous solution 5
A hydrolyzate of γ-glycidoxypropyltrimethoxysilone and bis(triethoxysilylpropyl)epoxysuccinate was obtained in the same manner as in Example 1 except for adding 7 parts. Next, 0.8 parts of stannous chloride was added to this solution, and the mixture was stirred at room temperature for 30 minutes. Furthermore, 20 parts of 14-iodide of 50 to 100 nμ and 20 parts of silver bromide were dispersed, and the mixture was heated with a homogenizer at 200 rpm. The mixture was mixed for 1 hour to form a paint. The obtained coating liquid was immersed in a polycarbonate bath under the same conditions as in Example 1, and was dried and cured. The obtained lens was transparent with a slight yellowish tinge, and the thickness of the coating was 7 μm.

Table 1 shows the characteristics of the obtained lens.

1

Claims (1)

[Claims] (11) A synthetic resin photochromic lens coated with a coating composition containing the following components A, B, C, and D. A, a silicon compound represented by the general formula an organic group containing at least one type selected from one or more hydrolysates of (V, R1 is vinyl, Aξ), imino, epoxy, methacryloxy, phenyl, and 13H group. R1 is hydrogen, A carbon hydrogen group having 1 to 6 carbon atoms, or a vinyl group, R''tj a hydrocarbon group having 1 to 5 carbon atoms, an alkoxyalkyl group or an acyl group having 1 to 4 carbon atoms, αll1O,
1 or 2. b is 0 to 1, and α+b≦2). 1-B, hydrolyzate of one or more silicon compounds represented by the general formula (C, where R4 is a hydrocarbon group having 1 to 5 carbon atoms, an alkoxyalkyl group), R'Fi hydrogen, 1 carbon number ~5 hydrocarbons, C is an integer from 0 to 3, dFi. C+d=3).・C, silver halide, curing catalyst