JPH067203B2 - Method for producing glass lens having dye-cured surface layer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a colored glass lens, and more particularly to a method for producing a colored glass lens having a dye-cured surface layer.

[Conventional technology]

Glass lenses for spectacles have excellent physical properties such as a surface having a high hardness, being hard to be scratched, and being small in deformation due to rigidity so that a thin shape can be maintained. However, when compared with synthetic resin (for example, diethylene glycol bisallyl carbonate) lenses, they have the drawback of being difficult to dye.

As a method for coloring a glass lens, a method of adhering a coloring substance to the surface of the glass lens by vacuum deposition or the like, a method of mixing a coloring substance during the melting step of glass lens production to give the glass composition itself a coloring property, and A method of providing a polymer film on the concave surface of a glass lens and dyeing with a disperse dye, which is disclosed in Japanese Patent Laid-Open No. 60-90422, has been proposed.

[Problems to be solved by the invention]

In the former two methods of directly coloring glass, there are problems that the coloring substance is limited and it is not possible to produce a free color, the coloring density is limited, and the coloring requires a complicated manufacturing process and sophisticated technology. was there.

In the latter method of providing a polymer coating on the surface and dyeing, a polymer having sufficient film hardness and satisfying the conditions that the film performance such as film hardness and adhesion does not change before and after dyeing. A coating composition and a surface treatment method have not been found, and further, in a coating film containing an epoxy-containing alkoxysilane, colloidal silica, etc. as a main component, in a disperse dye usually used for dyeing plastic lenses for the eyes,
There was a problem that dyeing was difficult.

[Means for solving problems]

 The present invention solves the above problems.

That is, the present invention, (a) a step of preparing an organic hard film solution containing a hydrolysis-condensation product shown below as a main component, (b) a step of applying the organic hard film solution to a glass lens surface and curing the same, and (c) dyeing the glass lens having a cured surface layer obtained in step (b) at a temperature of 40 to 100 ° C. using a dye bath of a cationic dye having a concentration of 0.001 to 5% by weight. The present invention also relates to a method for producing a glass lens having a characteristic dye-cured surface layer.

General formula (1) [However, R ₁ is an alkyl group having 1 to 4 carbon atoms, R ₂ is an alkyl group having 1 to 4 carbon atoms, —CH═CH ₂ , _{NH 2, -CH 2 CH 2 CH} 2 NHCH 2 CH 2 NH 2
Is an organic group selected from. ] At least one hydrolysis-condensation product of an alkoxysilane represented by or at least one of the above alkoxysilanes
Species and general formula (2) [However, R ₄ is an alkyl group having 1 to ₄ carbon atoms] Hydrolyzate of alkoxysilane or colloidal silica.

The organic hard film solution used in the present invention comprises the above-mentioned hydrolysis condensate as a main component, a curing agent and a solvent.

The alkoxysilane represented by the general formula (1) in the present invention, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycid Xypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane,
Phenyltriethoxysilane, cyclohexyltrimethoxysilane, γ-aminopropyltriethoxysilane,
N- (β-aminoethyl) -γ-aminopropyltrimethogsysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-
Examples thereof include chloropropylmethoxysilane and γ-mercaptopropyltriethoxysilane.

Examples of the alkoxysilane represented by the general formula (2) include tetramethoxysilane and tetraethoxysilane.

As the colloidal silica, those having a particle size of 5 mμ to 30 mμ dispersed in water or alcohol are preferable.

Hydrochloric acid and acetic acid are preferable as the acid for hydrolyzing these alkoxysilanes.

As the curing agent used in the organic hard film solution containing alkoxysilane or colloidal silica as a main component, there are imidazole derivatives and the like, but acetylacetone metal salt is particularly effective.

The addition amount thereof is an amount sufficient to cure a hydrolyzed condensate of an organosilicon compound of colloidal silica and an alkoxysilane, for example, 1 mol in total of hydrolyzed condensate of colloidal silica (SiO ₂ conversion) and alkoxysilane. On the other hand, it is 1 to 10 g.

Examples of the solvent used for the organic hard film solution include lower alcohols, esters, ethers, ketones, and the like, with isopropyl alcohol, butanol, methyl celloflube and the like being particularly preferable.

A silicone-based surfactant may be added to the organic hard film solution, that is, the coating liquid, for the purpose of improving the smoothness of the coating film. Further, for the purpose of improving weather resistance or preventing deterioration of the coating film, it is possible to add an ultraviolet absorber, an antioxidant or the like.

Further, various additives may be added for the purpose of improving practicality such as adhesion to glass lenses and improvement of physical properties.

Further, it is not preferable to add sodium acetate, which is generally used as a catalyst for stabilizing the pH of the coating solution and as a catalyst. The reason is that sodium acetate tends to precipitate toward the film surface after coating and curing the coating composition, which adversely affects the film formation of the vapor deposition material, and the lens surface must be cleaned by hand-wiping or washing before vapor deposition. Even if it is present, it is deposited during vacuum or heating, and similarly has an adverse effect.

Examples of the coating method for coating and curing the silicone-based organic hard film solution on the surface of the glass lens include a dipping and pulling method (a dipping method), a spin coater method, a roll coater method and a spray method which are generally used. .

Curing of the surface film is mainly performed by heat treatment.
The heating temperature can be in a wide range, but is preferably 40 to 150 ° C, particularly preferably 80 to 120 ° C. Good results are obtained with heating times of 1 to 4 hours or more.

Before applying the coating liquid, it is preferable to pretreat the plastic lens by alkali treatment, plasma treatment, ultraviolet irradiation treatment, or the like.

The organic hard coat film obtained by the heat curing treatment is
It has excellent abrasion resistance (hardness), flexibility (flexibility), weather resistance, and chemical resistance (alkali resistance).

As the cationic dye used in the present invention for dyeing the organic hard film, all so-called cationic dyes can be used. Cationic dyes are those that are distinguished by basic dyes, especially those with excellent dyeability and fastness to acrylic fibers, which are generally referred to as cationic dyes, and their onium groups and color resonance systems are conjugated. It is roughly classified into a conjugated type and an insulated type depending on whether it is present or not.

(a) In the conjugated type, a positive charge is distributed throughout the dye matrix, and a quaternary ammonium group is contained in a chain of conjugated double bonds.

(Example) CIYellow 11: CIBlue 54: CIRed 13: CIBlue 3: Most of the cationic dyes, including conventional basic dyes, belong to this group and are characterized by their beautiful hue and high tinting strength.

(b) Insulation type is one in which the positive charge is unevenly distributed locally on the dye matrix, and the quaternary ammonium group is attached to the end of the disperse dye. Is a structure introduced.

(Example) The color tone is similar to that of disperse dyes, and many of them are particularly high in fastness even in a light color, and are often used for dyeing medium-light colors and intermediate colors.

Examples of commercially available products include the following.

Aizen Cathilon (Hodogaya) Diacryl (Mitsubishi) Sumiacryl (Sumitomo) Kayacryl (Nikka) Astrazon (FBY) Maxilon (CG) Basacryl (BASF) The preferred dye concentration in the dyeing bath is 0.001-5% by weight, Is used at 40 ° C to 100 ° C. 0.001
If the concentration is less than wt%, the dyeing speed is too slow for practical use,
When it exceeds 5% by weight, the dye tends to stick to the surface to be dyed, and the concentration dependency of the dyeing speed is almost eliminated, so that it is practically impossible to mix the dye to produce the desired color. At a dyeing temperature of less than 40 ° C, the dyeing speed is too slow, and it is not necessary to exceed 100 ° C.

As the material of the glass lens used in the present invention, any inorganic glass having ordinary glass lens characteristics such as surface accuracy, surface cleanliness and heat resistance can be used, and the hard film of the present invention can be coated. For example, commonly used UV glass (mainly containing silicon oxide, boron oxide, sodium oxide, potassium oxide, magnesium oxide, calcium oxide, barium oxide, lead oxide, cerium oxide, etc.) and a lens with a higher refractive index ( LHI-II lens,
Hoya Co., Ltd.'s silicon oxide, titanium oxide, sodium oxide, potassium oxide and the like) are preferably used.

The hard coat film thickness is preferably 0.1 to 10 μ, particularly 1 to 10 μm.
5μ is preferable. If the film thickness is too thick, it affects the optical surface of the lens, and problems such as image distortion and aberration tend to occur, and dyeing time becomes long, which causes a problem in productivity. Also, 0.1μ
If it is less than the above range, a dyeing layer is formed in the film, so that it is difficult to obtain a suitable dyeing density and color, which is not preferable.

〔Example〕

Production Example 1 Production of Organic Hard Film Solution 472 parts by weight of γ-glycidoxypropyltrimethoxysilane, 2.0 parts by weight of 0.5N hydrochloric acid, 20 parts by weight of acetic acid, 100 parts by weight of water were stirred at room temperature for 8 hours at room temperature. Left for 16 hours. Add 12 parts of isopropyl alcohol to this hydrolysis solution.
0 parts by weight, butyl alcohol 120 parts by weight, aluminum acetylacetone 16 parts by weight, silicone surfactant 0.2
By weight, 0.1 part by weight of an ultraviolet absorber was added, and the mixture was stirred for 8 hours and aged at room temperature for 24 hours to obtain a coating composition.

Production Example 2 Production of Hard Film-Coated Lens The coating composition obtained in Production Example 1 was applied to LHI-II.
A hard coat lens was obtained by coating the surface of a lens (high refractive index glass lens manufactured by HOYA Co., Ltd.) by a dipping and pulling method, followed by heat curing at 110 ° C. for 2 hours. The film thickness was 3μ.

Example 1 Dyeing of hard film-coated lens Three hard film-coated lenses obtained in Production Example 2 were prepared as follows.
Dyes were dyed with an aqueous solution of 0.1 g / of the cationic dyes 1 to 3 and 1 of water at 80 ° C. for 10 minutes.

The spectral transmittance curves are shown in FIG.

No. 1: Diacryl Yellow Au-N manufactured by Mitsubishi Kasei Co., Ltd., No. 2: Diacryl Red Au-N manufactured by Mitsubishi Kasei Co., Ltd., No. 3: Diacryl Blue Au-N manufactured by Mitsubishi Kasei Co., Ltd.

Example 2 An example of dyeing by mixing red, yellow and blue primary color dyes will be described. Generally, all colors can be freely produced by mixing the three primary color dyes.

No.4: Compounded dye (green) Diacryl Yellow Au-N 0.2g Diacryl Blue Au-N 0.2g Water 1 No.5: Compounded dye (in case of gray) Diacryl Yellow 0.2g Diacryl Red 0.13g Diacryl Blue 0.2g Water 1 Using the compounded dye, the lens of Production Example 2 at 80 ° C
Stained for 10 minutes. The spectral transmittance curve is shown in FIG.
Curve 4 shows No. 4 and curve 5 shows No. 5.

Example 3 The hard film-coated lens obtained in Production Example 2 was coated with Diacryl Re
Dyeing was performed by changing the dye concentration and dyeing temperature of the dye bath using d Au-N, and the transmittance of the product at 540 nm is shown in Table 1.

Example 4 The coating composition obtained in Production Example 1 was applied to the surface of a UV lens (crown gas) by a dipping and pulling method, and 110
A hard lens was obtained by heating and curing at 2 ° C for 2 hours. Film thickness is 3
It was μ.

Next, three hard lenses obtained by the above method were dyed with a cationic dye of 0.1 g / water 1 at 80 ° C. for 10 minutes. The spectral transmission curves are shown in Fig. 3 in order of No.
Shown by 0 and 11.

No. 9: Mitsubishi Kasei Co., Ltd. Diacryl Yellow AU-N, No. 10: Mitsubishi Kasei Co., Ltd. Diacryl Red AU-N, No. 11: Mitsubishi Kasei Co., Ltd. Diacryl Blue AU-N.

The spectral transmittance curves shown in FIGS. 1 to 3 show that the dyes are dyed in a dark color by the absorption at the wavelength of each color.

The results of the performance test after dyeing the coating film in the examples are shown in Table 2.

The performance test of the coating film of the example was carried out as follows.

(a) Abrasion resistance # 0000 with steel wool applied surface 200g
Then, the abrasion resistance was judged by rubbing 1000 times (reciprocating) as follows.

A: Almost no scratches.

B: A little scratched.

C: Many scratches.

D: Film peeling occurs.

(b) Adhesiveness In accordance with JIS-Z-1522, 10 × 10 goggles were made, and a peeling test was performed 3 times with cellophane adhesive tape, and the number of gobangs remaining was examined.

(c) A plastic lens dyed by coating and curing the coating composition of the present invention was placed in a constant temperature oven having heat resistance and hot water resistance of 150 ° C., and it was examined whether or not the coating film had cracks.

It was immersed in boiling water for 1 hour and examined for changes due to appearance.

〔The invention's effect〕

According to the method of the present invention, glass lenses having various color densities can be easily obtained.

[Brief description of drawings]

FIGS. 1, 2, and 3 show spectral transmittance curves of glass lenses having a dye-cured surface layer according to an example of the present invention.

Claims (1)

[Claims] 1. A step of (a) preparing an organic hard film solution containing a hydrolysis-condensation product as a main component shown below, (b) a step of applying the organic hard film solution to a glass lens surface and curing the same, and ( c) dyeing the glass lens having the cured surface layer obtained in step (b) at a temperature of 40 to 100 ° C. using a dye bath of a cationic dye having a concentration of 0.001 to 5% by weight And a method for producing a glass lens having a dye-cured surface layer. General formula (1) [However, R ₁ is an alkyl group having 1 to 4 carbon atoms, R ₂ is an alkyl group having 1 to 4 carbon atoms, —CH═CH ₂ , -CH ₂ CH ₂ CH ₂ SH, _{-CH 2 CH 2 CH 2 NH 2} , an organic group selected from _{-CH 2 CH 2 CH 2 NHCH 2} CH 2 NH 2. ] At least one hydrolysis-condensation product of an alkoxysilane represented by or at least one of the above alkoxysilanes and a general formula (2) [Wherein R ₄ is an alkyl group having 1 to ₄ carbon atoms], which is a hydrolyzed condensate of alkoxysilane or colloidal silica.