JPH0323882B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD The present invention relates to a synthetic resin lens having a hard coat layer made of a synthetic resin film on the surface of a synthetic resin lens substrate. "Prior Art and its Problems" In recent years, synthetic resins have begun to be used in optical products such as lenses. Synthetic resin lenses have advantages over glass lenses, such as being lightweight, easy to process, easy to dye, and have excellent impact resistance, but on the other hand, they have a major drawback of being easily scratched. For this reason, many methods for improving the scratch resistance of synthetic resin lenses have been studied, and can be roughly divided into two methods. One method is to form an inorganic hard coat film on the surface of a synthetic resin lens by vacuum evaporation, sputtering, ion plating, etc., and the other is to form an acrylic hard coat film on the surface of a synthetic resin lens. ,
This is a method of forming an organic hard coat film such as a melamine-based or silicon-based film by a dip coating method, a spray coating method, or the like. However, inorganic coating films have the disadvantage that impact resistance and heat resistance are significantly reduced when they are provided with both hard coating and antireflection coating properties. On the other hand, organic hard coat films do not reduce impact resistance even if they are thick enough to provide scratch resistance, but they do not have an antireflection function by themselves. Products with an inorganic antireflection film formed on a coat film are commercially available. However, these synthetic resin lenses also have the disadvantage that their heat resistance and impact resistance are reduced due to the introduction of an inorganic coating layer, and furthermore, their dyeability is also lost. ``Object of the Invention'' The object of the present invention is to solve the problems of the prior art described above, and to provide a synthetic resin lens that has excellent heat resistance, impact resistance, scratch resistance, and antireflection ability, and can be dyed. It is in. "Structure of the Invention" The synthetic resin lens of the present invention has a refractive index of 1.49 to 1.65.
On the surface of a synthetic resin lens substrate of general formula aR ₂ -Si-(OR ₁ ) _4-a ... [wherein R ₁ represents a methyl group, ethyl group, propyl group or hydrogen, and R ₂ represents an amino group] , epoxy group,
represents an organic group containing at least one of a vinyl group and a methacryloxy group, and a represents an integer of 0 to 3] as a main component, and as a refractive index adjusting agent, the general formula (YO) _o TiX _n ... [In the formula, Y represents an alkoxy group having 1 to 12 carbon atoms or an ethylenedioxy group, X represents a hydroxyl group-containing phosphite group or a hydroxyl group-containing pyrophosphate group, and n is an integer of 1 to 4 and m represents 2 or 3] or the formula Contains γ-anilinopropyltrimethoxysilane represented by
It is characterized by having a hard coat layer made of a synthetic resin film of m. Furthermore, the synthetic resin lens of the present invention has a refractive index of
The hard coat layer is provided on the surface of a synthetic resin lens substrate with a thickness of 1.49 to 1.65, and the thickness of each layer is 60 to 60.
It may be provided with an antireflection layer consisting of a 150 nm single layer or multilayer synthetic resin film. In this way, by providing a hard coat layer made of a synthetic resin film with a refractive index difference of within ±0.06 from the synthetic resin lens substrate and a film thickness of 0.5 to 10 μm, heat resistance and impact resistance are reduced. It is possible to maintain good antireflection ability without causing damage, and to provide sufficient scratch resistance without losing dyeability. Furthermore, by providing an antireflection layer also made of a synthetic resin film on the hard coat layer, it is possible to improve the antireflection ability and prevent loss of dyeability. The present invention will be explained in more detail below. As shown in FIG. 1, the synthetic resin lens of the present invention includes a hard coat layer 12 and an antireflection layer 13 formed on the surface of a synthetic resin lens substrate 11. Note that the synthetic resin lens of the present invention may be one in which only the hard coat layer 12 is formed on the surface of the synthetic resin lens substrate 11. The synthetic resin lens substrate 11 has a refractive index of 1.49 to 1.65.
For example, a resin (refractive index 1.600) prepared by copolymerizing 70 parts by weight of tribromophenyl methacrylate, 20 parts by weight of styrene, and 10 parts by weight of ethylene glycol dimethacrylate using benzoyl peroxide as an initiator is preferably used. be able to.
Note that the synthetic resin lens substrate 11 can be of various shapes as well as one having irregularities, and may be a flat plate such as a filter, for example. As the hard coat layer 12, a synthetic resin film having a refractive index difference within ±0.06 with respect to the synthetic resin lens substrate 11 and a film thickness of 0.5 to 10 μm is used. In this case, synthetic resin lens substrate 1
If the difference in refractive index from 1 is greater than ±0.06, interference colors will become noticeable and the image as a lens will be impaired. Further, if the film thickness is less than 0.5 μm, sufficient effect on scratch resistance cannot be obtained, and if it is thicker than 10 μm, a problem arises in that stress between the lens substrate and the synthetic resin film increases. As the antireflection layer 13, each film thickness is 60 to 150n.
A single layer or multilayer synthetic resin film of m is used, and each film may have a thickness of 60 to 150 nm as long as it satisfies the antireflection condition. As the synthetic resin films of the hard coat layer 12 and the antireflection layer 13, those whose main component is an organic silane compound represented by the above general formula are used. More preferable compositions for such a synthetic resin film include (A) an organic silane compound represented by the above general formula, (B) a colloidal silica sol with a particle size of 1 to 100 nm, (C) an acidic aqueous solution, and (D) curing. It consists of a mixed solution of one or two of maleic anhydride and dibutyltin dilaurylate as a catalyst, and when the total of the above components (A), (B) and (C) is 100 parts by weight, component (A) is A composition containing 10 to 50 parts by weight of component (B), 40 to 85 parts by weight of component (C), 1 to 10 parts by weight of component (D), and 0.01 to 5.0 parts by weight of component (D) can be used. In the above, examples of the organic silane compound represented by the general formula of component (A) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-
Examples include epoxycyclohexyl)ethyltrimethoxysilane. As mentioned above, the blending amount of component (A) is preferably 10 to 50 parts by weight when the total of components (A), (B), and (C) is 100 parts by weight. (A) Ingredients
If the amount of component (A) is less than 10 parts by weight, the adhesion between the coating film and the lens will decrease, and if the component (A) exceeds 50 parts by weight, the wettability of the coating liquid onto the lens will deteriorate, and furthermore, the dyeability will decrease. Component (B) is colloidal silica dispersed in a solvent. In this case, as a dispersion solvent for colloidal silica, for example, water, methanol, ethanol, butanol, normal propanol, ethyl cellosolve, ethylene glycol, isopropyl alcohol, etc. are used, and alcohols are particularly preferred. The blending amount of component (B) is preferably 40 to 85 parts by weight when the total of components (A), (B), and (C) is 100 parts by weight. By adjusting this blending ratio, it is possible to control the refractive index when forming the synthetic resin film. Component (C) is used to hydrolyze the compound represented by the general formula of component (A). Examples of the acidic aqueous solution of component (C) include phosphoric acid, acetic acid, nitric acid, sulfuric acid, and hydrochloric acid, and an aqueous solution with a pH of 1 to 4 is preferable. The blending amount of component (C) is preferably 1 to 10 parts by weight, when the total of components (A), (B), and (C) is 100 parts by weight. If the amount of component (C) is less than 1 part by weight, the compound of the above general formula will not be sufficiently hydrolyzed, and the coated film will be prone to cracks. Furthermore, if the amount of component (C) exceeds 10 parts by weight, the dyeability and wettability will decrease. Component (D), a curing catalyst, is added to improve the storage stability of the coating liquid. As the curing catalyst for component (D), maleic anhydride, dibutyltin laurylate, etc. can be used. The blending amount of component (D) is preferably 0.01 to 5.0 parts by weight when the total of components (A), (B), and (C) is 100 parts by weight. A synthetic resin film having the above composition is especially used for hard coat layer 1.
2, it is necessary to adjust its refractive index so that the difference in refractive index with the synthetic resin lens substrate 11 is within ±0.06. Therefore, when using a synthetic resin film having the above composition particularly as the hard coat layer 12, a film obtained by adding the above organic titanate or γ-anilinopropyltrimethoxysilane as a refractive index adjusting agent. It is preferable to adjust the refractive index so that it falls within the above range. In the present invention, the organic titanate used as a refractive index adjusting agent has the general formula (YO) _o TiX _n ... [wherein, Y represents an alkoxy group or ethylenedioxy group having 1 to 12 carbon atoms, and X represents represents a hydroxyl group-containing phosphite group or a hydroxyl group-containing pyrophosphate group, n represents an integer of 1 to 4, and m represents 2 or 3]. Examples of the compound represented by the above general formula include tetraoctyl bis _{( ditridecylphosphite} ) titanate of the formula ( _C8H17O ) _-4Ti [-P(O- _C13H27 ) _2OH ] ₂ . ,formula Tetra(2,2-diallyloxymethyl-1-
butyl)bis(ditridecylphosphite) titanate, formula Bis(dioctylpyrophosphate) ethylene titanate, formula Isopropyl tri(dioctylpyrophosphate) titanate, formula Examples include tetraisopropylbis(dioctylphosphite) titanate. In the present invention, metal alkoxides such as titanium butoxide, aluminum butoxide, zirconium butoxide, niobium butoxide, titanium propoxide, aluminum propoxide, zirconium poloxide are used together with the above-mentioned organic titanates or γ-anilinopropyltrimethoxysilanes. It is also possible to use one type or a combination of two or more types. These metal alkoxides are added after preparing a solution using acetic acid esters, acid solutions, and the like. In this case, as the acetate ester, one or more types such as ethyl acetate, butyl acetate, methyl acetate, etc. can be used, and as the acid solution, propionic acid, phthalic acid, isophthalic acid, terephthalic acid, hydrochloric acid, etc. One or more of these can be used. The above refractive index adjusting agent may be added to the composition of the synthetic resin film in an amount of 60 parts by weight or less, when the total of the components (A), (B), and (C) is 100 parts by weight. preferable. The synthetic resin film of the antireflection layer 13 is as follows:
Those containing fluoroalkylsilane as a main component can also be used. Examples of such fluoroalkylsilanes include the following. CF ₃ CH ₂ CH ₂ Si (OMe) ₃ CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OMe) ₃ CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OMe) ₃ Hard coat layer 12, antireflection The layer 13 can be formed by applying a coating liquid having the composition as described above onto the surface of the synthetic lens substrate 11 by a dip coating method, a spray coating method, or the like, and then heating and curing the coating liquid. and,
These hard coat layer 12 and antireflection layer 1
3, it is possible to stain the membrane after forming it. "Embodiments of the Invention" Example 1 () 35 parts by weight of γ-glycidoxypropyltrimethoxysilane, 50 parts by weight of methanol silica sol (manufactured by Catalysts & Chemicals, OSCAL1132), 10 parts by weight of 0.01N hydrochloric acid, 5 parts by weight of maleic anhydride The components were mixed and reacted at room temperature for 24 hours to prepare a coating solution for an antireflection layer. The refractive index evaluated from the spectral characteristics after application of this coating liquid was 1.48.
It was hot. () 35 parts by weight of γ-glycidoxypropyltrimethoxysilane, 50 parts by weight of methanol silica sol, 10 parts by weight of 0.01N hydrochloric acid, 5 parts by weight of maleic anhydride
To 100 parts by weight of mixture (A), add tetraisopropyl bis(dioctyl phosphite) titanate (trade name "Plenact 41B", Ajinomoto
Co., Ltd.) was added to prepare a coating liquid for a hard coat layer. The refractive index evaluated from the spectral characteristics after application of this coating liquid was 1.57.
It was hot. The synthetic resin lens substrate used was a product obtained by copolymerizing 70 parts by weight of tribromophenyl methacrylate, 20 parts by weight of styrene, and 10 parts by weight of ethylene glycol dimethacrylate using benzoyl peroxide as an initiator (refractive index of 1600). . This synthetic resin lens substrate is cleaned in advance,
First, apply the coating liquid () for the hard coat layer.
Dip coat at 12cm/min pulling speed, 80℃
It was made to harden for 1 hour to form a hard coat layer. Next, dip coat the anti-reflection layer coating liquid () at a pulling speed of 6 cm/min.
An antireflection layer was formed by curing at 120°C for 3 hours.
The thickness of the hard coat layer was 2 μm, and the thickness of the antireflection layer was 85 nm. The spectral characteristics of this synthetic resin lens due to reflection are shown in FIG. Example 2 γ-glycidoxypropyltrimethoxysilane
35 parts by weight, methanol silica sol 50 parts by weight, 0.01
To 100 parts by weight of a mixture (A) of 10 parts by weight of normal hydrochloric acid and 5 parts by weight of maleic anhydride, 30 parts by weight of tetraoctyl bis(ditridecylphosphite) titanate (trade name "Plenact 46B", manufactured by Ajinomoto Co., Inc.) was added. A coating liquid for a hard coat layer was prepared. The refractive index evaluated from the spectral characteristics after application of this coating liquid was 1.57. A synthetic resin lens substrate with a refractive index of 1.60 similar to that in Example 1 was cleaned in advance, and the hard coat layer coating solution was dip coated at a pulling speed of 12 cm/min and cured at 80°C for 30 minutes to form the hard coat layer. Formed. Further, the antireflection layer coating liquid () of Example 1 was dip coated at a pulling rate of 6 cm/min, and cured at 120° C. for 3 hours to form an antireflection layer. The thickness of the hard coat layer was 2 μm, and the thickness of the antireflection layer was 85 nm. The spectral characteristics due to reflection of this synthetic resin lens were similar to those shown in FIG. Example 3 A synthetic resin lens substrate with a refractive index of 1.60 similar to that in Example 1 was cleaned in advance, and the hard coat layer coating solution () of Example 1 was dip coated at a pulling speed of 13 cm/min, and then heated at 70°C for 50 minutes. It was cured to form a hard coat layer. Furthermore, 1,
A coating solution for antireflection layer mixed with 2 parts by weight of 1,1-trifluoropropyltrimethoxysilane and 98 parts by weight of methanol was dip coated at a pulling speed of 6 cm/min, and cured at 120°C for 3 hours to form the antireflection layer. was formed. The thickness of the hard coat layer is 2μm, the refractive index is 1.57, and the thickness of the antireflection layer is 100n.
m, and the refractive index was 1.38. The spectral characteristics of this synthetic resin lens are shown in FIG. Example 4 A synthetic resin lens substrate with a refractive index of 1.60 similar to Example 1 was cleaned in advance, and the hard coat layer coating solution of Example 2 was dip coated at a pulling speed of 12 cm/min, and cured at 80°C for 30 minutes. A hard coat layer was formed. Furthermore, 1, 1, 1
- An anti-reflective layer coating solution containing 2 parts by weight of trifluoropropyltrimethoxysilane and 98 parts by weight of methanol was dip coated at a pulling speed of 6 cm/min and cured at 120°C for 3 hours to form an anti-reflective layer. . Hard coat layer thickness is 2μ
m, refractive index is 1.57, anti-reflection layer thickness is 100 nm,
The refractive index was 1.38. The spectral characteristics of this synthetic resin lens were similar to those shown in FIG. Example 5 Formula 65 parts by weight of γ-anilinopropyltrimethoxysilane, isopropyl alcohol silica sol (manufactured by Catalysts Kasei Kogyo, trade name "OSCAL1432")
130 parts by weight, 20 parts by weight of 0.01N hydrochloric acid, ethyl acetate
30 parts by weight of propionic acid, 30 parts by weight of propionic acid, and 2 parts by weight of silicone surfactant were mixed and reacted at room temperature for 16 hours to prepare a coating liquid for a hard coat layer. The refractive index of this coating liquid was 1.582 as evaluated by the spectral characteristics of the coating liquid. A synthetic resin lens substrate with a refractive index of 1.60 similar to that in Example 1 was cleaned in advance, and the hard coat layer coating solution was dip coated at a pulling speed of 1.2 cm/min and cured at 100°C for 5 hours to form the hard coat layer. Formed. The thickness of the hard coat layer is
It was 3 μm and had a refractive index of 1.582. The spectral characteristics of this synthetic resin lens due to reflection are shown in FIG. Example 6 A synthetic resin lens substrate with a refractive index of 1.60 similar to that in Example 1 was cleaned in advance, and the hard coat layer coating solution of Example 5 was dip coated at a pulling rate of 1.2 cm/min, and cured at 100°C for 5 hours. In this way, a hard coat layer was formed. Furthermore, 3 parts of a coating liquid for an anti-reflection layer was mixed with 2 parts by weight of fluoroalkylsilane [CF ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , manufactured by Toshiba Silicon Corporation] and 98 parts by weight of methanol.
Dip coat at a pulling speed of cm/min, 120
The antireflection layer was formed by curing at ℃ for 1 hour. The thickness of the hard coat layer is 3.5μm, the refractive index is 1.582,
The antireflection layer had a thickness of 98 nm and a refractive index of 1.40. The spectral characteristics of this synthetic resin lens due to reflection are shown in FIG. Comparative Example 1 On a synthetic resin lens substrate with a refractive index of 1.60 similar to that in Example 1, the hard coat layer coating liquid () of Example 1 was dip coated and cured at 80°C for 1 hour to form a hard coat layer. . moreover,
On this hard coat layer, by vacuum evaporation method,
Y ₂ O ₃ , TiO ₂ , and SiO ₂ were laminated in order to each have a thickness of λ/4 wavelength (λ=520) to form an antireflection layer. The hard coat layer had a refractive index of 1.57 and a film thickness of 2 μm. Comparative Example 2 On a synthetic resin lens substrate with a refractive index of 1.60 similar to that in Example 1, the antireflection layer coating liquid () of Example 1 was directly dip-coated at a pulling rate of 6 cm/min, and the coating was heated at a temperature of 120°C. It was cured for 3 hours to form an antireflection layer. This antireflection layer had a refractive index of 1.48 and a film thickness of 130 nm. Next, Table 1 shows the characteristics of the synthetic resin lenses obtained in Examples 1 to 6 and Comparative Examples 1 and 2. The test method for the characteristic values determined in Table 1 is as follows. (1) Adhesion After coating a synthetic resin lens substrate, 100 stitches were cross-cut at 1 mm intervals, and cellophane tape was removed three times to measure the number of stitches remaining in the coating during the 100 stitches. (2) Scratch resistance The coating surface was abraded 50 times with #0000 steel wool under a load of 1 kg to examine its resistance to scratches. A
indicates no scratches, B indicates slight scratches, and C indicates severe scratches. (3) Dyeability A coated synthetic resin lens is immersed in a dye bath at 90°C for 5 minutes, and it is considered good if the light attenuation rate at 550 nm is 20% or more. ○
indicates that the dyeability is good, Δ indicates that the dyeability is somewhat difficult, and × indicates that the dyeability is extremely difficult. (4) Heat resistance After a synthetic resin lens substrate was coated, a test was repeated three times in which it was left in a 100°C oven for 10 minutes and at room temperature for 10 minutes, and cracks in the formed film were evaluated. A: No cracks are observed; B: cracks are partially observed; C:
indicates that cracks are observed on the entire surface.

[Table] As is clear from Table 1, the synthetic resin lenses of Examples 1 to 6 have excellent adhesion, scratch resistance, stainability, and heat resistance, and also meet eyeglass specifications in terms of antireflection function. It was hot. "Effects of the Invention" As explained above, the synthetic resin lens of the present invention satisfies scratch resistance and antireflection functions, and
It has excellent heat resistance and impact resistance. Further, by providing an antireflection layer made of a synthetic resin film further above the hard coat layer, the antireflection function is further improved and dyeing becomes possible even after the antireflection layer is formed. Furthermore, since the synthetic resin film can be formed by a dip coating method, a spin coating method, etc., it is also excellent in mass production.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view schematically showing a synthetic resin lens of the present invention, and FIGS. 2, 3, 4, and 5 are spectral characteristics due to reflection of synthetic resin lenses obtained in Examples of the present invention. This is a chart showing the following. In the figure, 11 is a synthetic resin lens substrate, 12 is a hard coat layer, and 13 is an antireflection layer.

Claims (1)

[Claims] 1. On the surface of a synthetic resin lens substrate with a refractive index of 1.49 to 1.65, a compound having the general formula aR ₂ −Si−(OR ₁ ) _4-a ... [wherein R ₁ is a methyl group or an ethyl group] , represents a propyl group or hydrogen, R ₂ is an amino group, an epoxy group,
represents an organic group containing at least one of a vinyl group and a methacryloxy group, and a represents an integer of 0 to 3] as a main component, and as a refractive index adjusting agent, the general formula (YO) _o TiX _n [In the formula, Y represents an alkoxy group having 1 to 12 carbon atoms or an ethylenedioxy group, X represents a hydroxyl group-containing phosphite group or a hydroxyl group-containing pyrophosphate group, and n represents an integer of 1 to 4. , m represents 2 or 3], and has a refractive index difference within ±0.06 with the synthetic resin lens substrate, and has a film thickness of 0.5 to 10 μm. A synthetic resin lens characterized by having a coating layer. 2 On top of the hard coat layer, the film thickness of each layer is
The synthetic resin lens according to claim 1, which is provided with an antireflection layer consisting of a single layer or multilayer synthetic resin film of 60 to 150 nm. 3. On the surface of a synthetic resin lens substrate with a refractive index of 1.49 to 1.65, a compound of the general formula aR ₂ −Si−(OR ₁ ) _4-a ... [wherein R ₁ is a methyl group, ethyl group, propyl group, or hydrogen and R ₂ is an amino group, an epoxy group,
represents an organic group containing at least one of a vinyl group and a methacryloxy group, and a represents an integer of 0 to 3] as a main component, and contains as a refractive index adjusting agent an organic silane compound represented by the formula Contains γ-anilinopropyltrimethoxysilane represented by
A synthetic resin lens characterized by having a hard coat layer made of a synthetic resin film of m. 4. The synthetic resin lens according to claim 3, further comprising an antireflection layer made of a single layer or multilayer synthetic resin film, each layer having a thickness of 60 to 150 nm, on the hard coat layer.