JPH01219701A - Synthetic resin lens - Google Patents

Abstract

PURPOSE:To provide a synthetic resin lens which is increased in refractive index, is decreased in coloration and is improved in durability by forming a thin resin film consisting of a specific component, cured silicone film and antireflection layer successively on the surface of the synthetic resin lens obtd. by copolymerizing two comonomers consisting of specific compsns. CONSTITUTION:The thin resin film of 0.1-2mum thickness essentially consisting of a copolymer C of an acrylic and/or methacrylic compd. and arom. vinyl compd. is provided on the surface of the synthetic resin lens obtd. by copolymerizing the comonomers essentially consisting of >=one kinds of the monomers A expressed by general formula I and >=one kinds of the monomers B expressed by general formula II. The compsn. essentially consisting of the hydrolyzate and/or partial condensation product D of one or >=two kinds of the silane compds. expressed by general formula III and colloidal silica E of 1-100mum grain size is cured by heating on the front layer of such resin to provide the cured silicone film of 1-10mum film thickness; further, the antireflection layer consisting of an inorg. compd. is formed on the front layer thereof.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a synthetic resin with a relatively high refractive index, which has a hard coat layer made of a synthetic resin with excellent wear resistance and an antireflection film made of an inorganic material on the surface. Regarding manufactured lenses.

[Conventional technology]

Synthetic resin lenses, especially diethylene glycol bis(allyl carbonate) resin lenses, are superior to glass lenses in terms of safety, ease of processing, and fashionability.In recent years, anti-reflection technology, hard coat technology,
With the development of anti-reflection technology, hard coats are rapidly becoming popular. The use of plastic eyeglass lenses has increased the demand for higher quality lenses, that is, thinner plastic lenses made of high refractive index resin materials, and several technical proposals have been made.

For example, an example of a copolymer of diethylene glycol bis(allyl carbonate) and benzyl methacrylate in JP-A-54-419Ei5, an example of a copolymer of diethylene glycol bis(allyl carbonate) and 4-iodostyrene in JP-A-54-77686, There is an example of a copolymer of diallyl isophthalate or diallyl refthalate and methyl meccrylate brevolimer disclosed in 15513/1983.

Furthermore, examples of copolymers of bisphenol A dimethacrylate and 7-enyl methacrylate or benzyl methacrylate, disclosed in JP-A-57-13747, JP-A-57-54
No. 901 and JP-A-58-18E302 disclose copolymers of styrene monomers, di(meth)acrylates containing a nuclear halogen-substituted aromatic ring, and allyl compounds or di(meth)acrylates.

[Problem to be solved by the invention]

However, with the above-mentioned conventional technology,
In the case of JP-A-54-77688 and JP-A-58-15513, allyl groups with different reactivities are reacted with (meth)acrylic groups or vinyl groups, so (meth)acrylic groups or vinyl groups with a fast reaction rate are reacted. The vinyl group polymerizes first,
Because the allyl group polymerizes later due to the reaction rate, not only is the copolymerization not possible, but the allyl compound is not completely polymerized, which causes a decrease in solvent resistance.

Also, JP-A-55-13747, JP-A-57-5490
1. In the case of JP-A-58-18602, the reaction is between a reactive (meth)acrylic group and a vinyl group, but because the reaction is fast, it is difficult to control the casting conditions, and distortion occurs inside and on the lens surface. However, it has the disadvantage of being susceptible to optical defects. In addition, in the above examples, in the case of monofunctional monomers as the main component, it is impossible for the monomer to completely polymerize and be incorporated into the polymer chain, so the heat resistance due to unreacted and This may have an adverse effect on properties and solvent resistance.

As described above, the conventional technology has problems with lens quality, manufacturing process, etc.

Therefore, the present invention solves the above-mentioned problems.
The purpose is to provide a synthetic resin lens that has a relatively high refractive index, is easy to mold, has little color appearance, and has improved durability. It uses a lens that is fast, easy to control reactions, and has excellent durability and various properties as a lens, and has a coating on its surface that has low surface reflection and excellent wear resistance, making it highly popular among the general public. This invention relates to synthetic resin lenses.

[Means to solve the problem]

The synthetic resin lens of the present invention is produced by copolymerizing comonomers containing the following A and B as main components, and coats the surface of the synthetic resin lens with a film of 0.1 to 2 μm containing the following C as a main component. A thin resin film with a thickness of 1 to 10 μm is formed on the surface layer by heating and curing a composition containing D and E as main components, and a reflective film made of an inorganic compound is formed on the surface layer. It is characterized by having received a notification of prevention.

A, one or more monomers whose general formula is represented by [1].

(wherein R' and R' are different groups, one represents
X represents halogen or hydrogen excluding fluorine. ) B, one or more monomers whose general formula is represented by [2].

R3-4COCH2CH=CH2)2 (
2) (In the formula, R3 is )OCH2CHzkO-C
, a copolymer of an acrylic and/or methacrylic compound and an aromatic vinyl compound.

D, a hydrolyzate and/or partial condensate of one or more silane compounds whose general formula is represented by [3].

Tomoe R'-3i (OR'h-, (3) (in the formula, R4 is a child group containing an epoxy group, R1 is a hydrocarbon group having 1 to 4 carbon atoms, and R@ is a hydrocarbon group having 1 to 4 carbon atoms. Represents a hydrocarbon group, alkoxyalkyl group, acyl group,
a is 0 or 1. ) E, colloidal silica with a particle size of 1 to 100 mμ.

Next, the present invention will be explained in detail.

The composition ratio of the A component and the B component in the present invention depends on the refractive index of the synthetic resin lens to be obtained, Abe's heat resistance, impact resistance, solvent resistance, dyeability, sour color, precipitation temperature of the A component, or It is best to determine this by taking into consideration the balance of the decomposition temperature of the polymerization initiator. The weight ratio of component A to component B is preferably from 1:9 to 8:2 in terms of the objective lens being a high refractive index resin and improving durability.

The component that can exhibit the highest refractive index is the component A. Compounds whose general formula is [1] are those in which X excludes fluorine (it can be a halogen or hydrogen, but in terms of refractive index and durability From the viewpoint of coloring water resistance and specific gravity, hydrogen is suitable.

Typical examples of component A include bis(2-chlorobenzyl) itaconate, bis(2-bromobenzyl) itaconate, dibenzylytaphnate bis(2-chlorobenozyl) mesaconate, and bis(2-chlorobenzyl) itaconate.
(bromobenzyl) mesaconate, dibenzyl mesafnate, etc.

Next, component B will be explained.

Even if component B is polymerized alone, it can be molded into a lens, but it cannot be used as a lens material due to poor blue color or poor adhesiveness of the coating formed on the surface.The purpose of using component B is to use a diallyl compound. Therefore, it has good copolymerizability with the compound of component A and is easy to control the reaction, and because it is bifunctional, it creates a three-dimensional ti IIv structure and has little unreacted monomer that does not bond to the polymer chain. can be given.

Furthermore, in order to improve the sealability of the coating, it is desirable to add diethylene glycol bis(allyl carbonate).

The polymerization initiator used in the present invention is not particularly limited, and any known radical polymerization initiator may be used. For example, hydroperoxides such as t-butyl hydroperoxide, dialkyl peroxides such as di-t-butyl peroxide, diacyl peroxides such as benzoyl peroxide, and diimpropyl peroxide dihydrobonates. Peroxydicarbonate, -
Examples include peroxyesters such as butyl peroxypivalate, peroxides such as ketone peroxide and peroxyketal, and azo compounds such as azobis (imbutyrylonitrile). The amount of radical polymerization initiator used depends on the monomer composition of the copolymerization component, precipitation temperature,
It varies depending on the prepolymerization conditions and the thermal polymerization conditions in the mold.
It is preferable to use it in a range of 0% by weight.

When performing casting molding, ultraviolet absorbers, antioxidants, antistatic agents, dyes,
Pigments, fluorescent agents, 7 otochromic substances, various stabilizers, F
! Additives such as i-type agents can be used as necessary.

Next, the coating provided on the surface of the synthetic resin lens in the present invention will be explained.

The resin thin film composed of the main component C is a primer layer for ensuring adhesion between the lens base material and the silicone-based cured coating. In the copolymer of acrylic and methacrylic compounds and aromatic vinyl compounds used for C, examples of acrylic and methacrylic monomers include acrylic acid and methacrylic acid, methanol, ethanol, i-
Examples include esters with lower alcohols such as propatool and n-butanol, and esters of aromatic compounds having alcoholic hydroxyl groups such as benzyl alcohol. In addition, examples of the remaining aromatic vinyl compound include styrene, chlorostyrene/promostyrene 7, and the like. Ingredients other than these, within 5 weight percent of the resin components, include glycidyl methacrylate, glycidyl acrylate, aminoethyl acrylate, dimethylaminoethyl acrylate, 3,4-epoxycyclohexylethyl acrylate, tetrahydrofurfuryl acrylate, 2-hydroxy-3-7enyloxy Probyl acrylate Ethyl acrylate Carpitol 2-Hydroxyethyl acrylate 2-Hydroxypropyl acrylate 2-Acrylic acid Ethyl succinic acid 2- Acrylic acid Ethyl phthalic acid or methacrylates of the above substances and ethylene glycol Diethylene glycol Polyethylene glycol Glycerin Trimethylol propane Neopentyl glycol 1 Acrylate or methacrylate logo of polyhydric alcohol such as 6-hexanesiol octylene glycol, acrylic acid, methacrylic acid, vinyl acetate, etc. can be included.

The composition of this acrylic and/or methacrylic resin and aromatic vinyl resin is determined by the combination of compounds, but it is a copolymer containing at least 20% by weight of methyl methacrylate and at least 10% by weight of styrene. It is a good thing that it is. In addition, these monomers can also be produced by radical copolymerization in a secondary solvent.
A copolymer can be obtained, but in order to generate stronger adhesion, a nonionic or anionic surfactant, a reactive surfactant, or a water-soluble polymeric protective colloid such as polyacrylamide is used in water. It is preferable to use an emulsion which is radically polymerized in the dispersion obtained in this way. carbitols such as methylcarpitol, ethylcarpitol, butylcarpitol, selonrubes such as methylcellosolve, ethylcellosolve, butylcellosolve, dioxane, tetrahydrofuran,
An aqueous medium such as acetone is used after being diluted with an im medium. Also,
Furthermore, solvents with appropriate evaporation rates and viscosity, such as propylene carbonate, methyl isobutyl ketone, methyl ethyl ketone, methyl acetate, ethyl acetate, butyl acetate, dimethyl formamide, propylene glycol monomethyl ether, toluene, and xylene, are added to suit the coating work. It is useful to make improvements as necessary.
It is also possible to improve the durability by adding a silicone-based or fluorine-based surfactant.

The thickness of this primer layer can be selected between 0.1 μm and 2 μm. More preferably from 0.2μm to 1.5μm
A film thickness of m is desirable. If the film thickness is less than 0.1 μm, the adhesion between the fabric material and the abrasion-resistant cured film will not be sufficiently improved. Further, if the thickness of the primer layer is 2 μm or more, water resistance tends to be poor, and whitening of the coating film occurs when immersed in hot water for a long time, which is not preferable.

The coating method for this primer layer can be arbitrarily selected from the dipping method, spin-coating method, flow coating method, and spraying method.

In addition, after coating, this resin thin film is dried or cured at a temperature of 10 to 130 @ C, and the resin thin film is semi-dry.
Alternatively, by applying a silico/based coating liquid while swollen with a solvent, partially impregnating it with the composition for forming a cured film, and then heating it sufficiently to remove the solvent and complete the curing reaction. , a primer layer impregnated with a silica component can be formed.

Next, a coating liquid composition for forming a silicone-based cured film will be explained.

First, the epoxy group R4 of the sila/compound represented by the one-step formula [3] of the components is represented by the following: It is something. Further, R'' is a hydrocarbon group having 1 to 4 carbon atoms, and a is O or 1. Specific examples of this compound include γ-glycidoxypropyltrimethoxysilane γ-glycidoxypropyl (methyl) Dimethoxysilane γ-glycidodipropyl(ethyl)dimethoxysilane γ-glycidoxypropyl(propyl)dimethoxysilane β-glycidoxyethoxyprobyltrimethoxysilane β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane β- Examples include (3,4-epoxycyclohexyl)ethyl(methyl)dimethoxysilane.This alkoxy group (methoxy group) is
Since it is ultimately used after hydrolysis or dehydration condensation, other alkoxy groups, alkoxyalkoxy groups,
Alkoxy groups etc. can be used.

Furthermore, even if this OR' group is a halogen group or a hydrogen group, it is considered to be equivalent if it undergoes hydrolysis2 and becomes a hydroxyl group. Therefore, although this component may be used as it is, it is usually used after being hydrolyzed in water or in a solvent such as alcohol, keto/cellosolve, etc. using a mineral acid or a mineral acid as a catalyst.

This component is essential for increasing the durability and flexibility of the cured film made of silicone resin, and is also effective in improving the adhesion with the primer layer. In addition, 25% by weight to 65% by weight can be used, calculated as the effect of alleviating the volumetric shrinkage caused by dehydration condensation due to the ring-opening reaction of the epoxy residue.

Further, if this component is less than 25% by weight, cracks will occur in the cured film, and if it is more than 65% by weight, the adhesion with the antireflection film will be poor, which is not preferable.

Next, the colloidal silica having a particle size of 1 to 100 mμ as component E is silica fine particles having a particle size of 1 to 100 mμ, more preferably silica fine particles having a particle size of 5 to 40 mμ dispersed in a solvent. Examples of the dispersion medium include alcohols such as methanol, ethanol, 1-propanol, and n-butanol, carpitol solvents such as methylceronelube and ethylcellosolve, and water. This component is indispensable for increasing the rigidity, moisture resistance, and durability of the cured film, as well as for obtaining affinity or adhesion with the antireflection film applied thereon. Furthermore,
Silica microparticles are also effective in improving the compactness and robustness of the deposited material, due to the fact that increasing the amount of this component in the cured film increases the strength and hardness of the inorganic material deposited on it. it is conceivable that. The amount used is from 75 weight percent to 35 weight percent, more preferably from 75 weight percent to 50 weight percent of the cured film components at the heated stage.

If the amount of this component used is 75% by weight or more, cracks will occur in the cured film, and if it is less than 35% by weight, the adhesion with the antireflection film will be insufficient, which is not preferable. In addition, the silica concentration in the dispersion medium is 20
~35% by weight is stable and convenient for use.

These compositions are best used after being diluted with the various solvents mentioned above. In addition, this includes ultraviolet absorbers,
It is possible to add a dye, a photochromic compound, a temporary pigment, etc., and it is also good to add a leveling agent and an antistatic agent, if necessary. Examples of these include various nonionic surfactants, anionic surfactants, silicone surfactants, and fluorine surfactants.

The coating method can be arbitrarily selected from dipping, spin-coating, flow coating, spraying, and the like. Subsequently, with or without air drying, 80 color 150'C (
7) By curing for 30 to 300 minutes, a cured film with the desired characteristics can be obtained. Cure temperature is limited by the heat resistance of the fabric material, so 15
060°C or higher is difficult, and if the temperature is 80°C or lower, it takes a long time to cure. Also, the cure time is 30
If it is less than 300 minutes, the curing reaction will not be completed, which is not preferable, and if it is more than 300 minutes, it will be uneconomical in terms of productivity, so it is not preferable.

Infrared ray treatment is also available as a preliminary curing method. The transparent material thus obtained may be directly proceeded to the next step. In addition, cleaning or chemical treatment with acids, alkalis, solvents such as alcohol and Freon, ozone gas, etc., or surface activation using physicochemical means such as activated gases such as plasma, electron beam irradiation, and ultraviolet irradiation. is also effective.

The present invention can be achieved by providing an antireflection thin film made of an inorganic dielectric material on the surface layer thus obtained.

That is, vacuum evaporation method, ion sputtering method
O1S io, S ion, S li Na
, Ti0m , ZrOs , A! 2s Os + M
By laminating a single layer or multilayer thin film made of a dielectric material such as gFs + Ta t 03, a layer is formed that suppresses reflection at the interface between the atmosphere and the resin base material.
The optical thickness of the 7-preventive film is λ/4 (λ=450~G
50 mm> single layer or λ/4-λ/2-λ/
A multilayer coating consisting of three layers having different refractive indexes of 4 or λ/4 - λ/4 - λ/4, or a multilayer coating of three or more layers is suitable. The refractive index at this time is determined by the material close to the physically calculated value. It is also useful to replace the material with the desired refractive index with an equivalent film.

The synthetic resin lens of the present invention obtained in this way has excellent abrasion resistance, heat resistance, water resistance, oil resistance, and multilayer film adhesion, and also suppresses surface reflection and improves visible light transmittance. This is what I did.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these examples. In addition, all parts in the examples represent parts by weight.

Example 1 (1) Production of synthetic resin lens base material (A1) 10 parts of dibenzyl itaconate, 10 parts of dibenzyl mesaconate
Part, diethylene glycol bis(allyl carbonate)
30 parts of diallylisophthalate and 50 parts of diallylisophthalate were stirred during mixing, and 0.1 part of 2(2'-hydroxy-5'-methylphenyl)be/citriazole was added. Thereafter, 2.8 parts of diisopropyl peroxydicarbonate (Perloyl IPP, manufactured by NOF Corporation) was added and mixed well.

After filtering the insoluble matter of this mixture, -6 in degrees, OOD
The mixture was injected into a space formed by a glass mold designed to release (D; diopters) and a gasket made of ethylene-vinyl acetate copolymer designed to have a center thickness of 2.0 mm. Polymerization was carried out at 40° in a Kounin tank.
5 hours at C, 10 hours from 40@C to 50''C, 5
The temperature was increased from 0°C to 100°C for 5 hours and then at 100°C for 2 hours. The glass mold and gasket were then separated from the lens. With this method, the diameter is 75mmφ, -6, OOD
When the lens was cast-polymerized, the incidence of poor tightness between the glass mold and the lens was less than 0.1%. Next, post-curing was performed at 100°C for 2 hours to remove distortion inside the lens. The obtained lens had good optical surface deafness, no internal distortion, and was satisfactory as an optical material.

(2) Add 800 parts of distilled water and sodium dodecylbenzenesulfonate (manufactured by Nippon I Yuki Co., Ltd., trade name) to a U3-made primer coating solution (Pl) and a 3β SUS autoclave equipped with a coating curing stirrer. 4 parts of “Nurex R”) were added and the mixture was kept at 30-35°C and
Stir at ~60 rpm to dissolve the contents.

Next, 300 parts of methyl methacrylate from which the polymerization inhibitor was removed by distillation, 20 parts of 〇-butyl acrylate, and 2 parts of styrene were added.
215 parts of n-dodecyl mercap was dissolved in 0.00 parts and added to the autoclave. After replacing the atmosphere in the container with a sufficient amount of nitrogen, stirring was started at 500 revolutions per minute.

Subsequently, 4 parts of potassium persulfate was dissolved in 36 parts of distilled water and added dropwise over 1 hour.

Subsequently, the speed was reduced to 50 revolutions per minute, the internal temperature was heated to 80°C, and the reaction was carried out for about 3 hours.

After the reaction was completed, a solution prepared by dissolving 3 parts of sodium dimethyldithiocarbamate in 100 parts of distilled water was injected as a stop solution to stop the reaction.

The emulsion solution thus obtained had a solid content concentration of 37% and a particle size of 500 mμ or less. Further, the molecular weight of the polymer was approximately 100,000 as approximated by the viscosity method.

Next, 60 parts of methanol was added to 30 parts of this emulsion solution while stirring, followed by 50 parts of methyl cellosolve, 10 parts of dimethyl formamide, and a silicone surfactant (manufactured by Nippon Unicar Co., Ltd.). Name "Y-700"
2'') was added to prepare a primer solution (Pl).

This primer solution was thoroughly filtered through a membrane filter with pores of 1 μm, and then applied to the base lens obtained in (1) by a dipping method. By setting the pulling speed at this time to 10 cm/min, a primer film having a thickness of 0.5 μm after curing was obtained.

The coated lenses were dried and cured in a hot air drying oven at 70° C. for 1 hour, resulting in lenses with good appearance.

(3) Preparation and application of silicone coating liquid (HI), coating, curing, and dispersion of colloidal silica (“03CAL-1432” manufactured by Catalysts & Chemicals Co., Ltd., “03CAL-1432” by Catalysts & Chemicals Co., Ltd.) in a flask equipped with a stirring device under a nitrogen atmosphere. %), 220 parts of inpropatol, and 108 parts of γ-glycidoxypropyltrimethoxysilane were added in this order with stirring, and 52 parts of 0.05N hydrochloric acid was added dropwise over 30 minutes. Subsequently, 0.1 part of the silicone surfactant mentioned above was added, and the mixture was allowed to stand at 0°C for 24 hours to ripen, thereby obtaining a coating liquid. Let this be Hl.

Subsequently, the lens obtained in (2) was coated with the coating liquid by dipping. The lifting speed at this time is
The speed was 20 cm/min. This lens is dried in a hot air drying oven.
It was heated and cured at 100°C for 2 hours. The cured layer thus obtained was hard, transparent, and had good adhesion. Further, the thickness of this cured layer was 2.4 μm including the thickness of the previous primer layer.

(4) Formation of anti-reflection layer The lens obtained in step (3) was exposed to Ar gas plasma at an output of 20oW for 30 seconds in a vacuum, and then formed into a film structure as shown in Figure 1 using a vacuum evaporation method. It has an anti-reflection layer. That is, from the lens side to the atmosphere side, SiOt
, Z r Ot , S iO* , Z rOs,
A five-layer thin film with a thickness of 5ift is formed, and its optical thickness is sequentially composed of ZrO2 and SiO2 with SiOx of approximately λo/42nd order.
*The total film thickness of Zr01 of order 70742 is approximately λ0/4.
5ift of the top layer is approximately λo/4. Note that the design wavelength λ0 is 510 parts m.

The lens thus obtained had low surface reflection and excellent wear resistance.

Incidentally, FIG. 2 shows a spectrum diagram of surface reflection.

(5) Regarding synthetic resin lenses obtained through testing and evaluation methods,
The following performance evaluation test was conducted. The evaluation results are shown in Table 1.

a. Scratch resistance: #0000 steel wool under load I
The state of the coating was observed after 10 reciprocations at K g/cm''.

A: It hardly gets scratched.

B: Slight damage.

C: Many scratches occur.

b. Adhesion After immersing in warm water at 280°C for 2 hours,
11 on the lens surface with a knife at 1mm intervals vertically and horizontally.
Make 100 squares by making scratches on the book's parallel lines,
Seal the cellophane tape? It is expressed as the number of squares in which the film remained unbroken after removal.

c. Nt weatherability: Using a xenon long life fade meter (manufactured by Suga Test Instruments Co., Ltd.), the surface condition was examined after exposure for 200 hours.

Example 2 (1) Production of synthetic resin lens base material (A2) 30 parts of dibenzyl itaconate, diethylene glycol bis(
10 parts of allyl carbonate) and 60 parts of diallyl terephthalate were mixed and stirred, and 0.2 part of 2-hydroxy-4-methoxybensiphenone was added. Thereafter, 3.0 parts of di-normal propyl baroxydicarbonate (manufactured by NOF Corporation; Baroyl NPP) was added and mixed well. After filtering out insoluble matter from this mixture, cast polymerization was performed in the same manner as in Example 1.

(2) Preparation and curing of primer coating liquid (P2) F430 (manufactured by Showa Kobunshi Co., Ltd., solid content concentration 45%) was used as a commercially available acrylic-styrene aqueous emulsion. That is, 20 parts of pure water was added to 29,720 parts of the aqueous emul with strong stirring.

20 parts of methanol was slowly added, followed by 180 parts of ethylcelonol and 10 parts of propylene glycol monomethyl ether. Then, 2.5 parts of Valar t-butylphenyl salicylate and a polymer stabilizer (Sankyo Co., Ltd.) were added. Co., Ltd., trade name "S/-L LS-770") was added, and further an ultraviolet absorber 2-(2'-hydroxy-3'-
Add 0.2 part of methylphenyl)be/citriazole,
After sufficient dissolution, insoluble matter was removed by filtration to obtain a primer coating liquid (P2).

This coating liquid was applied in the same manner as in Example 1, and heated at 60°C for 30 minutes.
A primer layer was formed by drying for 0 minutes.

The thickness of this primer layer was 0.5μ.

(3) Silico/based coating liquid (H2): Methanol-dispersed colloidal silica (8san Kagaku Kogyo Co., Ltd. Steel Manufacturing Methanol Silica Sol) solid content 1c13 [f30%] in a flask equipped with A and coating hardening stirring device. 580 parts, and Improper Tool, 350 parts, 220 parts of γ-glycidoxypropyl(methyl)jethoxysilane, 3 parts of 0.1N hydrochloric acid.
After adding 5 parts and 0.1 part of a silicone surfactant and sufficiently stirring to obtain a uniform solution, the mixture was left to mature at 0°C for 24 hours to obtain a coating liquid. This liquid was applied to the previously obtained lens and cured in the same manner as in Example 1. The thickness of the cured film thus obtained, including that of the primer, was 2.2 μm.

(4) Formation of anti-reflection layer The obtained lens was treated with 200 W oxygen plasma for 30 seconds, and then an anti-reflection layer was provided by vacuum evaporation.

That is, from the lens side to the atmosphere side, ZrO3,Aρ
A four-layer thin film of t Os , Z r Os , S I On is formed, and its optical thickness is as follows:
The next Z r O* is about λo/4, and the top layer S i
Ox is approximately λ0/4. In addition, the design wavelength λQ is 51
It is 0 nm.

(5) Testing and evaluation Synthetic resin lenses obtained by the above method were used in Example 1.
Evaluation was made in the same manner as in Table 1, and the results are shown in Table 1.

Example 3 (11 Production of synthetic resin lens base material (A3)) 30 parts of dibenzyl itaconate, 10 gL of diethylene glycol bis(allyl carbonate), 6 diallyl isophthalate
0 parts were mixed and stirred, and 0.2 parts of 2-hydroxy-4-methoxybenzophenone was added. Then, benzoyl peroxide (manufactured by Nippon Oil & Fats Co., Ltd.: Niper B) 3
．． 5 parts were added (mixed). After filtering out insoluble matter from this mixture, polymerization was carried out in a glass mold.

Polymerization was carried out in a constant temperature bath for 4 hours at 51°C and 4 hours at 55”C.
time, 3.5 hours at 60°C, 3 hours at 65°C, 71
2.5 hours at °C, 2.5 hours at 75°C, 2 hours at 799C.
The temperature was 84°C for 1 hour and 90°C for 2 hours. The subsequent operations were performed in the same manner as in Example 1.

(2) Preparation and coating curing of primer coating liquid' (P3) As a commercially available aqueous acrylic-styrene emulsion, 20 parts of Cevian A4719 (product of Daicel Chemical Industries, Ltd., solid content concentration 50%) and 50 parts of water were used. , methanol 70
parts, 80 parts of ethyl cellosolve, 2 parts of dimethylformamide
0 parts was added to prepare a primer coating liquid (P3).

The base lens was immersed in this primer coating solution for 10 c.
A homogeneous primer film with a film thickness of 0.4 μm was obtained by pulling up at a speed of m/min, air drying, and drying and curing at 60° C. for 30 minutes.

(3) Hard coat treatment and antireflection treatment The base material thus obtained was subjected to hard coat treatment and an antireflection film formed in the same manner as in Example 1.

(4) Testing and evaluation Example 1 Synthetic resin lenses obtained by the above method
Evaluation was made in the same manner as in Table 1, and the results are shown in Table 1.

Example 4 (1) Manufacturing screws for synthetic resin lens base material (A4) (
10 parts of itaconate (2-chlorobenzyl), bis(2-
10 parts of diethylene glycol bis(allyl carbonate), 40 parts of diallyl isophthalate were mixed and stirred, and ethyl-2-
0.2 part of cyano-3,3-9 phenyl acrylate was added.

Thereafter, 2.9 parts of di-2-ethylhexyl peroxydicarbonate (manufactured by NOF Corporation; Baroyl 0PP) was added and mixed well. After filtering out insoluble matter from this mixture, cast polymerization was performed in the same manner as in Example 1.

■ Coating and curing of primer coating liquid, hard coating and anti-reflection processing The base material thus obtained was subjected to coating and curing of primer coating liquid (Pl) and hard coating (H1) in the same manner as in Example 1. (used) and an antireflection film was formed.

(3) Testing and evaluation Example 1 Synthetic resin lenses obtained by the above method
Evaluation was made in the same manner as in Table 1, and the results are shown in Table 1.

Example 5 (1) Manufacturing screws for synthetic resin lens base material (A5) (
30 parts of 2-bromobenzyl) itaconate, 10 parts of diethylene glycol bis(allyl carbonate), and 60 parts of diallyl isophthalate were mixed and stirred, and 2 (2'-
0.1 part of hydroxy-5'-methylphenyl)be/citriazole was added. Thereafter, 2.8 parts of diimpropyl peroxydicarbonate was added and mixed well. After filtering out insoluble matter from this mixture, cast polymerization was performed in the same manner as in Example 1.

(2) Coating and curing of primer coating liquid, hard coating and anti-reflection processing The base material thus obtained was coated and cured with primer coating liquid (P2) and hard coated in the same manner as in Example 2. (using H2) and an antireflection film was formed.

(3) Testing and evaluation Example 1 Synthetic resin lenses obtained by the above method
The results were shown in Table 1.

Comparative Example 1 The synthetic resin lens base material (A1) in Example 1 was coated with a silicone coating liquid (I) without a primer layer.
]1) The coating hardening and antireflection treatment were performed in the same manner as in Example 1.

Example 1 Synthetic resin lens obtained by the above method
Evaluation was made in the same manner as in Table 1, and the results are shown in Table 1.

Comparative Example 2 The synthetic resin lens base material (A2) in Example 2 was coated with a silicone coating liquid (I) without a primer layer.
The coating hardening and antireflection treatment of 42) were performed in the same manner as in Example 2.

Example 1 Synthetic resin glasses obtained by the above method
Evaluation was made in the same manner as in Table 1, and the results are shown in Table 1.

Table - Table 〔Effect of the invention〕 As described above, composition A in the present invention.

By using B, a high refractive index resin can be obtained, and at the same time, a synthetic resin lens base material that is easy to mold, has little discoloration, and has improved durability such as heat resistance, solvent resistance, and impact resistance. Obtainable. Moreover, the composition in the present invention is
Since the reaction rate is slow and the reaction rates of each component monomer are similar, the reaction can be easily controlled (and the selection of polymerization initiators is wide), making polymerization operations and process control easier.

In addition, by forming a coating on the lens surface consisting of a primer layer and an anti-reflection layer, the synthetic resin lens has low surface reflection, is dense, and has excellent abrasion resistance, making it highly popular among the general public. It became possible to obtain.

[Brief explanation of the drawing]

FIG. 1 is a film configuration diagram on the lens surface in Example 1. A
1 is a base lens, Pl is a primer layer, Hl is a silicon-based hardened coating, 11 to 15 are antireflection layers, and thin film 11
is Sin, 12 is Zr01, 13 is SiO, 14 is ZrO, 15 is 5iOW. FIG. 2 is a reflection spectrum diagram of the lens surface in Example 1. that's all

Claims (1)

[Claims] On the surface of a synthetic resin lens obtained by copolymerizing comonomers containing the following A and B as main components, a resin having a thickness of 0.1 to 2 μm and containing the following C as a main component is applied. A thin film is formed, and a silicon-based cured film with a thickness of 1 to 10 μm is formed by heating and curing a composition containing the following D and E as main components, and a reflective film made of an inorganic compound is formed on the surface layer. A synthetic resin lens characterized by having a protective layer. A, one or more monomers whose general formula is represented by [1]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [1] (In the formula, R^1 and R^2 are different groups, and one is -H
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ where X represents halogen or hydrogen excluding fluorine. ) B, one or more monomers whose general formula is represented by [2]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [2] (R^3 in the formula is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or ▲Mathematical formulas, chemical formulas, tables, etc. ▼ represents an integer from 1 to 3. C: A copolymer of an acrylic and/or methacrylic compound and an aromatic vinyl compound. D: A silane compound whose general formula is represented by [3] A hydrolyzate and/or partial condensate of one or more of the following. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [3] (In the formula, R^4 is an organic group having an epoxy group, and R^5 is an organic group having an epoxy group. , a hydrocarbon group having 1 to 4 carbon atoms, R^6 represents a hydrocarbon group having 1 to 4 carbon atoms, an alkoxyalkyl group, or an acyl group, and a is 0 or 1.) E, particle size 1 Colloidal silica of 100 mμ.