JPH01216301A - Plastic lens - Google Patents

Abstract

PURPOSE:To facilitate molding, to reduce coloring, and to improve heat resistance and durability, of a plastic lens comprising a resin having high refractive index prepd. from a specified composition. CONSTITUTION:A thin resin film having 0.1-2mum thickness consisting primarily of a copolymer of an acrylic and/or methacrylic compd. and an aromatic vinyl compd. is formed on the surface of a plastic lens obtd. by copolymerizing comonomers consisting of at least one kind of monomer expressed by formula I with at least one kind of monomer expressed by formula II. A silicone heat- cured film having 1-10mum thickness consisting of a compsn. consisting primarily of at least one kind selected from at least one kind of hydrolyzate of silane compds. expressed by formula III and/or partial condensates thereof, colloidal silica having 1-100mum particle size, and a beta-diketone compd. and/or a beta- ketoester compd. is formed on a surface layer of the plastic lens. Further, a reflection reducing layer comprising an inorganic material is formed on the surface layer of said silicone cured film. Thus, the durability is improved.

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 hard coat + anti-reflection technology, it is rapidly becoming popular. The use of plastic for eyeglass lenses has increased the demand for higher quality lenses, that is, thinner plastic lenses made of high refractive index resin materials (some technical proposals have been made).

For example, an example of a copolymer of diethylene glycol bis(allyl carbonate) and benzyl methacrylate in JP-A-54-41965, 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 terephthalate and methyl methacrylate prepolymer disclosed in 1983-15513.

Further, examples of copolymers of bisphenol A dimethacrylate and phenyl methacrylate or benzyl methacrylate, disclosed in JP-A-57-13747, JP-A-57-54
There is a copolymer of a styrene monomer, a di(meth)acrylate having a nuclear halogen-substituted aromatic ring, and an allyl compound or di(meth)acrylate, as disclosed in No. 901 and JP-A-58-18602.

[Problem to be solved by the invention]

However, with the above-mentioned conventional technology,
In the case of JP-A-54-77686 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,
Since the allyl group, which has a slow reaction rate, is polymerized later, not only is the copolymerization not possible, but also 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 heat resistance due to unreacted monomers and Possible adverse effect on 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 objective is to provide a synthetic resin lens that has a relatively high refractive index, is easy to mold, has little coloring, and has improved durability. More specifically, we used a lens that has a relatively slow reaction rate, is easy to control the reaction, and has excellent durability and properties as a lens, and a coating on its surface that has low surface reflection and excellent wear resistance. This invention relates to synthetic resin lenses that are highly popular among the general public.

[Means to solve the problem]

The synthetic resin lens of the present invention is a synthetic resin lens surface obtained by copolymerizing comonomers containing the following A and B as main components, and a 0.1-2 um thick film containing the following C as a main component. 1 to 10 um formed by forming a thick resin thin film and heat-curing a composition containing D, E, and F as main components on the surface layer.
It is characterized by having a silicon-based cured film with a film thickness of 100 ml, and further having an antireflection layer made of an inorganic compound on the surface layer.

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

(In the formula, R1 and R2 are different groups, one of which represents
X represents halogen or hydrogen excluding fluorine;) B, one or more monomers whose general formula is represented by [2];

R' -1-(-1 COCH2CH=CH2)20
[2] (In the formula, R'' is -←OCH2CH2+O-1/n represents an integer from 1 to 3.) 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].

Ra' C3E R'Si(OR') 5-a (In the formula, R4 is an organic group having an epoxy group, R5 is a hydrocarbon group having 1 to 4 carbon atoms, and R6 is a carbonized group having 1 to 4 carbon atoms. Represents a hydrogen group, an alkoxyalkyl group, an acyl group,
a is 0 or 1. )E0 particle size 1 to 100mμ
Colloidal silica.

F, one or more selected from β-diketones and/or β-getoester compounds.

Next, the present invention will be explained in detail.

In the present invention, the composition ratio of component A and component B is determined by the refractive index, heat resistance, impact resistance, solvent resistance, dyeability, coloring, precipitation temperature of component A, or polymerization of the synthetic resin lens to be obtained. The weight ratio of component A to component B should be determined by taking into account the balance of the decomposition temperature of the initiator.The weight ratio of component A to component B is Preferably, the ratio is from 1:9 to 8:2.

The compound having the general formula [1], which is component A, can exhibit the highest refractive index, in which X can be a halogen other than fluorine or hydrogen, but from the viewpoint of refractive index and durability Chlorine is preferable, and hydrogen is suitable from the viewpoint of coloring water resistance and specific gravity.

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

Next, component B will be explained.

Lenses can be molded even if component B is polymerized alone, but it cannot be used as a lens material due to poor coloring or poor adhesion of the film formed on the surface.The purpose of using component B is to use diallyl. Because it is a compound, it has good copolymerizability with the compound of component A, and reaction control is easy.D. Also, because it is trifunctional, it forms a three-dimensional crosslinked structure.D. There is less unreacted monomer that does not bond to the polymer chain. There are many things that can be mentioned. Furthermore, in order to improve the adhesion 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 may be any known radical polymerization initiator.

For example, hydroperoxides such as t-butyl hydroperoxide, dialkyl peroxides such as di-t-butyl peroxide, diacyl peroxides such as benzoyl peroxide, and peroxygen peroxides such as diisopropyl peroxydicarbonate. carbonate, peroxyesters such as t-butyl peroxypivalate, peroxides such as getone peroxide, peroxyketal, or azobis(
Examples include azo compounds such as imbutyrilonitrile).

The amount of the radical polymerization initiator used varies depending on the monomer composition of the copolymerization component, precipitation temperature, prepolymerization conditions, and thermal polymerization conditions in the mold. Preferably, it is used in a range of 0 weight percent.

When performing casting molding, UV absorbers, antioxidants, antistatic agents, dyes, etc. are added to the monomer mixture to improve the process.
Additives such as pigments, fluorescent agents, photochromic substances, various stabilizers, and mold release 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 made of 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, talolstyrene, bromostyrene, and the like. As components other than these, glycidyl methacrylate glycidyl acrylate aminoethyl acrylate dimethylaminoethyl acrylate 3.4-epoxycyclohexylethyl acrylate tetrahydrofurfuryl acrylate 2-hydroxy-3-phenyloxypropyl acrylate Ethyl carpitol acrylate 2-hydroxyethyl acrylate 2-droxypropyl acrylate 2-acrylic acid ethyl succinic acid 2-acrylic acid ethyl phthalic acid or methacrylates of the above substances, ethylene glycol diethylene glycol polyethylene glycol glycerin trimethylol propane neopentyl glycol , acrylates or methacrylates of polyhydric alcohols such as octylene glycol, 6-hexanesiol, acrylic acid, methacrylic acid, vinyl acetate, and the like.

The composition of the acrylic and/or methacrylic resin and the aromatic vinyl resin is determined by the combination of compounds, but the composition includes at least 20 weight percent methyl methacrylate and at least 10 weight percent styrene. Preferably, it is a polymer. Copolymers can also be obtained by radical copolymerization of these monomers in an organic solvent, but in order to generate stronger adhesion, nonionic or anionic surfactants or It is preferable to use an emulsion radically polymerized in a dispersion obtained using a reactive surfactant or a water-soluble polymeric protective colloid such as polyacrylamide. Alcohols such as methanol, ethanol, I-propertool, n-butanol, carpitols such as methyl calpitol, ethyl carpitol, butyl carpitol, cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, dioxane, tetrahydrofuran, Use by diluting with a water-soluble organic solvent such as acetone. Additionally, solvents with various evaporation rates and viscosities 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 the coating process. It would be useful to improve it accordingly. In addition, if necessary, silicone-based or fluorine-based surfactants may be added.
It is also possible to improve the coating properties.

The thickness of this single layer of limer 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 this film thickness is less than 0.1 μm, the adhesion between the fabric material and the palm abrasion resistant cured film will not be improved sufficiently, and if the thickness of the primer layer is more than 2 μm. This is not preferable because it tends to have poor water resistance and whitening of the coating film occurs when immersed in hot water for a long time.

The method for applying one layer of limer can be arbitrarily selected from among the dipping method, spin cord method, flow coating method, and spray method.

After coating, this resin thin film is dried or cured at a temperature of 10 to 130°C, and while the resin thin film is semi-dry or swollen with a solvent, a silicone coating liquid is applied and cured. After partially impregnating the film-forming composition, sufficient heating is performed to remove the solvent and complete the curing reaction, thereby forming a primer layer impregnated with D. the silica component.

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

First, the epoxy group R4 of the silane compound represented by the general formula [3] (where p and q are 1 to 6, and r is O to 2).

). Further, R5 is a hydrocarbon group having 1 to 4 carbon atoms, and a is O or! It is. Specific examples of this compound include γ-glycidoxypropyltrimethoxysilane γ-glycidoxypropyl(methyl)dimethoxysilane γ-glycidoxypropyl(ethyl)dimethoxysilane γ-glycidoxypropyl(propyl)dimethoxy Examples include silane β-glycidoxyethoxypropyltrimethoxysilane β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane β-(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,
Acyloxy groups etc. can be used.

Further, even if this OR' group is a halogen group or a hydrogen group, it is considered to be equivalent if it undergoes hydrolysis 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, ketone, or cellosolve using a mineral acid or an organic 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. It also has the effect of alleviating the volumetric contraction caused by D and dehydration condensation due to the ring-opening reaction of epoxy residues.

R' a This usage amount is calculated as R' -31-03-a,
From 25 weight percent to 65 weight percent can be used. 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 component E, colloidal silica having a particle size of 1 to 100 mμ, refers to fine silica particles having a particle size of 1 to 100 mμ, more preferably fine silica 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, i-propanol, and n-butanol, carpitol solvents such as methyl cellosolve and ethyl cellosolve, 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% to 35% by weight, more preferably from 75% to 50% by weight of the cured film components at the heated stage. If the amount of this component used is more than 75% by weight, 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 undesirable. A silica concentration of 20 to 35 weight percent is stable and convenient for use.

Representative examples of the β-diketone and β-ketoester compounds of component F include keto-enol type compounds such as acetylacetone butyrylacetone dimedone acetoacetate methylacetoacetate and the like.

This is useful for fluid life. It can be inferred that this substance suppresses the dehydration condensation reaction caused by the approach and collision of D and silanol, which form intermolecular hydrogen bonds with the surface of colloidal silica and the silanol groups of silane compounds in solution. This can be inferred from the fact that the shift of the peak toward the polymer side and the increase in viscosity of -E in oral changes by liquid chromatography are suppressed. The cured film obtained from a coating solution with increased viscosity and polymerization is inferior in external hardness to the cured film obtained from an initial coating solution, so dehydration condensation of silanol groups in the coating solution does not progress. Therefore, these β-diketones and β-ketoesters extend the life of the solution and
Its main function is to maintain hardness at a high level. Also,
This addition amount is effective as a catalytic amount, but there is no adverse effect even if added in excess.
It is recommended to use 0°001 parts by weight or more, preferably 0.05 parts by weight or more.

It is useful to use these compositions after diluting them with the various solvents mentioned above. In addition, this includes ultraviolet absorbers,
Dyeing agents, photochromic compounds, coloring pigments, etc. can be added, and if necessary, leveling agents and antistatic agents may be added. Examples of these include various nonionic surfactants, Examples include 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, by performing curing for 30 to 300 minutes at a temperature of 8° to 150° C. with or without air drying, a cured film having the desired characteristics can be obtained. The curing temperature is limited by the heat resistance of the fabric material, so it is difficult to exceed 150°C, and below 80°C, it takes a long time to cure, and the curing time is 30 minutes or less. If the curing reaction takes longer than 300 minutes, the curing reaction will not be completed, and if the curing reaction takes longer than 300 minutes, it becomes uneconomical in terms of productivity.

Furthermore, treatment with infrared rays is also effective as a preliminary curing method. The transparent material obtained in this way may be proceeded to the next step as it is, or it may be washed with an acid, alkali, a solvent such as alcohol or Freon, or chemically treated with ozone gas, etc., or it may be processed with plasma, etc. Activation of the surface using physicochemical means such as activated gas, 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, D and S are formed by vacuum evaporation method and ion sputtering method.
in, 5i02.5i3Na, TiO2, ZrO2,
Aj203, MgF2, Ta20. By stacking single or multilayer thin films made of dielectric materials such as D, a layer that suppresses reflection at the interface between the atmosphere and the resin base material is formed.

This anti-reflection film has an optical thin film of λ/4 (λ-4
50-650) 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, and further a multilayer coating of three or more layers, is useful. The refractive index at this time is determined by the material close to the physically calculated value. It is also effective 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 is
It has excellent abrasion resistance, heat resistance, water and oil resistance, and multilayer adhesion, and also has low surface reflection and improved visible light transmittance.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these Examples, and all parts in the Examples represent heavy fitting parts.

Example 1 <1) Production of synthetic resin lens base material (A1) 10 parts of dibenzyl itaconate, 10 parts of dibenzyl mesaconate,
Diethylene glycol bis(allyl carbonate) 30
2 parts, and 50 parts of diallyl isotucrate were mixed and stirred.
0.1 part of (2'-hydroxy-5'-methylphenyl)benzotriazole was added, and then 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, the temperature was -6, OOD (D
, di-1 tree) and a gas get made of ethylene-vinyl acetate copolymer designed to have a center thickness of 2.0 cm. Polymerization is permanent! 5 at 40℃ in a bath
Time 10 hours from 40℃ to 50℃, 10 hours from 50℃
The temperature was reduced to 0°C for 5 hours, and the temperature was heated to 100°C for 2 hours. Thereafter, the glass mold and gas get were separated from the lens.

When a lens with a diameter of 75 mm and a -6 mm OOD was cast-polymerized using this method, the incidence of poor adhesion 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 a good optical surface condition, no internal distortion, and was satisfactory as an optical material.

(2) Preparation and application of the brimer coating liquid (Pl) and curing In a 3J SUS autoclave equipped with a stirrer, add 800 parts of distilled water and sodium dodecylbenzenesulfonate (manufactured by Nippon Oil & Fats ■, product name: "Newlex R") ) and keep this mixture at 30-35°C, at 40-60 m/min.
Stir by rotation to dissolve the contents.

Next, 300 parts of methyl methacrylate, which had been distilled to remove the polymerization inhibitor, 20 parts of n-butyl acrylate, and 2 parts of styrene.
5 parts of n-dodecyl mercaptan 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 the solution was 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% (D) and a particle size of 500 mμ or less. Further, the molecular weight of this polymer approximated by the viscosity method was about 100,000.

Next, slowly add D to 30 parts of this emulsion solution while stirring.
, 60 parts of methanol was added, followed by 50 parts of methyl cellosolve, 10 parts of dimethylformamide, and a silicone surfactant (manufactured by Nippon Unicar, trade name "Y-7002").
) 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 10QII/min, D, with a primer film thickness of 0.5 μm after curing, was obtained.

The coated lens was dried and cured in a hot air drying oven at 70° C. for 1 hour to obtain a lens exhibiting a good appearance.

(3) Preparation of silicone coating liquid (Hl), coating and curing In a flask equipped with a stirring device, colloidal silica dispersed with isopropanol (“0
3CAL-1432" solid content concentration 30%), 220 parts of In10panol, and 108 parts of γ-glycidoxypropyltrimethoxysilane were added in order with stirring, and 52 parts of 0.05N hydrochloric acid was added over 30 minutes. dripped.

Subsequently, 0.45 part of acetylacetone and 0.1 part of the above-mentioned silicone surfactant were added, and the mixture was left to ripen at 0° C. for 24 hours to obtain a coating liquid. This is H
Let it be l.

Subsequently, the coating liquid was applied to the lens obtained in (2) by a dipping method. The lifting speed at this time is
20> per minute. This lens is dried in a hot air drying oven for 1
It was kept at 00° C. for 2 hours and cured by heating. 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 placed in an Ar gas plasma for 30 seconds at an output of 200 W in a vacuum, and then formed into a film as shown in Figure 1 using a vacuum evaporation method. It has an anti-reflection layer. That is, from the lens side toward the atmosphere side, 5i02,
A five-layer thin film of ZrO2,5i02 and ZrO2,5i02 is formed, and the optical thickness of the film is approximately λ.
o/4, the total thin film of next ZrO2 and 5i02 is about λ
. /4, the next ZrO2 is about λo/4, and the top layer 5tO2 is about λ. /4. Furthermore, the design wavelength λ. is 5
10 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) Testing and evaluation Regarding synthetic resin lenses obtained by the above methods,
The following performance evaluation test was conducted. The evaluation results are shown in Table 1.

a. Scratch resistance: Load 1 with #0OOO steel wool
The state of the coating was observed after 10 reciprocations at -/-.

A: It hardly gets scratched.

B: Slight damage.

C: Many scratches are created. Adhesion: After immersing in warm water at 80℃ for 2 hours, 11 scratches were made on the lens surface with a knife at intervals of 1 part in each direction, resulting in 100 scratches. Marking D is indicated by the number of squares remaining without the film peeling off after adhering and peeling off the cellophane tape.

C0 Weather Resistance: Xenon Long Life Fade Meter (
The surface condition after 200 hours of exposure was examined using Suga Test Il@ (manufactured by Suga Test Il@).

d. Silicone coating, liquid lifespan: The etymological term ``liquid life'' refers to coating and curing under exactly the same conditions on the 7th day, 144th day, 21st day, and 30th day 0 after adjustment to form an antireflection layer. Thereafter, the tests a to C above were conducted, and the number of days in which the characteristics deteriorated was defined as the liquid life.

Example 2 (1) Production of synthetic resin lens base material (A2) 30 parts of dibenzyl itaconate, 10 parts of diethylene glycol bis(allyl carbonate), 60 parts of diallyl terephthalate
The mixture was mixed and stirred, and 0.2 parts of 2-hydroxy-4-methoxybenzophenone was added. Thereafter, 3.0 parts of di-normal probylno(-oxydicarbonate (manufactured by NOF Corporation; Perloil NPP) was added and mixed well. After filtering the insoluble matter from this mixture, the same procedure as in Example 1 was carried out. Cast polymerization was carried out by.

(2) Preparation and coating curing of brimer coating liquid (P2) As a commercially available acrylic-styrene aqueous emulsion, F430 (Showa Kobunshi ■ product, solid content concentration 45
%) was used. That is, 20 parts of pure water and 20 parts of methanol were slowly added to 20 parts of the aqueous emulsion under strong stirring, and then 80 parts of ethyl cellosolve and 10 parts of propylene glycol monomethyl ether were added. Subsequently, 2.5 parts of para-t-butylphenyl salicylate and a polymer stabilizer (manufactured by Sankyo ■, trade name "Sanol LS-770") were added.
Add 0.5 part of UV absorber 2-(2'-hydroxy-3'-methylphenyl)benzotriazole and dissolve thoroughly, then remove insoluble matter by filtration and apply primer. It was made into a liquid (P2).

This coating liquid was applied in the same manner as in Example 1, and
A primer layer was formed by drying for a minute. The thickness of this primer layer was 0.5μ.

(3) In a flask equipped with a stirring device for preparing and applying a silicone-based coating liquid (H2), put 580 parts of methanol-dispersed colloidal silica (“Methanol Silica Sol” manufactured by Nissei Kagaku Kogyo ■, solid content concentration 30%) and Impropatool. 350 parts, 220 parts of γ-glycidoxyprobyl(methyl)jethoxysilane, 0.1N salt! Add 35 parts of ethyl acetohydrochloride, 12 parts of ethyl acetohydrochloride, and 0.1 part of silicone surfactant, stir thoroughly to make a homogeneous solution, and stir at 0°C for 24 hours.
The mixture was left to ripen for a period of time 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 the brimer, 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, Z r
A four-layer thin film consisting of ZrO2, Aj201, and Zr02.5i02 was formed, and the optical thickness of the film was approximately λ. /4, the next ZrO2 is about λ. /4, and the top layer 5i02 is about λ
. /4.

Note that the design wavelength λ0 is 510 parts m.

(5) Test and evaluation Example 1 Synthetic resin lens obtained by the above method
The results are shown in Table 1.

Example 3 (1) Production of synthetic resin lens base material (A3) 30 parts of dibenzyl itaconate, 10 parts of diethylene glycol bis(allyl carbonate), 60 parts of diallyl isophthalate
The mixture was mixed and stirred, and 0.2 parts of 2-droxy-4-methoxybenzophenone was added. After that, benzoyl peroxide (manufactured by NOF Corporation: Niver B) 3.
5 parts were added and mixed well. 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 at 51°C for 4 hours, at 55°C for 4 hours, at 60°C for 3.5 hours, at 65°C for 3 hours, and at 71°C for 2 hours.
5 hours, 2.5 hours at 75°C, 2 hours at 79°C, 84°C
for 1 hour at 90°C and 2 hours at 90°C. The subsequent operations were performed in the same manner as in Example 1.

(2) Adjustment and coating curing of primer coating liquid (P3) As a commercially available acrylic-styrene aqueous emulsion, Cevian A4719 (Daicel Chemical Industry ■ product, solid content concentration 5
A primer coating liquid (P3) was prepared by adding 20 parts of 0%), 50 parts of water, 70 parts of methanol, 80 parts of ethyl heptatosolve, and 20 parts of dimethylformamide.

The base lens was immersed in this primer coating liquid, pulled up at 10 parts m/min, air-dried, and then dried and cured at 60°C for 30 minutes to obtain a homogeneous primer film with a thickness of 0.4μ. Ta.

(3) Hard coat processing and anti-reflection processing The base material thus obtained was subjected to hard coat processing and anti-reflection film formation in the same manner as in Example 1.

(4) Test and evaluation Example 1 Synthetic resin lens obtained by the above method
The results are shown in Table 1.

Example 4 (1) Production screw (2-
10 parts of chlorobenzyl) itaconate, 10 parts of bis(2-chlorobenzyl) mesaconate, 10 parts of diethylene glycol bis(allyl carbonate), and 40 parts of diallyl isophthalate were mixed and stirred, and ethyl-2-cyano-
0.2 part of 3,3-diphenylacrylate was added.

Thereafter, 2.9 parts of di-2-ethylhexyl peroxide (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.

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

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

Example 5 (1) Production screw (2-
30 parts of itaconate (bromobenzyl), 10 parts of diethylene glycol bis(allyl carbonate), and 60 parts of diallyl isophthalate were mixed and stirred, and 0.
1 part was added. Thereafter, 2.8 parts of diisopropyl peroxydicarbonate was added and mixed well. After filtering out insoluble matter from this mixture, cast polymerization was carried out in the same manner as in Example 1.

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

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

Comparative Example 1 A silicon-based coating liquid (Hl) in Example 1 without adding acetylacetone was prepared (H1).
'), followed by the synthetic resin lens in Example 1 (A
1) in the same manner as in Example 1 using 1 limer solution (
Pl) coating and curing, silicone coating liquid (H1'
) was coated and hardened and anti-reflection treated.

The synthetic resin lenses obtained by the method described below were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 2 The silicone-based coating liquid (H2) in Example 2 was prepared without adding ethyl acetoacetate (H2).
'), followed by the synthetic resin lens in Example 2, (
A 2 ), apply and harden the primer liquid (P2) in the same manner as in Example 2, and apply and cure the silicone coating liquid (
H2') coating was cured and anti-reflection processing was performed.

Example 1 Synthetic resin lens obtained by the above method
The results are shown in Table 1.

Table 1 [Effects of the Invention] As described above, by using the compositions A and B of the present invention, D, a high refractive index resin can be obtained, and at the same time, it is easy to mold, has little coloring, is heat resistant, A synthetic resin lens base material that is solvent resistant and has improved durability such as impact resistance can be obtained. In addition, the composition of the present invention has a slow reaction rate and the reaction rates of each component monomer are close to each other, making it easy to control the reaction, allowing a wide selection of polymerization initiators, and facilitating polymerization operations and process control. be able to.

Furthermore, by forming a coating on the lens surface consisting of a primer layer, hard coat layer, and anti-reflection layer, we have created a synthetic resin lens that has low surface reflection, excellent adhesion, and abrasion resistance, and is highly popular among the general public. It became possible to obtain. Furthermore, in the present invention, we have succeeded in obtaining a longer liquid life by adding β-diketone and/or β-ketonistyl compound to the coating liquid for forming a silicone-based cured film. be.

[Brief explanation of the drawing]

FIG. 1 is a WAr4 diagram of the lens surface in Example 1, where AI is the base lens, Pl is the primer layer, Hl is the silicone-based hardened coating, and 11-15 are the antireflection layers.
Film 11 is 5iOz, 12 is ZrO2, 13 is 5i02.
14 is ZrO2, and 15 is 5i02. FIG. 2 is a reflection spectrum diagram of the lens surface in Example 1. that's all'! l! J1 caries surface (nm) ′@2rgJ

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 film thickness of 0.1 to 2 um 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 um is formed by heating and curing a composition containing the following D, E, and F as main components. A synthetic resin lens characterized by having an anti-reflection layer. A, one or more monomers represented by general formula [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
, the other represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and 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 hydrolyzate and/or partial condensate of one or more silane compounds whose general formula is represented by [3]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [3] (In the formula, R^4 is an organic group having an epoxy group, R^5 is a hydrocarbon group having 1 to 4 carbon atoms, and R^6 is a carbon number Represents 1 to 4 hydrocarbon group, alkoxyalkyl group, or acyl group, a is 0 or 1.) E, particle size 1 to 10
0mμ colloidal silica. F, one or more selected from β-diketones and/or β-ketoester compounds.