JPH07205164A - Manufacture of plastic optical element - Google Patents

Abstract

PURPOSE:To provide a plastic optical element having a cured film having surface hardness and excellent close contact with a base material and excellent durable stability of a reflection preventive film. CONSTITUTION:The method for manufacturing a plastic optical element comprises the steps of cast polymerizing a mixture containing at least one type methacrylic monomer selected from monofunctional methacrylic ester and at least one monomer selected from multifunctional methacrylic acid and epoxy group-containing (meth)acrylic ester as main ingredients to obtain a plastic molded form, and plasma treating the form. The element is obtained by the steps of coating the form with coating composition containing organic silicide having silanol group and epoxy group and colloidal silica as main ingredients, and curing it to form a cured film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic having a cured film having high hardness and excellent adhesion, and an antireflection film provided on a plastic optical element having excellent durability stability and being stably maintained for a long period of time. The present invention relates to a method for manufacturing an optical element.

[0002]

2. Description of the Related Art Transparent plastics, particularly acrylic resins represented by methyl methacrylate polymers, have good transparency and light weight, and are easy to process. It is used in various fields as an optical element such as a prism. However, since acrylic resins generally do not have sufficient surface hardness, it has been attempted to solve this problem by forming a surface-cured film on the surface by coating if necessary. It is known to use a curing liquid such as an organopolysiloxane type, a polyfunctional acrylate type, or an amino resin type for the surface-cured film. Among them, when the base material is an acrylic resin, a polyfunctional acrylate type curing liquid is used. The method used is the mainstream.
However, in the method using a polyfunctional acrylate-based curing liquid, strong ultraviolet rays are generally used during curing, but dyes, infrared absorbers, photochromic substances, etc. are added to the base material or cured film for the purpose of increasing product value. If you do, the effect of UV irradiation at the time of curing diminishes and tends to disappear,
There is a problem that the base material or the cured film turns yellow and deteriorates. Therefore, it is known to use an organopolysiloxane-based curing liquid for these improvements. JP-A-61-166824 discloses a coating composition comprising a hydrolyzate of an organosilicon compound, an epoxy resin compound and an epoxy curing agent as an example of using an organopolysiloxane curing liquid for the acrylic resin. ing.

However, the above-mentioned Japanese Patent Laid-Open No. 61-166.
The coating film obtained from the organopolysiloxane composition disclosed in Japanese Patent No. 824 has an insufficient surface hardness, and, for example, is poor in abrasion resistance against physical cleaning and contact. Therefore, when a metal colloid, which is a general abrasion resistance improver, is added to this organopolysiloxane composition, the film hardness is improved, but there is a problem that the adhesiveness with the base resin is significantly reduced. It was This tendency becomes more remarkable when the crosslink density of the base resin is increased in order to improve strength, heat resistance, solvent resistance and the like.

Further, as a general method for improving the adhesion between the base resin and the cured film, a method of pretreating the base resin with a chemical such as an acid or an alkali or a method of plasma treating the base resin Examples include a method of providing a primer layer between the base resin and the cured film. However, in order to overcome such drawbacks of the acrylic resin and sufficiently adhere the cured film, the conventional treatment with acid or alkali or plasma treatment is completely insufficient, and the method of providing the primer layer is the only method. It was an effective method.

However, this method requires coating, drying and heat curing for each of the primer layer and the cured film, and the process is complicated, and the greatest problem is that the chances of contamination by foreign substances increase during this process. And, there were some aspects that were not practical.

Therefore, the present inventor conducted a study to eliminate the above-mentioned drawbacks of the prior art, and found that methacrylic acid ester
(Meth) acrylic acid and / or hydroxyl group-containing (meth)
By plasma-treating a plastic molded body obtained by casting polymerization of a monomer mixture containing an acrylate ester, a cured film is formed to provide excellent surface hardness and adhesion without providing a primer layer. It was found that an acrylic resin-based plastic lens having a cured film could be obtained,
A patent application has been filed for a method of manufacturing this plastic lens with a cured film (see Japanese Patent Laid-Open No. 4-353801).

[0007]

However, this Japanese Unexamined Patent Application Publication No.
In the method disclosed in Japanese Patent No. 353801, when an antireflection film is formed by vapor-depositing a plurality of metal oxides on the surface as is generally performed for eyeglass lenses, the antireflection film is used for a long period of time. It was found that an abnormality might appear on the surface of the.

An object of the present invention is to have a cured film having excellent surface hardness and adhesion to a substrate, and an antireflection film provided on a plastic optical element has excellent durability stability and is stably maintained for a long period of time. Another object of the present invention is to provide a method for manufacturing a plastic optical element.

[0009]

When attention is paid to the surface hardness of the cured film and the durability stability of the antireflection film, which are the objects of the present invention, the cured film, the material of the antireflection film, the film forming conditions, and the cured film Although it is considered that it is always a means to study the compatibility with the antireflection film, the present inventor has not taken the above-mentioned usual means, and the monomer for producing the base material of the plastic optical element The above object is achieved by using a monomer mixture containing (a) a methacrylic ester-based monomer and (b) an epoxy group-containing (meth) acrylic acid ester-based monomer as main components. I found out what to do.

That is, the method of manufacturing a plastic optical element of the present invention which achieves the above-mentioned object is as follows.
It is characterized by including (2) and (3). (1) A step of obtaining a plastic molded body by casting polymerization of a monomer mixture containing the following components (a) and (b) as main components. (A) At least one methacrylic monomer selected from monofunctional methacrylic acid ester and polyfunctional methacrylic acid ester. (B) At least one monomer selected from epoxy group-containing (meth) acrylic acid esters. (2) A step of plasma-treating the plastic molded body obtained in the step (1). (3) A plastic optical body made of plastic is coated with a coating composition containing the following components (c) and (d) as main components and cured to form a cured film. Process of obtaining a device. (C) An organosilicon compound having a silanol group and an epoxy group. (D) Colloidal silica.

As described above, the method for producing a plastic optical element of the present invention includes steps (1), (2) and (3). These steps will be sequentially described.

Step (1) Step (1) is a step of obtaining a plastic molding by casting polymerization of a monomer mixture containing the components (a) and (b) as the main components. The reason for using the methacrylic monomer of the component (a) as the monomer is to realize excellent optical characteristics such as high transparency and high Abbe number of the acrylic resin in the obtained plastic optical element. As the methacrylic monomer as the component (a), at least one selected from monofunctional methacrylic acid esters and polyfunctional methacrylic acid esters is used. Examples of the monofunctional methacrylic acid ester include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, ethylhexyl methacrylate, benzyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, adamantyl methacrylate, and the like. Further, as the polyfunctional methacrylic acid ester, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate,
Examples include trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, glycerin dimethacrylate, and the like. The preferred content of the methacrylic monomer as the component (a) is in the total monomer mixture (which may contain a third monomer as described below in addition to the components (a) and (b)). It is 30 to 95% by weight, and more preferably 50 to 95% by weight. When the amount of the monomer as the component (a) is less than 30% by weight based on the total amount of the monomer mixture, there are problems that the original excellent transparency and light resistance of the acrylic resin cannot be obtained and the strength is insufficient. When it exceeds 95% by weight, the content of the other essential components such as the component (b) is relatively decreased, so that the improvement of the adhesion to the cured film becomes insufficient.

The reason for using the epoxy group-containing (meth) acrylic acid ester-based monomer as the component (b) is that the adhesion of the plastic molded body to the cured film can be obtained without impairing the durability stability of the antireflection film. This is to improve. The monomer of the component (b) includes at least one epoxy group and at least one epoxy group.
As long as it has one kind of (meth) acrylate group, the kind is not limited, but for example, glycidyl (meth) acrylate; 2-glycidoxyethyl (meth) acrylate, 2-glycidoxypropyl (meth) acrylate,
Glycidoxyalkyl (meth) acrylates such as 4-glycidoxybutyl (meth) acrylate; 2- (glycidoxyethoxy) ethyl (meth) acrylate, 2-
(Glycidoxyethoxy) propyl (meth) acrylate, 4- (glycidoxyethoxy) butyl (meth) acrylate, 2- (glycidoxyisopropoxy) ethyl (meth) acrylate, 2- (glycidoxyisopropoxy) (Glycidoxyalkoxy) alkyl (meth) acrylates such as propyl (meth) acrylate and 4- (glycidoxyisopropoxy) butyl (meth) acrylate; monoglycidyl ether obtained by the reaction of bisphenol A and epichlorohydrin and (meth) Examples thereof include addition products with acrylic acid. Of these, glycidyl (meth) acrylate is particularly preferable. The above-mentioned (meth) acrylate means both acrylate and methacrylate. The preferable content of the monomer of the component (b) is 5 to 5 in the total monomer mixture (which may contain a third monomer as described below in addition to the components (a) and (b)). It is 50% by weight, more preferably 5 to 40% by weight. The monomer of component (b) is 5 in the total monomer mixture.
If it is less than wt%, the adhesion to the cured film will be insufficient,
If it exceeds 50% by weight, the water absorbency becomes large, the physical properties of the resin surface become unstable, and roughening, pocking, etc. are likely to occur.
Further, there are problems that the releasability at the time of imprinting deteriorates, good transferability cannot be obtained, and the imprinting becomes difficult, which is not preferable as an optical element.

In the present invention, a third other monomer copolymerizable with the monomers of the components (a) and (b) may be added within a range that does not impair the effects of the present invention. Examples of such a third monomer include methyl acrylate, ethyl acrylate, n-butyl acrylate, ethylhexyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, isobornyl acrylate, ethylene glycol diacrylate. Acrylate, triethylene glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate,
Acrylic esters such as pentaerythritol triacrylate, nuclear-substituted styrene such as styrene, methylstyrene, dimethylstyrene, chlorostyrene, dichlorostyrene, promstyrene, p-chloromethylstyrene, divinylbenzene, α-methylstyrene, acrylonitrile, Methacrylonitrile, maleic anhydride, N-substituted maleimide and the like and mixtures thereof can be mentioned. Third
The addition ratio of the monomer is preferably 0 to 65% by weight, and particularly preferably 0 to 55% by weight in the total monomer mixture.

In step (1), a cast polymerization method is used for producing a plastic molded body. From the viewpoint of polymerization energy, UV-curing polymerization and radiation-curing polymerization are also used, but thermosetting polymerization is usually adopted. That is, it is a method of adding an appropriate amount of a polymerization initiator to a monomer mixture, injecting it into a mold, and performing heat polymerization. As the polymerization initiator at this time,
Azo initiators such as 2,2'-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile) can be preferably used. Peroxide initiators such as benzoyl peroxide, lauroyl peroxide and t-butylperoxy-2-ethylhexanoate can also be used, but peroxides such as dyes and infrared absorbers can be used in the base material. In the case of adding a compound whose effect tends to decrease or disappear depending on the system initiator, it is better to use the azo system initiator. These initiators are usually 0.001 to 0.001 of the total amount of monomers.
It is preferably used in the range of 5.0% by weight. The heat polymerization temperature varies depending on the initiator used, but is usually 20.
It is in the range of -80 ° C. In addition to the above, a small amount of a heat stabilizer, an antioxidant, an ultraviolet absorber, a release agent, an antistatic agent, etc. may be contained in the plastic molded product, if necessary.

Step (2) The plastic molding obtained in the step (1) is plasma-treated in the step (2). This plasma treatment improves the adhesion between the plastic molded body obtained in step (1) and the cured film provided in step (3). The conditions of the plasma treatment are somewhat different depending on the size, type and shape of the apparatus used, but in the present invention, it is usually in the atmosphere of non-polymerizable gas such as air, helium, argon, hydrogen, oxygen and nitrogen in the range of 0.01 to 10 Torr It takes less than 60 seconds.

Step (3) In the step (3), the coating composition is applied and cured to form a cured film on the plastic molded body which has been subjected to the plasma treatment in the step (2), preferably within 24 hours.

The coating composition used in the present invention comprises an organosilicon compound having a silanol group and an epoxy group in the molecule [component (c)], colloidal silica [component (d)].
Must be included. The component (c) is preferably an organosilicon compound having at least two silanol groups and at least one epoxy group in the molecule, and specific examples thereof include general formula

[Chemical 1] A hydrolyzate obtained by hydrolyzing a trifunctional organosilicon compound represented by the formula (wherein R ¹ is an alkyl group having 1 to 4 carbon atoms and R ² is an alkylene group having 1 to 4 carbon atoms). Is mentioned. It is more preferable that R ¹ in the formula is a methyl group, an ethyl group, a propyl group or a butyl group, and R ² is a methylene group, an ethylene group, a propylene group or a butylene group.

On the other hand, as the colloidal silica as the component (d), a high concentration of water-dispersed colloidal silica (for example, SiO ₂ solid content of 40% is used) in order to prevent excess water from being left after the hydrolysis of the organosilicon compound. The above) are preferably used. The average particle size is preferably in the range of 5 to 100 mμ, and more preferably 5 to 30 mμ. By using the organopolysiloxane-based coating composition containing a high concentration of colloidal silica, a cured film having higher hardness can be obtained. Therefore, the coating composition used in the present invention exhibits its usefulness when it contains a high concentration of colloidal silica. From that point of view, in the present invention, the amount of colloidal silica in the coating composition is preferably set to 55 to 90 mol% (SiO ₂ solid content conversion value) based on the total amount of the colloidal silica and the organosilicon compound. The preferred range is 75-9
It is 0 mol%.

Hardeners are usually used, and examples thereof include imidazole derivatives, but acetylacetone metal complex compounds, particularly acetylacetone aluminum complex compounds, are particularly effective. The amount added is an amount sufficient to cure the colloidal silica and the hydrolyzate of the organosilicon compound, that is, 1 to 10 g per 1 mol of the total of the hydrolyzate of the colloidal silica (SiO ₂ conversion) and the organosilicon compound. Is preferred.

An organic acid is used for the hydrolysis of the organosilicon compound of the formula (I). Examples thereof include formic acid, acetic acid, propionic acid, and the like, and acetic acid is preferably used because of the stability of the coating composition. The amount of the organic acid added is preferably 5 to 30 g per 1 mol of the total amount of the colloidal silica and the organic silicon compound. If it is less than this range, gelation of the coating composition is likely to occur, and if it is more than this range, the odor becomes strong and it is not preferable in the work.

Further, in order to make the hydrolysis uniform and adjust the degree of hydrolysis appropriately, it is preferable to add a suitable solvent to the coating composition. As such a solvent, cellosolves such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve are preferable, and combination with isopropyl alcohol, butanol and the like is more preferable. The proportion of cellosolve is preferably 3% by weight or more, and particularly preferably 10% by weight or more based on the total amount of the solvent. If the proportion of colloidal silica is high and the proportion of cellosolve in the solvent is less than 3% by weight of the total amount of solvent, gelation tends to occur during the preparation of the coating composition.

A silicone-based surfactant may be added to the coating composition used in the present invention for the purpose of improving the smoothness of the coating film. Further, for the purpose of improving the light resistance or preventing the deterioration of the coating film, it is possible to add an ultraviolet absorber, an antioxidant or the like.

The coating composition can be applied to the plastic molding by a dipping method, a spin coating method, a roll coating method, a spray method or the like. Curing of the applied coating composition is carried out by heat treatment, and the heating temperature is preferably 40 to 150 ° C, particularly preferably 80 to 130 ° C. The heating time is preferably 1 to 4 hours. The cured film obtained after coating and curing of the coating composition has excellent adhesion to the plastic molded body because the plastic molded body is plasma-treated in the step (2). After forming the cured film, it is usual to form an antireflection film on the cured film by vapor deposition.

Such an antireflection film is formed of SiO, SiO ₂ , Si ₃ N ₄ , TiO ₂ , ZrO by a vacuum deposition method, an ion sputtering method, an ion plating method or the like.
It is formed by laminating a single layer or a multi-layered thin film made of a dielectric material such as ₂ , Al ₂ O ₃ , MgF ₂ or the like, whereby the reflection at the interface with the atmosphere can be suppressed low. When the antireflection film is composed of a single layer, its optical thickness is λ
_It is preferably 0/4 (λ ₀ = 450 to 650 nm). The different bilayer refractive index of the optical film thickness of _{λ 0/4-λ 0/} 4, the optical thickness of _{λ 0/4-λ 0/} 2-λ 0 /
4 or _{λ 0/4-λ 0/} 4-λ 0/4 of the refractive index of different three-layered film from the consisting multilayer antireflection film or useful consist antireflection film according to the multilayer coating was replaced with some equivalent layer, Is.

The method for producing a plastic optical element of the present invention is remarkable in that the cured film provided on the plastic molded body has high hardness and excellent adhesiveness, and the antireflection film is stably retained for a long period of time. Have a significant effect.

The reason why the above-mentioned effects are obtained by selecting the monomer for the plastic molded article is that plasma treatment is carried out because the epoxy group-containing (meth) acrylic acid ester is used as the monomer for the plastic molded article in the present invention. As a result, a cured film having a high hardness containing a high concentration of colloidal silica can be provided, and a hydroxyl group-containing (meth) acrylic acid ester is used as a monomer for a plastic molded product, which is disclosed in JP-A-4-353801. This is because the antireflection film provided on the cured film is more durable than the optical element. The reason for this is not clear, but it is considered that there is a difference in water absorption of the plastic molding or in the microscopic surface accuracy retention of the cured film due to this repetition.

[0028]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The methods for evaluating physical properties in Examples and Comparative Examples are as follows.

(A) Surface Hardness The surface was rubbed 50 times (reciprocating) with steel wool # 0000 under an additional load of 1000 g, and the scratch resistance was judged according to the following criteria. A: Almost no scratches. B: Very slightly scratched. C: A little scratched. D: Many scratches.

(B) Adhesion: The surface of the cured film was cut into 1 mm intervals to form burdock (10 × 10 pieces), and a cellophane adhesive tape (No. 1 manufactured by Nichiban Co., Ltd.) was used.
405) was strongly adhered, and it was rapidly peeled off in the direction of 90 degrees, and the number of gobang eyes left was examined.

(C) Appearance The transparency, the colored state, the surface state and the like were visually inspected.

(D) Durability stability of antireflection film An antireflection film was applied to an optical element with a cured film in the following manner. SiO ₂ as an underlayer at a pressure of 5 × 10 ⁻⁵ Torr or less
Is vacuum-deposited to a film thickness of 0.5 microns, and Zr
After vaporizing O ₂ by about 1 / 17λ (λ is 550mμ), S
iO ₂ was evaporated until the total film thickness of these two materials was about λ / 4. Then, ZrO ₂ was vapor-deposited thereon to a film thickness of λ / 4 to form an antireflection film. The obtained optical element with an antireflection film was allowed to stand at 50 ° C. and a humidity of 90% for 100 hours, and then the surface condition was visually inspected. The case where no abnormality was observed in the surface condition was indicated by ◯, and the case where fine cracks, strains, etc. were observed were indicated by x.

[Preparation of coating composition] Colloidal silica having a SiO ₂ concentration of 40% (Snowtex-40,
Water-dispersed silica, average particle size 10 to 20 mμ, manufactured by Nissan Chemical Co., Ltd.) 240 parts by weight, 0.5 N hydrochloric acid 2.0 parts by weight,
A solution containing 20 parts by weight of acetic acid was added at 95 ° C. with stirring to add 95 parts by weight of γ-glycidoxypropyltrimethoxysilane (trifunctional organosilicon compound), and the mixture was stirred at room temperature for 8 hours and then left for 16 hours. . This hydrolysis solution 32
To 0 parts by weight, 80 parts by weight of methyl cellosolve, 120 parts by weight of isopropyl alcohol, 40 parts by weight of butyl alcohol, 16 parts by weight of aluminum acetylacetone, 0.2 parts by weight of silicone surfactant, and 0.1 parts by weight of ultraviolet absorber were added. After stirring for 8 hours, it was aged at room temperature for 24 hours to obtain a coating composition. This is designated as coating composition (A). At this time, the amount of colloidal silica in the coating composition was 80 based on the total amount of colloidal silica and γ-glycidoxypropyltrimethoxysilane.
It was mol% (SiO ₂ solid content conversion value).

A coating composition (B) was obtained in the same manner as the preparation of the coating composition (A) except that the amount of γ-glycidoxypropyltrimethoxysilane was 67 parts by weight. The amount of colloidal silica in the coating composition at this time was 85 mol% based on the total amount of colloidal silica and γ-glycidoxypropyltrimethoxysilane.
(SiO ₂ solid content conversion value).

The coating composition (C) was prepared in the same manner as in the preparation of the coating composition (A) except that the amount of γ-glycidoxypropyltrimethoxysilane was changed to 253 parts by weight.
Got The amount of colloidal silica in the coating composition at this time was 60 mol based on the total amount of colloidal silica and γ-glycidoxypropyltrimethoxysilane.
% (SiO ₂ solid content conversion value).

Ion-exchanged water 1 instead of colloidal silica
A coating composition (D) was obtained in the same manner as in the preparation of the coating composition (A) except that 20 parts by weight was used.

Example 1 Production of Optical Element with Cured Film 60 parts by weight of methyl methacrylate, 20 parts by weight of glycidyl methacrylate, 20 parts by weight of ethylene glycol dimethacrylate, azobis radical polymerization initiator (azobisisobutyronitrile) 0.30 parts by weight, ultraviolet absorber (Tinuvin P manufactured by Ciba-Geigy) 0.05 parts by weight, release agent (Shin-Etsu Silicone KF353A manufactured by Shin-Etsu Chemical Co., Ltd.)
0.01 parts by weight was added and mixed and dissolved. This compounded solution was poured into a mold composed of two glass molds and a plastic gasket, and this was placed in a hot air circulation type heating furnace and heated to 50
The mixture was heated at 8 ° C for 12 hours, then heated to 85 ° C over 4 hours, and then heated for 2 hours to carry out polymerization. The polymer obtained by removing the mold was a highly transparent plastic molded product forming a meniscus lens having a diameter of 75 mm, a thickness of 2.0 mm and a power of 0.00 diopter. Add this to 120 ℃
Annealing was performed by heating for 2 hours.

This plastic molded body was subjected to plasma treatment for 1 second under an atmosphere of 0.6 Torr of nitrogen using PR-501A manufactured by Yamato Scientific Co., Ltd.

Subsequently, the coating composition (A) was applied by a dipping method (pulling speed: 20 cm / min), and this was cured by heating at 120 ° C. for 90 minutes to form a cured film.

The evaluation results of the optical element with a cured film thus obtained are shown in Table 1 below.
The durability and stability of the antireflection film were excellent.

[Examples 2 to 10] Production of optical element with cured film Except that the plasma treatment conditions shown in Table 1 and coating compositions (A), (B) and (C) containing SiO ₂ were used. In the same manner as in Example 1, a cured film-coated optical element was produced and evaluated in the same manner. As shown in Table 1, the surface hardness, adhesion, appearance, and durability stability of the antireflection film were excellent.

[Comparative Examples 1 to 3] An optical element with a cured film was prepared in the same manner as in Example 1 except that the plasma treatment conditions shown in Table 1 and the coating composition (D) containing no SiO ₂ were used. It was produced (Comparative Example 1). Further, a coating composition (A) containing SiO ₂ without plasma treatment
An optical element with a cured film was obtained in the same manner as in Example 1 except that the coating composition (D) containing no and SiO ₂ was used, respectively (Comparative Examples 2 and 3). The results of these evaluations were inferior in film hardness and adhesion as shown in Table 1.

[Comparative Examples 4 to 6] An optical element with a cured film was prepared and evaluated in the same manner as in Example 1 except that the chemical treatment as shown in Table 1 was performed instead of the plasma treatment. It was The results were inferior in film hardness and adhesion as shown in Table 1.

[0044]

[Table 1]

[Examples 11 to 18] Production of optical element with cured film An optical element with a cured film was produced in the same manner as in Example 1 except that the composition of the monomer mixture was changed as shown in Table 2. , And similarly evaluated. As a result, since the composition of the monomer composition satisfies the requirements of the invention, the surface hardness, adhesion, appearance and durability stability of the antireflection film were excellent as shown in Table 2.

[Comparative Example 7] The composition of the monomer mixture is shown in Table 2.
A cured film-coated optical element was prepared in the same manner as in Example 1 except that the component (b) was not used, and the same evaluation was performed. As a result, the composition of the monomer mixture did not satisfy the requirements of the present invention, and thus the surface hardness and the adhesion were inferior as shown in Table 2.

[0047]

[Table 2]

Example 19 Production of Optical Element with Cured Film 0.06 parts by weight of a near-infrared absorber (SIR-114 manufactured by Mitsui Toatsu Dye Co., Ltd.) was added to the monomer mixture of Example 1,
Thereafter, an optical element was produced in the same manner as in Example 1. This optical element is excellent in surface hardness A and cured film adhesion of 100/100, and selectively absorbs light having a wavelength of 650 to 780 nm, and thus can be suitably used as a lens for laser protection eyeglasses. . Further, the durability of the antireflection film of this lens was also good.

[Comparative Examples 8 to 13] In the same manner as in Example 1 except that the hydrophilic monomer shown in Table 3 was used in place of the monomer of the component (b) in the monomer mixture. An optical element with a cured film was prepared and evaluated in the same manner. The results were excellent in surface hardness, adhesion, and appearance as shown in Table 3, but after the durability stability test of the antireflection film, all had fine crack-like abnormalities on the surface and were preferable as optical elements. It wasn't something.

From Comparative Examples 8 to 13, among the requirements constituting the present invention, even if the requirements for the plasma treatment and the coating composition are satisfied but the requirements for the monomer for the plastic molded article are not satisfied, the durability of the antireflection film is improved. It is clear that an optical element having excellent stability cannot be obtained.

[0051]

[Table 3]

[0052]

According to the present invention, a plastic optical element having a cured film excellent in surface hardness and adhesion to a plastic molded body and having excellent durability stability of an antireflection film provided on the plastic optical element. Will be provided. The obtained plastic optical element is particularly preferably used for eyeglasses and sunglasses, but is also used for various instrument covers, lighting equipment, automobile mirrors, cameras, lenses for optical machines such as microscopes, etc. To be

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Claims (2)

[Claims] 1. The following steps (1), (2) and (3):
A method of manufacturing a plastic optical element, comprising: (1) A step of obtaining a plastic molded body by casting polymerization of a monomer mixture containing the following components (a) and (b) as main components. (A) At least one methacrylic monomer selected from monofunctional methacrylic acid ester and polyfunctional methacrylic acid ester. (B) At least one monomer selected from epoxy group-containing (meth) acrylic acid esters. (2) A step of plasma-treating the plastic molded body obtained in the step (1). (3) A plastic optical body made of plastic is coated with a coating composition containing the following components (c) and (d) as main components and cured to form a cured film. Process of obtaining a device. (C) An organosilicon compound having a silanol group and an epoxy group. (D) Colloidal silica. 2. The method according to claim 1, wherein the plastic optical element is an eyeglass lens.