JP3073546B2 - Method for manufacturing laser protective eyeglass lens - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a lens for laser protective eyeglasses made of an acrylic resin having a cured film having a high hardness and excellent adhesion on the surface and having an absorption in a wavelength region of 600 nm or more. It is. The laser protective eyeglass lens obtained according to the present invention is particularly suitable for semiconductors, YAG, H
It is used as a lens for protective glasses when handling a laser device having an oscillation wavelength in the above wavelength range such as e-Ne, ruby, Kr, and the like.

[0002]

2. Description of the Related Art Currently He-Ne, Ar, Kr, He-C
d, CO2 gas, gas laser such as excimer, YA
Various lasers such as solid-state lasers such as G, ruby, and glass, and semiconductor lasers have gained wide application fields and are becoming more widely used.

[0003] However, it is known that the laser irradiation on the eye tissue is dangerous, and on the other hand, it is necessary to provide a sufficient optical density so as to shield the laser and protect the eye from laser light. It is necessary to wear safety glasses.

[0004] Conventional laser protective eyeglass lenses include:
Absorption filters such as colored glass and colored plastics are known, and the colored glass usually has absorption in a required wavelength range in materials such as blue plate and white plate glass, and optical lens materials such as BK-7. It contains ions and elements. The colored plastic lens is obtained by mixing a plastic resin having transparency, such as polycarbonate or acrylic resin, with a pigment orange, pigment blue-based organic or inorganic pigment, etc., into the resin base before molding and injection molding.

[0005]

However, the colored glass is not only heavy and easily broken due to physical impact, but also when irradiated with a laser beam having a high energy density, the irradiated portion partially undergoes thermal expansion and suddenly expands. It can be destroyed and is very dangerous and undesired in the unlikely event.

[0006] The polycarbonate resin constituting the colored plastic lens is excellent in impact resistance, but is particularly low in Abbe number and inferior in transparency. There is a problem that. In addition, acrylic plastic lenses obtained by injection molding generally have poor heat resistance, and when used in laser protective glasses, the laser receiving surface may melt or have holes. In addition, polycarbonate and acrylic resin are obtained by an injection molding method, and since a mold having an optical surface polished to a mirror surface is used in the production thereof, the exchange of the mold in a molding apparatus is complicated. Therefore, it is suitable for mass production of small varieties,
It has a wide range of lens powers, such as eyeglass lenses for eyesight correction, and in the case of a high-mix, low-volume production system, it requires time for mold replacement and a large number of mold stocks, resulting in cost burdens. However, many problems remain practically.

[0007] Further, since acrylic resin has insufficient surface hardness, especially when used as laser protective glasses, it does not have durability enough to withstand its normal use. For example, Japanese Patent Application Laid-Open No. 61-166824. As disclosed in Japanese Patent Application Laid-Open Publication No. H11-260, there is a practice of providing an organopolysiloxane cured film. However, the cured organopolysiloxane film disclosed in this publication has a basic problem that the degree of adhesion to the base resin has not reached a practical range that can be used as laser protective glasses, and furthermore,
In order to increase the film hardness and its durability, when an additive such as a metal colloid sol is contained in the above-mentioned cured film,
There is a further problem that the degree of adhesion is reduced.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and has as its object to have an optical density sufficiently high to block laser light, and to have abrasion resistance, a high Abbe number, and heat resistance. It is an object of the present invention to provide a method for producing a laser protective eyeglass lens having optical characteristics required as a spectacle lens such as properties.

[0009]

According to the present invention, there is provided a method for manufacturing a lens for laser protective glasses according to the present invention, which comprises the following steps (1), (2) and (3).

(1) A step of casting a monomer mixture containing the following components (a), (b), (c) and (d) as main components to obtain a lens. (A) methyl methacrylate, (b) at least one hydrophilic monomer selected from (meth) acrylic acid and a hydroxyl group-containing (meth) acrylate, (c) component (a) and component (b) (D) an oil-soluble dye and / or a near-infrared absorber, (2) a non-polymerizable gas for the lens obtained in the step (1).
Treating under-flops plasma atmosphere. (3) A step of applying a coating composition containing the following components (e), (f) and (g) as main components to the lens subjected to the plasma treatment in the step (2), and curing the lens to form a cured film. (E) an organosilicon compound having a silanol group and an epoxy group, (f) colloidal silica, and (g) an acetylacetone metal complex compound. As described above, the method for manufacturing a lens for laser protective glasses according to the present invention includes steps (1), (2) and (3). These steps will be described sequentially.

Step (1) Step (1) is a step of casting a monomer mixture containing the components (a), (b), (c) and (d) as main components to obtain a lens. is there.

The reason for using methyl methacrylate as the component (a) as a monomer is to realize excellent optical characteristics such as high transparency and high Abbe number of an acrylic resin in a laser protective eyeglass lens obtained. is there. In addition, together with the methyl methacrylate of the component (a), a monofunctional monomer copolymerizable therewith can be used. Examples of such monofunctional monomers include methacrylates such as ethyl methacrylate, n-butyl methacrylate, ethylhexyl methacrylate, benzyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, and adamantyl methacrylate; Acrylic esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, ethylhexyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, isobornyl acrylate, styrene, methyl styrene, dimethyl styrene, chlorostyrene Nucleus substituted styrene such as dichlorostyrene, bromostyrene, p-chloromethylstyrene, α-methylstyrene, acrylonitrile, methacrylonitrile, maleic anhydride, N- Conversion maleimide and the like. The preferable content of the methyl methacrylate of the component (a) and the above-mentioned monofunctional monomer optionally used is 30 to 92% by weight, more preferably 40 to 85% by weight of the total monomer mixture. is there. These monomers represent 30% of the total monomer mixture.
If the amount is less than 10% by weight, problems such as the inability to obtain excellent transparency and light resistance inherent in the acrylic resin and insufficient strength occur. If the amount is more than 92% by weight, the monomer has a hydrophilic group. Since the content of the component (b) or the component (c), which is a crosslinkable monomer, is relatively reduced, improvement in heat resistance and adhesion to a cured film becomes insufficient.

As the hydrophilic monomer as the component (b), at least one selected from (meth) acrylic acid and a hydroxyl group-containing (meth) acrylate is used. In this specification, “(meth) acrylic acid” means both “acrylic acid” and “methacrylic acid”.
Examples of these include acrylic acid, methacrylic acid, hydroxyethyl ester of acrylic acid or methacrylic acid,
Chlorohydroxypropyl ester of acrylic acid or methacrylic acid; The preferred content of these monomers is from 5 to 50% by weight, more preferably from 5 to 30% by weight, based on the total monomer mixture. When the amount of these monomers is less than 5% by weight of the total monomer mixture, the improvement in adhesion to the cured film becomes insufficient, and when the amount exceeds 50% by weight, the water absorption becomes large and the physical properties of the resin surface become poor. Become unstable, rough,
Pocking and the like are likely to occur. In addition, the releasability at the time of molding is deteriorated, and problems such as difficulty in obtaining good transferability and difficulty in molding occur.

As the crosslinkable polyfunctional monomer as the component (c), those which can be copolymerized with the components (a) and (b) are used, and ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, and triethylene glycol dimethacrylate are used. Methacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate,
Multifunctional methacrylates such as pentaerythritol tetramethacrylate and glycerin trimethacrylate, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, and pentaerythritol tetraacrylate Functional acrylates, divinylbenzene and the like can be mentioned. The preferred content of these monomers varies depending on the type thereof, but generally ranges from 3 to 50 in the total monomer mixture.
% By weight. The reason is that if the crosslinkable monomer is less than 3% by weight, the heat resistance becomes insufficient, and the lens may be melted by irradiation with laser light, while if it exceeds 50% by weight, the impact resistance decreases. This is not preferable because problems such as molding and difficulty in shaping occur. Taking ethylene glycol dimethacrylate as an example, 3 to 30
% By weight is preferred.

The component (d) is used for the purpose of absorbing and blocking laser light. Applicant filed Japanese Patent Application Laid-Open No. 62-231925
In Japanese Unexamined Patent Publication, a reference model of safety glasses for laser light was proposed. It is based on the maximum permissible exposure (MPE) in the cornea (ocular surface) when laser radiation directly exposes the eye, as set forth in the Radiation Safety Standard for Laser Products (JIS). The MPE means a laser intensity of 1/100 at which the rate of injury to the eyeball is 50% level, and is used as an index for controlling the laser exposure. Therefore, the laser intensity was calculated from the laser oscillation wavelength, the emission time, and the like, and finally, based on the average laser output, a lens optical density (OD) satisfying the MPE was derived. The values are OD = 3.2 for Ar laser and OD = 1.6 for He-Ne laser.
8. OD = 1.10 for Ga-As laser and OD = 3.33 for YAG laser. Therefore, although it differs depending on the type and output of the laser used, at least OD
Is 1.10 or more, it is determined that the lens is useful as a laser protective eyeglass lens. In the present invention, a dye and / or a near-infrared absorbing agent is used as a component for imparting the OD. Of course, these dyes and near-infrared absorbers are determined in consideration of the oscillation wavelength of the laser to be used, but as shown in Examples described later, generally have a peak of absorption at 600 nm to 1200 nm. If there is, an absorption band also exists in the surrounding wavelength band at the same time. For example, a helium neon laser (63
A laser having an oscillation wavelength in the range from 2.8 nm) to a YAG laser (1060 nm) can be suitably used. or,
From the viewpoint of workability when wearing laser protective glasses, it is preferable that the absorption band has as little influence as possible on the visible region. In particular, in the present invention, the component (d) is directly contained in the monomer mixture.
No dyeing (post-dyeing) after lens molding as shown in the method of manufacturing a lens for laser protective glasses disclosed in JP-A No. 5 (1993) -105, so that the content of the component (d) is wide and a sufficient OD can be imparted. it can. Specifically, the content varies depending on the molar extinction coefficient specific to the dye and the OD to be obtained, but is preferably such that the OD is about 4 to 5 as shown in Examples described later.

The dye of component (d) and the near-infrared absorber contained in the monomer mixture must be soluble in the above-mentioned monomers and stable with respect to the polymerization initiator. In the case of a dye having absorption in the visible region, many commercially available oil-soluble dyes can be used. However, as the near-infrared ray absorbing agent, a near-infrared ray absorbing agent such as an anthraquinone-based compound and a metal complex compound-based compound having excellent light resistance is preferable.

In step (1), the lens is produced by a casting polymerization method, and usually a thermosetting polymerization is employed. That is, this is a method in which an appropriate amount of a polymerization initiator is added to the monomer mixture, the mixture is injected into a mold, and heat polymerization is performed. As the polymerization initiator at this time, 2,2'-azobisisobutyronitrile,
An azo initiator such as 2,2'-azobis (2,4-dimethylvaleronitrile) can be suitably used. Peroxide initiators such as benzoyl peroxide, lauroyl peroxide and t-butylperoxy-2-ethylhexanoate are preferred because they reduce or eliminate the effects of oil-soluble dyes and near-infrared absorbers in the lens. Absent. These initiators are usually preferably used in the range of 0.001 to 5.0% by weight of the total amount of the monomers. The heating polymerization temperature varies depending on the initiator used, but is usually in the range of 20 to 80 ° C.

In addition, a small amount of a heat stabilizer, an antioxidant, an ultraviolet absorber, a release agent, an antistatic agent, and the like can be contained in the lens, if necessary.

Step (2) The lens obtained in step (1) is subjected to a plasma treatment in step (2). This plasma treatment improves the adhesion between the lens obtained in step (1) and the cured film provided in step (3). The conditions for plasma processing vary somewhat depending on the size, type, and shape of the equipment used,
In the present invention, the reaction is usually performed within 60 seconds in an atmosphere of a non-polymerizable gas such as air, helium, argon, hydrogen, oxygen and nitrogen of 0.01 to 10 Torr.

Step (3) After the plasma treatment in step (2), the coating composition is applied and cured in step (3), preferably within 24 hours, to form a cured film. The coating composition used in the present invention includes an organosilicon compound having a silanol group and an epoxy group in the molecule [component (e)],
It is necessary to include colloidal silica [component (f)] and acetylacetone metal complex compound [component (g)].
As the component (e), an organosilicon compound having at least two silanol groups and at least one epoxy group in a molecule is preferable.

[0021]

Embedded image

(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) obtained by hydrolyzing a trifunctional organosilicon compound represented by the formula: Hydrolyzate. R ¹ in the formula is a methyl group,
More preferably, they are 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 (f), in order to avoid leaving excess water as much as possible after the hydrolysis of the organosilicon compound, a high-concentration water-dispersed colloidal silica (for example, a SiO ₂ solid content of 40% Above) are preferably used. The average particle diameter is preferably in the range of 5 to 100 mμ, and more preferably 5 to 30 mμ. By using an 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. In that sense, in the present invention, the amount of colloidal silica in the coating composition is preferably set to 55 to 90 mol% (in terms of SiO ₂ solid content) based on the total amount of colloidal silica and the organosilicon compound. The preferred range is 75-9
0 mol%.

As the acetylacetone metal complex compound of the component (g) as a curing agent, an aluminum complex compound is particularly effective. The amount of addition is 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 (in terms of SiO ₂ ) and the organosilicon compound. It is preferred that

An organic acid is used for the hydrolysis of the organosilicon compound of the formula (I). These include formic acid, acetic acid, propionic acid and the like, but it is preferable to use acetic acid in view of the stability of the coating composition. The addition amount of the organic acid is preferably 5 to 30 g based on 1 mol of the total amount of the colloidal silica and the organosilicon compound. If the amount is less than this, gelling of the coating composition is apt to occur, and if it is more than this, odor becomes strong, which is not preferable in work.

Further, in order to make the hydrolysis uniform and to control the degree thereof 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 a combination with isopropyl alcohol, butanol and the like is more preferable. The proportion of cellosolve is preferably at least 3% by weight of the total solvent amount, particularly preferably at least 10% by weight. When the proportion of colloidal silica is large, if the proportion of cellosolve in the solvent is less than 3% by weight of the total solvent, gelation occurs during the preparation of the coating composition and the composition cannot be formed.

[0027] To the coating composition used in the present invention, a silicone surfactant may be added for the purpose of improving the smoothness of the coating film. Further, an ultraviolet absorber, an antioxidant and the like can be added for the purpose of improving light resistance or preventing deterioration of the coating film.

The coating composition can be applied to the lens by dipping, spin coating, roll coating, spraying, or the like. Curing of the applied coating composition is performed by heat treatment, and the heating temperature is preferably 40 to 150 ° C., particularly preferably 8 to 150 ° C.
0-130 ° C. The heating time is preferably 1 to 4 hours. The cured film obtained after application and curing of the coating composition has excellent adhesion to the lens since the lens is subjected to the plasma treatment in the step (2). After forming the cured film, the cured film may be coated by vapor deposition.

[0029]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In addition, the method of the physical property evaluation in an Example and a comparative example is as follows.

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

(B) Adhesion The surface of the cured film was cut into squares (10 × 10) at intervals of 1 mm, and a cellophane adhesive tape (No.
405) was strongly adhered, and the number of goban eyes remaining after being peeled off sharply in the direction of 90 degrees was examined.

(C) Appearance Transparency, colored state, surface state, etc. were examined with the naked eye.

(D) Spectrophotometry Spectrophotometer U-3410 manufactured by Hitachi, Ltd. was used to perform spectrophotometry to measure absorption characteristics and optical density.

[Preparation of Coating Composition] Colloidal silica having a SiO ₂ concentration of 40% (Snowtex-40,
Water-dispersed silica, average particle size of 10 to 20 mμ, manufactured by Nissan Chemical Co., Ltd.
95 parts by weight of γ-glycidoxypropyltrimethoxysilane (trifunctional organosilicon compound) was added dropwise while stirring the solution containing 20 parts by weight of acetic acid at 35 ° C., and the mixture was stirred at room temperature for 8 hours, and then allowed to stand for 16 hours. . 80 parts by weight of methyl cellosolve, isopropyl alcohol 1
20 parts by weight, 40 parts by weight of butyl alcohol, 16 parts by weight of aluminum acetylacetone, 0.2 parts by weight of a silicone surfactant, and 0.1 parts by weight of an ultraviolet absorber,
After stirring for an hour, the mixture 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 mol% (SiO _{2) based on} the total amount of colloidal silica and γ-glycidoxypropyltrimethoxysilane.
(In terms of solid content).

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

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.
I got At this time, the amount of the colloidal silica in the coating composition was 60 mol based on the total amount of the colloidal silica and γ-glycidoxypropyltrimethoxysilane.
% (In terms of SiO ₂ solid content).

Ion-exchanged water 1 in place 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 20 parts by weight of methacrylic acid, 20 parts by weight of ethylene glycol dimethacrylate, 30 parts by weight of styrene, 30 parts by weight of methyl methacrylate, and a near-infrared absorbing agent (near-infrared absorbing agent manufactured by Mitsui Toatsu Dye Co., Ltd.) Agent SIR
-114) 0.06 parts by weight, azobis-based radical polymerization initiator (V-70 manufactured by Wako Pure Chemical Industries, Ltd.) 0.15 parts by weight, ultraviolet absorber (Tinuvin P manufactured by Ciba Geigy, Inc.)
0.10 parts by weight of a releasing agent (Shin-Etsu Chemical Co., Ltd. Shin-Etsu Silicone KF353A) 0.01 part by weight was added and mixed and dissolved. This mixture was poured into a mold composed of two glass molds and a plastic gasket, placed in a hot-air circulation heating furnace, heated at 37 ° C. for 8 hours, and then heated to 90 ° C. over 8 hours. The mixture was heated for 2 hours to carry out polymerization. The polymer obtained by removing the mold has a diameter of 75 m.
m, a thickness of 2.0 mm and a green color of 0.00 diopter. This was further heated at 120 ° C. for 2 hours for annealing.

The resin composition was added to a PR by Yamato Scientific Co., Ltd.
Plasma treatment was performed using -501A under a nitrogen atmosphere of 0.6 Torr for 1 second.

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

The evaluation results of the thus obtained lens with a cured film were excellent in surface hardness, adhesion and appearance as shown in Table 1. Further, as shown in FIG. 1, this cured film-coated lens selectively absorbs light having a wavelength of 650 to 790 nm, and the optical density (OD) particularly reaches 4 or more at 670 to 785 nm. Therefore, it could be suitably used as a lens for protective glasses such as a ruby laser (oscillation wavelength of about 600 to 694 nm) and a Ga-As laser (oscillation wavelength of about 740 to 790 nm).

Examples 2 to 10 In the same manner as in Example 1 except that the plasma treatment conditions shown in Table 1 and the coating compositions (A), (B) and (C) containing SiO ₂ were used. Thus, a lens for laser protective glasses was prepared and evaluated in the same manner. The results were excellent as shown in Table 1. These lenses are 650-7 as in the first embodiment.
It selectively absorbs light having a wavelength of 90 nm, especially 670-78.
At 5 nm, the optical density reached 4 or more. For this reason, it could be suitably used as a protective eyeglass lens such as a ruby or Ga-As laser.

Comparative Examples 1 to 3 A lens with a cured film was produced 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. (Comparative Example 1). Also without plasma treatment, to obtain a coating composition (A) and except that SiO ₂ and contained no coating composition (D) were used, respectively in the same manner as in Example 1 the cured film with lens comprising SiO ₂ (Comparative Example 2 and Comparative Example 3). These evaluation results were inferior in film hardness and adhesion as shown in Table 1.

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

[0045]

[Table 1]

[Examples 11 to 16] For laser protective glasses in the same manner as in Example 1 except that the hydrophilic monomer as the component (b) in the monomer mixture was changed as shown in Table 2. A lens was prepared and evaluated similarly. The results were excellent in surface hardness, adhesion and appearance as shown in Table-2. These lenses selectively absorb light having a wavelength of 650 to 790 nm, and particularly have an optical density of 4 or more at 670 to 785 nm. For this reason, it could be suitably used as a protective eyeglass lens such as a ruby or Ga-As laser.

[0047]

[Table 2]

[Examples 17 to 20] A lens with a cured film was prepared in the same manner as in Example 1 except that the composition of the monomer mixture was changed as shown in Table 3, and the evaluation was performed in the same manner. The results were excellent in surface hardness, adhesion and appearance as shown in Table-3. Also, these lenses are 650-790
selectively absorbs light having a wavelength of nm, especially 670-785 nm
The optical density reached 4 or more. For this, Ruby, G
It could be suitably used as a lens for protective glasses such as an a-As laser.

[Comparative Examples 7 and 8] A lens was produced in the same manner as in Example 1 except that the composition of the monomer mixture was changed as shown in Table 3, and evaluation was conducted in the same manner. As a result, when the composition of the monomer mixture did not satisfy the requirements of the present invention, the film hardness and adhesion were poor as shown in Table 3 (Comparative Example 7).
In addition, a good lens shape was not obtained (Comparative Example 8).

[0050]

[Table 3]

Example 21 60 parts by weight of methyl methacrylate, 20 parts by weight of methacrylic acid, 20 parts by weight of ethylene glycol dimethacrylate, and 0.04 part by weight of a near-infrared absorbing agent (SIR-114 manufactured by Mitsui Toatsu Dye Co., Ltd.) Department, same (S
IR-128) 0.07 part by weight, a radical polymerization initiator (V-70 manufactured by Wako Pure Chemical Industries, Ltd.) 0.30 part by weight, an ultraviolet absorber (Tinuvin P manufactured by Ciba Geigy) 0.1
0 parts by weight, release agent (Shin-Etsu Silicone K, manufactured by Shin-Etsu Chemical Co., Ltd.)
F353A) 0.01 part by weight was added and mixed and dissolved. Using this prepared liquid, a lens having a green surface-hardened film was obtained in the same manner as in Example 1. This lens had excellent surface hardness A and adhesion of the cured film of 100/100. This lens is 700 to 850 as shown in FIG.
Light having a wavelength of nm was selectively absorbed, and its optical density reached 5 or more. Therefore, it could be suitably used as a lens for protective glasses such as a Ga-As laser.

Example 22 60 parts by weight of methyl methacrylate, 20 parts by weight of methacrylic acid, 20 parts by weight of ethylene glycol dimethacrylate, and 0.05 part by weight of a near-infrared absorbing agent (IRG-002 manufactured by Nippon Kayaku Co., Ltd.) , The same (IRG
-022) 0.05 parts by weight, 0.20 parts by weight of a radical polymerization initiator (V-70 manufactured by Wako Pure Chemical Industries, Ltd.), 0.20 parts by weight of an ultraviolet absorber (Tinuvin P manufactured by Ciba Geigy, Inc.) Release agent (Shin-Etsu Silicone KF35 manufactured by Shin-Etsu Chemical Co., Ltd.)
3A) 0.01 part by weight was added and mixed and dissolved. Using this prepared liquid, a lens having a green surface-hardened film was obtained in the same manner as in Example 1. This lens had excellent surface hardness A and adhesion of the cured film of 100/100.
Also, this lens is 1000 to 1100 as shown in FIG.
Light having a wavelength of nm was selectively absorbed, and its optical density reached 5 or more. Therefore, YAG having an oscillation wavelength in this wavelength range
It could be suitably used as a lens for protective glasses such as a laser.

As can be seen from these examples, according to the present invention, it is possible to provide a good cured film having extremely high hardness and excellent adhesion to an acrylic resin lens having absorption in a wavelength region of 600 nm or more. This is extremely useful as a lens for laser protective glasses. On the other hand, as can be seen from the comparative examples, a good lens cannot be obtained when the requirements constituting the present invention, that is, any of the base lens composition, the plasma treatment, and the coating composition are inappropriate or missing.

[0054]

According to the present invention, the lens for laser protective eyeglasses obtained by the present invention is prepared by adding an effective amount of an oil-soluble dye and / or a near-infrared absorbing agent to a lens having a wavelength of about 600 nm.
It has a desired optical density in the above wavelength range. Further, by selecting the composition of the monomer composition constituting the lens and performing plasma treatment on the obtained lens, a cured film provided after the plasma treatment is firmly adhered to the lens. Accordingly, a laser protective eyeglass lens having absorption in a wavelength region of 600 nm or more and having excellent adhesion between the lens and the cured film can be obtained.

[Brief description of the drawings]

FIG. 1 is a spectral characteristic diagram of a laser protective eyeglass lens obtained in Example 1,

FIG. 2 is a spectral characteristic diagram of the laser protective eyeglass lens obtained in Example 21;

FIG. 3 is a spectral characteristic diagram of the laser protective eyeglass lens obtained in Example 22.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI G02B 1/04 G02B 1/04 1/10 1/10 Z (56) References JP-A-49-64691 (JP, A) JP-A-53-121642 (JP, A) JP-A-57-198413 (JP, A) JP-A-63-27565 (JP, A) JP-A-3-4201 (JP, A) JP-A-63-8602 (JP, A) JP, A) JP-A-54-87758 (JP, A) JP-A-62-239102 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C02C 7/10 C02B 1/04 C02B 1/10 C08J 7/00 306 C08J 7/06 C08F 220/06 C08F 220/18

Claims (2)

(57) [Claims] 1. The following steps (1), (2) and (3)
A method for producing a laser protective eyeglass lens, comprising: (1) A step of obtaining a lens by casting polymerization of a monomer mixture containing the following components (a), (b), (c) and (d) as main components. (A) methyl methacrylate, (b) at least one hydrophilic monomer selected from (meth) acrylic acid and a hydroxyl group-containing (meth) acrylate, (c) component (a) and component (b) (D) an oil-soluble dye and / or a near-infrared absorber, (2) a non-polymerizable gas for the lens obtained in the step (1).
Treating under-flops plasma atmosphere. (3) A step of applying a coating composition containing the following components (e), (f) and (g) as main components to the lens subjected to the plasma treatment in the step (2), and curing the lens to form a cured film. (E) an organosilicon compound having a silanol group and an epoxy group, (f) colloidal silica, and (g) an acetylacetone metal complex compound. 2. A lens for laser protective glasses obtained by the method according to claim 1.