JP2793236B2 - Plastic optical element - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a plastic optical element having anti-glare properties, and various types of display filters,
They are useful as lenses for optical equipment such as cameras, microscopes, and optical filters, in addition to lighting equipment, automobile mirrors, eyeglasses, and sunglasses.

[Prior Art] It is known that harmful rays affect the human body.
Eye tissue is no exception. As the harmful rays, ultraviolet rays and infrared rays are generally known, but depending on the conditions, even a visible ray (about 380 mm to about 780 mm) can be a harmful ray. For example, if it is unavoidably occupied to be excessively exposed to strong sunlight, it is not preferable from the viewpoint of the visual environment.

Therefore, sunglasses, filters with anti-glare effect,
Use of safety glasses and the like is preferable in a visual environment in such a situation. For example, Japanese Patent Publication No. 53-39910 discloses an antiglare lens in which a diethylene glycol bis allyl carbonate resin to which an ultraviolet absorber is added is dyed with a specific dye. Has been proposed.

[Problems to be Solved by the Invention] However, although the anti-glare lens proposed in Japanese Patent Publication No. 53-39910 has an effect of anti-glare yellow light in a wavelength range of 570 nm to 590 nm, the anti-glare effect is improved by a dye. It shows absorption over a wide wavelength range of 400 to 650 nm,
There is a disadvantage that the brightness of an object viewed through the lens is significantly lower than the brightness when viewed with the naked eye.

The present invention has been made to solve such problems, and an object of the present invention is to provide a lightweight plastic optical element having excellent antiglare effect and transparency, and having high brightness.

[Means for Solving the Problems] The object of the present invention is achieved by the following means. The present invention relates to (A) 0.1 to 20% by weight of neodymium methacrylate and / or neodymium acrylate, (B) 4 to 60% by weight of methacrylic acid and / or acrylic acid, and (C) a methacrylic ester having a benzene ring. And / or acrylic acid ester having a benzene ring 30 to 90
A plastic optical element characterized by being obtained by polymerizing a monomer mixture containing 1% by weight and particularly suitable for a lens for spectacles.

 Hereinafter, the present invention will be described in detail.

The neodymium methacrylate and / or neodymium acrylate as the component (A) of the present invention are used for imparting an antiglare property to an optical element while maintaining transparency, and yellow light having a wavelength range of about 570 nm to 590 nm is used. Is selectively absorbed. On the other hand, it is conceivable to use neodymium compounds such as neodymium oxide and neodymium sulfate for the same purpose as the present invention.
Poor compatibility with typical transparent plastic monomers such as methyl methacrylate, styrene, diethylene glycol bisallyl carbonate, and complete separation during polymerization,
It becomes difficult to obtain a good optical element due to cloudiness and clouding in the polymer. Therefore, neodymium methacrylate and / or neodymium acrylate are selectively used as neodymium compounds.

In the present invention, at least one of these components is used as an essential component, and the content is used in the range of 0.1 to 20% by weight. If it is less than 0.1% by weight, the antiglare effect is small, while if it exceeds 20% by weight, the compatibility with other monomers in the above-mentioned monomer mixture becomes poor, and the resulting plastic optical element becomes cloudy or white. Clouding occurs and transparency tends to be lost.

Next, the methacrylic acid and / or acrylic acid as the component (B) is a component necessary for dissolving neodymium methacrylate and neodymium acrylate and obtaining transparency, and the content is in the range of 4 to 60% by weight. It is used in. If the content is less than 4% by weight, it becomes difficult to uniformly disperse neodymium methacrylate or neodymium acrylate, and the necessary amount of neodymium methacrylate and / or neodymium acrylate to obtain a sufficient antiglare effect is obtained. It will be difficult to add. On the other hand, if the content exceeds 60% by weight, the obtained polymer tends to be clouded or cloudy.

Next, the component (C), a methacrylic acid ester having a benzene ring and / or an acrylic acid ester having a benzene ring, is a component necessary for obtaining the transparency of the polymer, and has a content of 30 to 90% by weight. If the content is less than 30% by weight or more than 90% by weight, it is difficult to obtain transparency of the polymer.

As the methacrylate having a benzene ring in the present invention, phenyl methacrylate, dimethylphenyl methacrylate, chlorophenyl methacrylate, dichlorophenyl methacrylate, trichlorophenyl methacrylate,
Bromophenyl methacrylate, benzyl methacrylate,
Examples include methylbenzyl methacrylate, dimethylbenzyl methacrylate, ethylbenzyl methacrylate, chlorobenzyl methacrylate, and phenoxyethyl methacrylate.

Further, the acrylate having a benzene ring in the present invention includes phenyl acrylate, methylphenyl acrylate, dimethylphenyl acrylate, chlorophenyl acrylate, dichlorophenyl acrylate, trichlorophenyl acrylate, bromophenyl acrylate, benzyl acrylate And methylbenzyl acrylate, dimethylbenzene acrylate, ethylbenzyl acrylate, chlorobenzyl acrylate, phenoxyethyl acrylate and the like.

Further, in the present invention, the following optional components can be added, and they can be added as long as the transparency of the optical element of the present invention is not impaired. Examples of such monomers include acrylates such as methyl acrylate, ethyl acrylate, n-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, methyl acrylate, ethyl methacrylate, and n-methacrylate. Methacrylates such as butyl, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, adamantyl methacrylate, fumaric acid, maleic acid, itaconic acid and their esters, styrene and chlorostyrene, α-
Examples include styrene derivatives such as methylstyrene, acrylonitrile, methacrylonitrile, maleic anhydride, N-substituted maleimide, and the like.

Further, in order to increase the crosslinking density, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1, 4−
Polyfunctional monomers such as butanediol dimethacrylate, glycerin dimethacrylate, divinylbenzene, diallyl phthalate, and diethylene glycol bisallyl carbonate can also be added. The preferable addition amount of these monomers is not uniform. For example, the addition of 40% by weight or more of methyl methacrylate does not impair the effect of the present invention, but the addition of diethylene glycol bisallyl carbonate does not impair the effects of the present invention.
When added in an amount of 20% by weight or more, transparency cannot be maintained. Therefore, it is necessary to appropriately determine the amount to be added depending on the additive. These monomers can be used alone or in combination of two or more.

Further, the method for producing the polymer of the present invention is preferably a bulk polymerization method. As the polymerization means, a thermosetting polymerization method is usually used, but a polymerization method using ultraviolet light or radiation can also be used. As the polymerization initiator, azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile)
And azo initiators such as benzoyl peroxide, lauroyl peroxide, and t-butyl peroxy-2-ethylhexanoate.

In the monomer mixture according to the present invention, a heat stabilizer, an antioxidant, an ultraviolet absorber, a release agent, a colorant and the like can be added in an appropriate amount, if necessary, and used.

[Examples] Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.

Incidentally, the optical elements obtained in the present example and the comparative example,
Various physical properties were measured by the following measurement methods.

<Refractive index> Measured by Abbe refractometer.

<Transmittance curve> Using a Hitachi 340 automatic recording spectrophotometer, wavelength 380 nm
Measure the spectral transmittance curve in the ~ 700 nm region.

<Transparency> An illuminator using a fluorescent lamp as a light source was visually observed to determine the presence or absence of cloudiness and cloudiness.

[Example 1] 8 parts of neodymium methacrylate was dissolved in 20 parts of methacrylic acid, and 72 parts of benzyl methacrylate, which is a methacrylate having a benzene ring, was used, and 0.30 part of azobisisobutyronitrile was used as a radical polymerization initiator. 0.05 parts of Tinuvin P manufactured by Ciba-Geigy Co., Ltd. as an ultraviolet absorber and Shin-Etsu Silicone KF353A manufactured by Shin-Etsu Chemical Co., Ltd. as a release agent
0.03 parts were added and mixed and dissolved.

This mixed solution was poured into a mold composed of two flat glass molds and a plastic gasket, placed in a heating furnace, heated at 50 ° C. for 12 hours, and then heated to 85 ° C. over 4 hours. The mixture was heated and kept at 85 ° C. for 2 hours to produce a plate-like polymer. Thereafter, the polymer was removed from the mold, and 11
By heating at 0 ° C. for 2 hours, a transparent plate having a thickness of 2.0 mm, a length of 150 mm and a width of 150 mm was obtained. The number of parts in the examples is by weight (the same applies hereinafter). The obtained transparent plate had a high refractive index of 1.56 and exhibited excellent transparency. Further, the transmittance curve is as shown in FIG. 1, which shields light of 380 nm or less, shows sharp absorption in a wavelength range of 570 to 590 nm, has excellent antiglare properties, and has a wavelength range other than that. Then it was a bright one.

[Example 2] 4 parts of neodymium methacrylate was dissolved in 36 parts of methacrylic acid, and 60 parts of benzene methacrylate and the same amounts of the radical polymerization initiator, ultraviolet absorber, and mold release agent used in Example 1 were used. Was added and mixed and dissolved. This mixture was poured into a mold composed of two glass molds and a gasket designed for lens production, and polymerized in the same manner as in Example 1. The center thickness was 2.0 mm, and the outer diameter was 65 mm. A lens having a high refractive index of 1.54 and a lens power of S-1.00D was obtained.

The transmittance curve of this lens is as shown in FIG. 2, which blocks light of 380 nm or less, has a sharp absorption in the wavelength range of 570 to 590 nm, has antiglare properties, and is transparent and has high brightness. Met.

[Examples 3 to 9] Hereinafter, an optical element was obtained by the same manufacturing method as in Example 2 except that the substance and its parts by weight were changed. The evaluation was as shown in Table 1, and all of them had excellent optical properties.

Comparative Example 1 An antiglare effect was imparted by dyeing with a disperse dye without using a neodymium compound, and the antiglare property was examined. 100 parts of diethylene glycol bisallyl carbonate and 3 parts of Paloyl IPP manufactured by NOF Corporation as a radical polymerization initiator, and
The same amount of the ultraviolet absorber used in Example 1 was added and mixed and dissolved. Using this mixed solution, polymerization was carried out in the same manner as in Example 1 to obtain a plate-shaped polymer of the same type as in Example 1. Further, the plate polymer was immersed in an aqueous solution containing the following dye at 90 ° C. for 10 minutes.

Water 1000 ml CID blue 56 0.5 g CID orange 13 0.1 g As shown in FIG. 3, the transmittance curve of this polymer shows a broader wavelength range of 400 to 650 nm and broader absorption. The brightness of the object viewed through was significantly lower than when viewed with the naked eye.

[Comparative Example 2] Without using a methacrylate having a benzene ring,
A plate-like polymer comprising neodymium methacrylate, methacrylic acid, and methyl methacrylate, which is a methacrylate ester having no benzene ring, was prepared, and the transparency of the plate-like polymer was examined.

8 parts of neodymium methacrylate were dissolved in 32 parts of methacrylic acid, and 60 parts of methyl methacrylate and the same amounts of a radical polymerization initiator, an ultraviolet absorber and a release agent as in Example 1 were added and mixed and dissolved. Using this mixed solution, polymerization was carried out in the same manner as in Example 1 to obtain a plate-shaped polymer of the same type as in Example 1. This polymer was cloudy and opaque, and could not be used as an optical element. The transmittance could not be measured due to cloudiness.

[Comparative Example 3] Without using a methacrylate having a benzene ring,
A plate-like polymer composed of neodymium acrylate, methacrylic acid, and diallyl terephthalate, which is a diallyl ester having a benzene ring, was prepared, and the transparency of the plate-like polymer was examined.

4 parts of neodymium acrylate are dissolved in 36 parts of methacrylic acid, and 60 parts of diallyl terephthalate, 0.50 part of lauroyl peroxide as a radical polymerization initiator, the same amounts of an ultraviolet absorber and a release agent as in Example 1 are added. It was mixed and dissolved. Using this mixed solution, polymerization was carried out in the same manner as in Example 1 to obtain a plate-shaped polymer of the same type as in Example 1. This polymer was opaque due to cloudiness and could not be used as an optical element. In addition, an antiglare effect is exhibited by cloudiness.
The transmittance at 0 nm could not be measured.

[Comparative Example 4] 4 parts of neodymium methacrylate was dissolved in 70 parts of methacrylic acid, and 26 parts of benzyl methacrylate and the same amounts of a radical polymerization initiator, an ultraviolet absorber and a release agent as in Example 1 were added thereto. It was mixed and dissolved. Example 1 using this mixture
Polymerization was carried out in the same manner as described above. The obtained 2.0 mm thick plate polymer was opaque and could not be used as an optical element.

Explanation of symbols in table Effect] The optical element of the present invention has excellent optical properties that are lightweight and transparent, and is further designed to have an antiglare effect by giving sharp absorption in a specific wavelength region of visible light. , Can provide a comfortable viewing environment.
That is, specifically, by using a neodymium compound, it absorbs yellow light particularly in the vicinity of 570 nm to 590 nm, does not reduce the light amount of the entire visible light by sufficiently passing light in other wavelength ranges, and is bright and high anti-glare. Since it has an effect, it is particularly excellent in an antiglare effect under yellow light of sunlight.

In addition, the optical element of the present invention has a large degree of freedom in composition, so that the physical properties such as the refractive index can be widely selected according to the application,
It can also create high refractive index lenses. Further, by using plastic as a base material, the specific gravity is smaller than that of a glass base material, and it can be used as an optical element having excellent impact resistance.

[Brief description of the drawings]

FIG. 1 is a transmittance curve diagram of the plate polymer of Example 1, FIG.
FIG. 3 is a transmittance curve diagram of the lens of Example 2, and FIG. 3 is a transmittance curve diagram of the plate polymer of Comparative Example 1.

Claims (2)

(57) [Claims] (A) 0.1 to 20% by weight of neodymium methacrylate and / or neodymium acrylate; (B) 4 to 60% by weight of methacrylic acid and / or acrylic acid; and (C) methacrylic acid having a benzene ring. Ester and / or acrylate ester having a benzene ring 30 to 90
A plastic optical element obtained by polymerizing a monomer mixture containing 1% by weight. 2. The plastic optical element according to claim 1, wherein the plastic optical element is a spectacle lens.