JP4678008B2 - Curable composition for plastic lens - Google Patents

Description

  The present invention has optical characteristics such as a refractive index, an Abbe number, and transparency, and excellent optical characteristics such as spectacle lenses and camera lenses, as well as adhesives and coating agents. It is related with the curable composition which can provide optical related products, such as.

  Since organic glass is lighter than inorganic glass, it has attracted attention as an optical material, particularly as a lens material. Currently, organic glass made of a polymer such as diethylene glycol bis (allyl carbonate) is often used. Organic glass made of diethylene glycol bis (allyl carbonate) is lightweight and has excellent impact resistance, dimensional stability, machinability, dyeability, and hard coat properties. It is a material that can replace inorganic glass as a lens for eyeglasses. As much used. However, diethylene glycol bis (allyl carbonate) has a high Abbe number of 58 and a small dispersion, but its refractive index is as low as about 1.50. The merit was lost and the appearance was bad.

In recent years, derivatives of bisphenol A have been presented as effective higher refractive index lens materials to overcome such drawbacks. Although this material has various properties such as good impact resistance and curability, it has a relatively high viscosity and its workability such as casting is poor by itself. Various lens material compositions having main components have been developed (Japanese Patent Laid-Open Nos. 55-13747 and 59-191708). However, many of the lens material compositions are cloudy or colored depending on the resin composition, and the Abbe number is not sufficient.
JP 55-13747 JP 59-191708 A

  It is an object of the present invention to have well-balanced good optical properties (refractive index, Abbe number, etc.), mechanical and thermal properties (heat resistance, impact resistance, etc.), and colorless transparency and resin. The present invention provides a curable resin composition capable of preparing an optical material (plastic lens) with improved brittleness.

［式中、Ｒ^１、Ｒ^２は、水素又はメチル基を表し、ｍとｎの合計値は０〜３０を表す。］
で表される第１単量体、および
（ｂ）構造式（２）：

［式中、Ｒは、水素又はメチル基を表し、ｎは１〜１０の数を表す。］
で表される第二単量体
を含んでなる硬化性組成物に関する。
特に、本発明は、単量体が第一単量体（ａ）および第二単量体（ｂ）からなる単量体を含んでなるプラスチックレンズ用硬化性組成物に関する。 The present invention
(A) Structural formula (1):

^[Wherein, R 1, ^{R 2} represents hydrogen or a methyl group, the sum of m and n represents 0 to 30. ]
(B) Structural formula (2):

[In formula, R represents hydrogen or a methyl group, and n represents the number of 1-10. ]
It relates to a curable composition comprising a second monomer represented by the formula:
In particular, the present invention relates to a curable composition for plastic lenses, wherein the monomer comprises a monomer composed of a first monomer (a) and a second monomer (b).

  The curable composition of the present invention can be used for optical components (particularly optical lenses) such as spectacle lenses and camera lenses, and optical related products such as adhesives and coating agents. The curable material of the present invention is particularly suitable for optical materials. The plastic lens of the present invention has good optical properties such as refractive index, Abbe number, and transparency, and various mechanical and physical properties (for example, heat resistance, light weight, impact resistance, dimensional stability). , Mechanical workability, and hard coat adhesion).

  The first monomer (a) used in the present invention is dimethacrylate or diacrylate having an aromatic ring. In the chemical formula (1), each of m and n is a number of 0 to 10, particularly 1 to 5. Specific examples of the first monomer (a) include bisphenol A ethylene oxide (EO) adduct dimethacrylate, bisphenol A EO adduct acrylate, bisphenol A propylene oxide (PO) adduct dimethacrylate, bisphenol A And PO adduct acrylate. These are used alone or in combination.

  The second monomer (b) is dimethacrylate or diacrylate having a tricyclodecane group. In the chemical formula (2), n is 1 to 10, for example, 1 to 5. Specific examples of the second monomer (b) are dimethylol tricyclodecane dimethacrylate, dimethylol tricyclodecane diacrylate, and the like.

  The amount of the second monomer (b) is preferably 10 to 900 parts by weight and more preferably 20 to 200 parts by weight with respect to 100 parts by weight of the first monomer (a).

  The third monomer (c) may or may not be used. The third monomer (c) can improve physical properties and mechanical properties such as impact resistance, shrinkage, and dyeability, and can improve or adjust optical properties such as refractive index. The third monomer (c) is a polymerizable compound having polymerizability. The third monomer (c) may be any polymer as long as the polymer obtained by polymerization using the monomer (c) does not impair the transparency. Specific examples of the third monomer (c) include acrylic acid or methacrylic acid esters such as methyl methacrylate, phenyl methacrylate, and benzyl methacrylate, and fragrance such as styrene, p-chlorostyrene, bromostyrene, divinylbenzene, and vinylnaphthalene. And aromatic di (meth) allyl compounds such as di (meth) allyl orthophthalate, di (meth) allyl isophthalate, and di (meth) allyl terephthalate.

  Acrylic acid or methacrylic acid esters such as methyl methacrylate, phenyl methacrylate, and benzyl methacrylate can function as a diluent. Aromatic vinyl compounds such as styrene, p-chlorostyrene, bromostyrene, divinylbenzene, and vinylnaphthalene can adjust the refractive index (for example, increase the refractive index).

  The amount of the third monomer (c) is preferably 0 to 80 parts by weight, more preferably 0 to 60 parts by weight (for example, 1 to 50 parts by weight) with respect to 100 parts by weight of the first monomer (a). preferable.

  By curing the curable composition of the present invention, an organic glass (particularly, a plastic lens) can be obtained. The organic glass can be obtained by heat copolymerizing a monomer by a known molding method such as a casting method in the presence of a polymerization initiator. The curable composition can be polymerized by adding a polymerization initiator, polymerizing it in advance at a predetermined temperature, charging it in a desired mold and curing it by heating. Alternatively, polymerization can be performed using ionizing radiation such as X-rays and α rays, or so-called light such as ultraviolet rays, visible rays, and infrared rays.

A cured product is obtained by polymerizing the monomer. The polymerization is generally radical polymerization or ionic polymerization. To initiate the polymerization, a polymerization initiator such as a radical polymerization initiator or an ionic polymerization initiator can be used.
Examples of radical polymerization initiators are organic peroxides and azo compounds. Examples include benzoyl peroxide, diisopropyl peroxydicarbonate, tertiary butyl peroxypiparate, tertiary butyl peroxyneodecanoate, azobisisobutyronitrile, azobisisobutyrovaleronitrile, and the like. .

An ion polymerization initiator may be used for the polymerization. As a cationic polymerization _initiator, and hydrogen acids such H ₂ SO 4, HClO _4, include Lewis acids such as BeCl _2, BF _3, and as an anionic polymerization initiator, Li, or an alkali metal such as Na, _{C 2} Alphine catalysts such as H ₅ Na and C ₂ H ₅ Li are listed.

The amount of the polymerization initiator used is preferably 10 parts by weight or less, for example, 0.05 to 5.0 parts by weight based on 100 parts by weight of the total weight of the raw material monomers.
If necessary, colorants such as dyes and pigments, ultraviolet absorbers, antioxidants, various stabilizers, antistatic agents, photochromic compounds, and the like can be further blended with the polymerizable composition.

The plastic lens can be manufactured as follows.
A polymerization initiator and an additive are mixed with the monomers (a) to (c), and after stirring, defoamed. The resulting mixture is then poured into a mold assembled from a mold and gasket under nitrogen or air pressure. Polymerization is carried out by heating at 20 to 120 ° C. for 1 to 48 hours, releasing the mold to obtain a lens. In the case of photopolymerization, an active energy ray, preferably an active energy ray having a wavelength of 200 to 600 nm, is used for about 1 to 10 minutes for each mold using a light source such as a known chemical lamp, xenon lamp, or low-pressure mercury lamp. By irradiating, a lens is obtained. In addition, the product can be obtained by finishing the outer periphery of the lens or finishing the lens to remove dirt.

Agitation may be shaken using a shaker or the like. The stirring time varies depending on the raw material, but is about 3 to 30 minutes if the viscosity of the system is 100 cps or less.
Defoaming usually shakes out the dissolved air from time to time by shaking under reduced pressure. If neglecting defoaming, many fine bubbles are generated in the molded product, which may cause product defects. If it is a 500 ml cube and a system of 100 cps, it takes about 3 to 30 minutes.

  The mold to be poured is supported by a ring-shaped gasket made of a suitable resin, in which glass molds having different curves are arranged in parallel. The gasket has a suitable injectable portion and the composition is injected using an injector with an injection needle. The polymerization is performed by gradually increasing the temperature from room temperature to a maximum of around 100 ° C. However, in consideration of the half-life of the polymerization initiator, it is preferable to increase the rate of temperature increase with the polymerization time. In the mold release step, after the polymerization is completed, the glass mold and the gasket cooled to about 60 ° C. are disassembled and removed. In the case of photopolymerization, after irradiating active energy rays and disassembling the hardened lens by removing the glass mold and the gasket, thermal polymerization can be performed for about 30 minutes to 2 hours as necessary. In finishing, the outer periphery of the product lens is scraped to adjust the size, and surface dirt is removed.

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the examples.
Evaluation of physical properties in Examples and Comparative Examples was performed as follows.
A refractive index and an Abbe number Abbe refractometer (manufactured by Atago Co., Ltd.) were used, and alpha bromonaphthalene was used as an intermediate solution at 25 ° C.
A negative 5 diopter lens with a center thickness of 1.6 mm obtained by impact-resistant casting polymerization, a US FDA standard drop ball test, that is, a 16.2 g steel ball having a diameter of 5/8 inch is 50 inches above the lens. A test of dropping from a height of about 127 cm was performed. In addition, the thing which a hardened | cured material does not break was made into the pass (it shows by (circle) mark).

Or dyeability of Sumikaron -E-FBL (manufactured by Sumitomo Chemical Co., Ltd.) 1 g, the liquid dispersed in 1L of water was heated to 90 ° C., the lens in this can be uniformly dyed without color unevenness was immersed for 10 minutes Was confirmed visually. Those that could be dyed uniformly were judged as acceptable (indicated by circles).
Heat distortion temperature (° C.) was measured using a heat distortion tester (manufactured by Toyo Seiki Seisakusho) in accordance with heat resistance JISK7206, 7207.

Example 1
Ethylene oxide (EO) adduct dimethacrylate of bisphenol A [In the above chemical formula (1), R ₁ is a methyl group, R ₂ is hydrogen, and the average value of the total of m and n is 2.6. 50 parts by weight, dimethylol tricyclodecane dimethacrylate [compound in which n is 1 in the above chemical formula (2)] 50 parts by weight of a mixture of 0.3 parts by weight of diisobutyl valeronitrile as a polymerization initiator And injected into a mold consisting of a gasket made of ethylene / vinyl acetate copolymer (EVA, Mitsui-DuPont Polychemical P-1407) and placed in a constant temperature bath gradually from 30 ° C to 105 ° C over 20 hours The temperature was raised to heating. After the obtained cured resin was released, it was further heated at 110 ° C. for 2 hours for post-polymerization. This cured resin was colorless and transparent, had a refractive index of 1.55, an Abbe number of 42, and a heat distortion temperature of 98 ° C. An impact resistance test was performed on a minus 5 diopter lens with a center thickness of 1.6 mm obtained by casting polymerization, but the lens was not broken.

Examples 2-5
A mixture having the composition (unit: part by weight) shown in Table 1 was cast and polymerized in the same manner as in Example 1 to measure the physical properties of the cured product. The results are shown in Table 2.

Comparative Example 1
A mixture of 100 parts by weight of dimethylol tricyclodecane dimethacrylate and 0.1 parts by weight of azobisisobutyronitrile as a polymerization initiator was cast in the same manner as in Example 1 to obtain a colorless and transparent resin. Although the refractive index of the resin was 1.529 and the Abbe number was 53, the impact resistance was poor.

Comparative Examples 2-4
A mixture having the composition (unit: part by weight) shown in Table 3 was cast and polymerized in the same manner as in Example 1 to measure the physical properties of the cured product. The results are shown in Table 4.

Claims (12)

A curable composition for a plastic lens comprising a monomer,
Monomer
(A) Structural formula (1):

^[Wherein, R 1, ^{R 2} represents hydrogen or a methyl group, the sum of m and n represents 0 to 30. ]
(B) Structural formula (2):

[In formula, R represents hydrogen or a methyl group, and n represents the number of 1-10. ]
A curable composition for plastic lenses, characterized by comprising a second monomer represented by the formula: The curable composition for plastic lenses according to claim 1, wherein the amount of the second monomer (b) is 10 to 900 parts by weight with respect to 100 parts by weight of the first monomer (a). The curable composition for plastic lenses according to claim 1 or 2, wherein the first monomer (a) is bisphenol A ethylene oxide addition diacrylate or methacrylate or bisphenol A propylene oxide addition diacrylate or dimethacrylate. The curable composition for plastic lenses according to any one of claims 1 to 3, wherein the second monomer (b) is dimethylol tricyclodecane diacrylate or dimethylol tricyclodecane dimethacrylate. The curable composition for plastic lenses according to any one of claims 1 to 4, comprising the first monomer (a) and the second monomer (b). The curable composition for plastic lenses according to any one of claims 1 to 5, which also contains a polymerization initiator. The plastic lens formed by hardening | curing the curable composition for plastic lenses in any one of Claims 1-6. A curable composition for a plastic lens comprising a monomer,
Monomer
(A) Structural formula (1):

[Wherein R ¹ , R ² Represents hydrogen or a methyl group, and the total value of m and n represents 0-30. ]
A first monomer represented by
  (B) Structural formula (2):

[In formula, R represents hydrogen or a methyl group, and n represents the number of 1-10. ]
A second monomer represented by
  (C) a third monomer selected from the group consisting of esters of acrylic acid or methacrylic acid, aromatic vinyl compounds and aromatic di (meth) allyl compounds
A curable composition for plastic lenses comprising: The amount of the second monomer (b) is 10 to 900 parts by weight and the amount of the third monomer (c) is 1 to 80 parts by weight with respect to 100 parts by weight of the first monomer (a). The curable composition for plastic lenses according to claim 8. The first monomer (a) is an ethylene oxide addition diacrylate or methacrylate of bisphenol A or a propylene oxide addition diacrylate or dimethacrylate of bisphenol A,
The curable composition for plastic lenses according to claim 8 or 9, wherein the second monomer (b) is dimethylol tricyclodecane diacrylate or dimethylol tricyclodecane dimethacrylate. Regarding the third monomer (c),
The ester of acrylic acid or methacrylic acid is selected from the group consisting of methyl methacrylate, phenyl methacrylate and benzyl methacrylate;
The aromatic vinyl compound is selected from the group consisting of styrene, p-chlorostyrene, bromostyrene, divinylbenzene and vinylnaphthalene;
The aromatic di (meth) allyl compound is selected from the group consisting of di (meth) allyl orthophthalate, di (meth) allyl isophthalate and di (meth) allyl terephthalate. A curable composition for plastic lenses according to claim 1. The plastic lens formed by hardening | curing the curable composition in any one of Claims 8-11.