JP2969816B2 - Composition for optical material, optical material and plastic lens - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention is a composition for optical materials which is excellent in optical properties such as refractive index, chromatic aberration, transparency and various mechanical properties and is useful for plastic lenses for eyeglasses and the like. To objects, optical materials and plastic lenses.

<Related Art> In recent years, synthetic resin materials excellent in light weight, moldability, impact resistance, dyeing properties, and the like have been used as plastic lens materials instead of inorganic glass. As the synthetic resin material, for example, polymethyl methacrylate, polydiethylene glycol bisallyl carbonate, polystyrene, and polycarbonate are known. However, the polymethyl methacrylate and polydiethylene glycol bisallyl carbonate themselves are lightweight and have excellent impact resistance, but when used as a lens because the refractive index is as low as about 1.49, they are thicker than inorganic glass. There is a drawback that a lens is required and is not suitable for high magnification and light weight. In addition, polystyrene and polycarbonate have a high refractive index of about 1.58 to 1.59, but since these are thermoplastic resins, there is a problem that optical distortion due to birefringence is likely to occur during injection molding. There are drawbacks such as lack of solvent resistance and scratch resistance.

Therefore, recently, various technical proposals have been made to improve these conventional disadvantages. For example, JP-A-1-30
No. 9002 discloses a distyryl-type organic sulfur compound and 3
Alternatively, a plastic lens obtained by curing a tetravalent thiol compound is also disclosed in JP-A-1-315701. A compound having 1.3 or more vinyl groups in the molecule on a molar average basis, and a thiol group in the molar average are also disclosed in JP-A-1-315701. A sulfur-containing plastic lens obtained by mixing and curing a compound having 1.1 or more compounds at a specific ratio is also disclosed in JP-A-2-58001. High refractive index optical resins obtained by reacting a compound having a reactive unsaturated group with each other have been proposed. However, in the optical resin according to the above proposal,
Although a high refractive index has been achieved, the chromatic aberration is poor, and when the raw material is charged into the lens mold or heated for curing, the odor due to the thiol compound in the raw material is strong,
It is inferior in handleability in resin production and has a problem in working environment.

<Problems to be Solved by the Invention> Therefore, an object of the present invention is to provide excellent optical properties such as transparency, refractive index, chromatic aberration, and optical distortion and various mechanical properties, furthermore, the odor is small, An object of the present invention is to provide a composition for an optical material, an optical material, and a plastic lens having good handleability.

<Means for Solving the Problems> The following general formula (I) (Wherein, R represents a hydrogen atom or a methyl group, X represents a chlorine atom or a bromine atom, and 1 represents 0 or 1, m, n
And p represents an integer of 0 to 2).

Further, according to the present invention, the composition for an optical material, obtained by radical polymerization, has the following structural units, and has a refractive index of 1.5
An optical material or a plastic lens characterized by the above is provided.

(Wherein, R represents a hydrogen atom or a methyl group, X represents a chlorine atom or a bromine atom, and 1 represents 0 or 1, m, n
And p represent an integer of 0 to 2).

 Hereinafter, the present invention will be described in more detail.

The optical material of the present invention is obtained by polymerizing an optical material composition containing a specific organic sulfur compound as an essential raw material monomer. The organic sulfur compound can be represented by the following general formula (I): In the formula, R represents a hydrogen atom or a methyl group, and X represents a chlorine atom or a bromine atom. Or 0 or 1 is shown, m, n and p show the integer of 0-2. Again, one, m, n and p
Is more than 2, it is difficult to manufacture. Examples of the organic sulfur compound represented by the general formula (I) include: And the like. When used, they can be used alone or as a mixture.

To prepare the organic sulfur compound, for example, a thiol compound obtained by the reaction of 1 molar equivalent of 1,2-thioethylene glycol and 1 molar equivalent of benzyl chloride in the presence of a basic catalyst such as triethylamine, It can be easily obtained by reaction with -3-chloropropyl methacrylate, 3-acryloyloxyglycerin monomethacrylate, or the like.

The mixing ratio of the organic sulfur compound to the whole raw material monomer is not particularly limited, but is preferably in the range of 1 to 100% by weight, and particularly preferably 50 to 1% by weight.
It is in the range of 00% by weight. Further, the organic sulfur compound is
When compounded in the range of 30% by weight, it can be used as a high-performance crosslinking agent having a high refractive index.

In the present invention, as the monomer other than the organic sulfur compound that can be used as a raw material monomer component,
For example, styrene, p-methylstyrene, p-chlorostyrene, o-chlorostyrene, p-bromostyrene, o
-Bromostyrene, vinyl acetate, vinyl propionate,
Methyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, benzyl methacrylate, bromophenyl methacrylate, acrylonitrile, methacrylonitrile, 2,2
-Bis (4-methacryloyloxyethoxyphenyl)
Propane, 2,2-bis (4-acryloyloxyethoxyphenyl) propane, diethylene glycol bisallyl carbonate, diallyl tetrachlorophthalate, diallyl phthalate, p-divinylbenzene, m-divinylbenzene, divinylbiphenyl, ethylene glycol bismethacrylate, diethylene glycol Bismethacrylate, ethylene glycol bisacrylate, diethylene bisacrylate, dipropylene glycol bismethacrylate, triethylene glycol bisacrylate, triethylene glycol bismethacrylate, tetraethylene glycol bisacrylate, bisphenol A bismethacrylate, diallyl tetrachlorophthalate, diallyl isophthalate , Allyl methacrylate,
Preferred examples include propylene glycol bisacrylate, hexaethylene glycol bisacrylate, octaethylene glycol bisacrylate, decane ethylene glycol bisacrylate, neopentyl glycol dimethacrylate, and polyethylene glycol # 200 dimethacrylate.

The optical material such as the high-refractive index plastic lens of the present invention can be prepared, for example, by subjecting each of the raw material monomers to heat polymerization in the presence of a radical polymerization initiator. As the radical polymerization initiator, an organic peroxide or an azo compound having a 10-hour half-life temperature of 160 ° C. or lower can be used. Specifically, for example, benzoyl peroxide, diisopropyl peroxydicarbonate, tertiary butyl Peroxy-2-ethylhexanoate, tertiary butyl peroxypivalate, tertiary butyl peroxydiisobutyrate, lauroyl peroxide, t
-Butyl peroxy acetate, tertiary peroxy octoate, tertiary butyl peroxy benzoate, azobisisobutyronitrile and a mixture thereof, and the like. The amount of the radical polymerization initiator used is preferably at most 10 parts by weight, particularly preferably at most 5 parts by weight, based on 100 parts by weight of the total charged monomers.

In order to carry out the heat polymerization, for example, a raw material monomer and a radical polymerization initiator are charged directly into a desired mold, and preferably polymerized by heating at a temperature of 0 to 200 ° C. for 1 to 48 hours. . At this time, the polymerization system is desirably placed in an atmosphere of an inert gas such as nitrogen, carbon dioxide, and helium. Before the polymerization, the raw material monomers may be preliminarily polymerized at, for example, 0 to 200 ° C. for 0.5 to 48 hours, then charged in a desired mold, and post-polymerized.

Further, additives such as a UV absorber and a coloring inhibitor can be added to the raw material monomer as needed. Further, for the purpose of improving the surface properties of the cured product, various surface treatments can be performed after the curing.

<Effect of the Invention> The optical material such as the plastic lens of the present invention has a refractive index of 1.5 or more, has small chromatic aberration and optical distortion, and has excellent optical transparency, heat resistance, solvent resistance and impact resistance. In addition, the specific gravity is small and the weight can be reduced. In addition, there is no odor peculiar to sulfur compounds during curing preparation or curing, and reaction control and molding at the time of curing polymerization are easy, so it is easy for plastic lenses such as eyeglass lenses, camera lenses, optical materials or other materials. It is useful as an optical resin material.

<Examples> Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1 80 parts by weight of an organic sulfur compound having the following structural formula: Polyethylene glycol 200 dimethacrylate (4
0.05 g of tertiary butyl peroxybenzoate was mixed with 20 parts by weight of a starting monomer (abbreviated as G) to prepare a starting monomer composition. Then, after charging the monomer composition in two glass molds, put in a constant temperature bath at 80 ° C., and heat at a curing temperature of 80 ° C. for 6 hours, and further for 3 hours.
The temperature was raised to 100 and heated at 100 ° C. for 3 hours. Finally 100
Annealing treatment was performed at 2 ° C. for 2 hours to obtain a cured resin. The obtained cured resin was taken out of the mold, and the refractive index, Abbe number, b * value and heat resistance were measured according to the following methods. Table 1 shows the results.

Refractive index and Abbe number: Measured using an Abbe refractometer (manufactured by Atago Co., Ltd.) and using a methyl iodide saturated solution as an intermediate solution.

b * value: Measured using a trade name "Photometer Model 1001" (manufactured by Nippon Denshoku Kogyo Co., Ltd.).

Heat resistance: 変 形 indicates no deformation or discoloration in an oil bath at 130 ° C., and X indicates deformation or discoloration in an oil bath.

Examples 2 to 16 80 parts by weight of an organic sulfur compound having the following structural formula, A raw material monomer (Example 2) consisting of 20 parts by weight of 4G was mixed with 85 parts by weight of an organic sulfur compound having the following structural formula, A raw material monomer (Example 3) consisting of 15 parts by weight of triethylene glycol dimethacrylate (hereinafter abbreviated as 3G) was mixed with 85 parts by weight of an organic sulfur compound having the following structural formula, A raw material monomer (Example 4) consisting of 15 parts by weight of 3G was mixed with 90 parts by weight of an organic sulfur compound having the following structural formula, A raw material monomer (Example 5) consisting of 10 parts by weight of diethylene glycol dimethacrylate (hereinafter abbreviated as 2G), 90 parts by weight of an organic sulfur compound having the following structural formula, A raw material monomer consisting of 10 parts by weight of 2G (Example 6) was mixed with 85 parts by weight of an organic sulfur compound having the following structural formula, A raw material monomer (Example 7) consisting of 15 parts by weight of 3G was mixed with 85 parts by weight of an organic sulfur compound having the following structural formula, A raw material monomer (Example 8) consisting of 3 parts by weight of 3G was mixed with 90 parts by weight of an organic sulfur compound having the following structural formula, Ethylene glycol dimethacrylate (hereinafter abbreviated as 1G)
90 parts by weight of an organic sulfur compound having the following structural formula: 1G10 parts by weight of a raw material monomer (Example 10), 90 parts by weight of an organic sulfur compound having the following structural formula, 1G10 parts by weight of a raw material monomer (Example 11), 90 parts by weight of an organic sulfur compound having the following structural formula, 1G10 parts by weight of a raw material monomer (Example 12), 90 parts by weight of an organic sulfur compound having the following structural formula, Raw material monomer consisting of 10 parts by weight of neopentyl glycol dimethacrylate (hereinafter abbreviated as NPG) (Example 13)
A, 90 parts by weight of an organic sulfur compound having the following structural formula, A raw material monomer consisting of 10 parts by weight of NPG (Example 14) was mixed with 90 parts by weight of an organic sulfur compound having the following structural formula, A raw material monomer consisting of 10 parts by weight of NPG (Example 15) was mixed with 90 parts by weight of an organic sulfur compound having the following structural formula, A cured resin was prepared in the same manner as in Example 1 except that a raw material monomer composition (Example 16) composed of 10 parts by weight of NPG was used, and each measurement was performed.
Table 1 shows the results.

Comparative Examples 1 to 3 Cured resins were prepared in the same manner as in Example 1 except that the raw material monomers shown in Table 2 were used, and each measurement was performed. Table 2 shows the results.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G08F 20 / 38,120 / 38,220 / 38 G08F 290 / 06,299 / 06 G02B 1/04 CA (STN)

Claims (4)

(57) [Claims] 1. A compound represented by the following general formula (I) (Wherein, R represents a hydrogen atom or a methyl group, X represents a chlorine atom or a bromine atom, and 1 represents 0 or 1, m, n
And p represents an integer of 0 to 2). 2. Styrene, p-methylstyrene, p-chlorostyrene, o-chlorostyrene, p-bromostyrene, o-bromostyrene, vinyl acetate, vinyl propionate, methyl methacrylate, butyl methacrylate,
Methyl acrylate, ethyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, benzyl methacrylate, bromophenyl methacrylate, acrylonitrile, methacrylonitrile,
2,2-bis (4-methacryloyloxyethoxyphenyl) propane, 2,2-bis (4-acryloyloxyethoxyphenyl) propane, diethylene glycol bisallyl carbonate, diallyl tetrachlorophthalate,
Diallyl phthalate, p-divinyl benzene, m-divinyl benzene, divinyl biphenyl, ethylene glycol bis methacrylate, diethylene glycol bis methacrylate, ethylene glycol bis acrylate, diethylene bis acrylate, dipropylene glycol bis methacrylate, triethylene glycol bis acrylate, triethylene glycol bis Methacrylate,
Tetraethylene glycol bis acrylate, bisphenol A bismethacrylate, diallyl tetrachlorophthalate, diallyl isophthalate, allyl methacrylate, propylene glycol bisacrylate, hexaethylene glycol bisacrylate, octaethylene glycol bisacrylate, decane ethylene glycol bisacrylate, neopentyl glycol 2. The composition for an optical material according to claim 1, further comprising dimethacrylate, polyethylene glycol @ 200 dimethacrylate, or a mixture thereof. 3. An optical material having the following structural unit and having a refractive index of 1.5 or more, obtained by subjecting the composition for optical material according to claim 1 or 2 to radical polymerization. (Wherein, R represents a hydrogen atom or a methyl group, X represents a chlorine atom or a bromine atom, and 1 represents 0 or 1, m, n
And p represent an integer of 0 to 2). 4. A plastic lens obtained by subjecting the composition for an optical material according to claim 1 or 2 to radical polymerization and having the following structural unit and having a refractive index of 1.5 or more. (Wherein, R represents a hydrogen atom or a methyl group, X represents a chlorine atom or a bromine atom, and 1 represents 0 or 1, m, n
And p represent an integer of 0 to 2).