JPH05303003A - Composition for optical material and optical material - Google Patents

Abstract

PURPOSE:To obtain an optical material having low odor with excellent handling property during hardening, having preferable refractive index, chromatic aberration, transparency for an optical resin and excellent mechanical characteristics by incorporating an org. sulfur compd. expressed by formula as the main component. CONSTITUTION:This compsn. contains an org. sulfur compd. expressed by formula I and formula II as the main component. In formula I, X is a halogen atom or methyl group, (1) is 1 or 2, and (m) and (n) are 0 or 1. In formula II, R1 and R2 are same or different groups representing hydrogen atoms or methyl groups, (p) an (q)are integers 0 to 5. Thereby, the obtd. compd. gives no bad odor specific to sulfur compds. and has low viscosity so that the compd. has excellent handling property and that molding and control for the hardening and polymn. reaction is made easy. The obtd. resin has >=1.55 refractive index and high Abbe's number, small chromatic aberration and optical strain, excellent optical transparency, heat resistance, solvent resistance and shock resistance, and small specific gravity, which realizes light-weight product.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for optical materials and an optical material. More specifically, the present invention relates to a composition for optical materials excellent in optical properties such as refractive index, chromatic aberration, transparency, and various mechanical properties, and optical materials. Regarding materials.

[0002]

2. Description of the Related Art In recent years, synthetic resin materials excellent in light weight, moldability, impact resistance and dyeability have been used as lens materials instead of inorganic glass. Known examples of the synthetic resin material include polymethyl methacrylate, polydiethylene glycol bisallyl carbonate, polystyrene, and polycarbonate. The polymethyl methacrylate and polydiethylene glycol bisallyl carbonate are excellent in lightness and impact resistance, but when used as a lens because of their low refractive index of about 1.49, a thicker lens than inorganic glass is required, It has a drawback that it is not suitable for high magnification and light weight.
Further, although the polystyrene and polycarbonate have a high refractive index of about 1.58 to 1.59, they are thermoplastic resins and therefore have a problem that optical distortion due to birefringence tends to occur during injection molding. There are drawbacks such as lack of solvent resistance and abrasion resistance.

Therefore, recently, some technical proposals have been made to improve these conventional drawbacks with a high refractive index. For example, JP-A-1-309002 discloses a plastic lens obtained by curing a distyryl-type organic sulfur compound and a trivalent or tetravalent thiol compound, and JP-A-1-315701 discloses a molecular lens. A compound having 1.3 or more vinyl groups on a molar average basis,
A sulfur-containing plastic lens obtained by mixing a compound having a thiol group at a molar average of 1.1 or more at a specific ratio and curing the mixture is further disclosed in JP-A-2-58001 with a dimercaptobenzene nucleus substitution product. High refractive index optical resins obtained by reacting a compound having at least two reactive unsaturated groups per molecule have been proposed.

[0004]

However, although the above-mentioned optical resin has a high refractive index, it has a problem in terms of chromatic aberration, and the odor of the thiol compound used as the raw material is strong, and the working environment is also low. There is a problem, and there is a problem that handling property is poor due to high viscosity of the raw material monomer.

Further, in the optical resin obtained by polyaddition and polycondensation, it is difficult to control the polymerization reaction, so that there are drawbacks such as poor yield.

Therefore, an object of the present invention is to provide a composition for optical materials which has a low odor and is excellent in handleability when being cured.

Another object of the present invention is to obtain a desired refractive index for plastic lenses or other optical resins,
An object of the present invention is to provide an optical material having chromatic aberration, transparency, etc. and excellent in various mechanical properties.

[0008]

According to the present invention, an organic sulfur compound represented by the following general formulas 3 and 4 as a main component (hereinafter, a compound represented by the chemical formula 3 is referred to as an organic sulfur compound 1 A compound for optical material is provided, which comprises a compound represented by

[0009]

[Chemical 3]

[0010]

[Chemical 4]

Further, according to the present invention, there is provided an optical material having a refractive index of 1.55 or more, which is obtained by polymerizing and curing the composition for optical material.

The present invention will be described in more detail below.

The composition for optical materials of the present invention is characterized by containing the organic sulfur compound 1 and the organic sulfur compound 2 represented by the general formulas 3 and 4 as the main components.

As the organic sulfur compound 1 used in the composition for optical materials of the present invention, specifically, the following chemical formulas 5 to 28 can be preferably mentioned, and they can be used alone or as a mixture in use. ..

[0015]

[Chemical 5]

[0016]

[Chemical 6]

[0017]

[Chemical 7]

[0018]

[Chemical 8]

[0019]

[Chemical 9]

[0020]

[Chemical 10]

[0021]

[Chemical 11]

[0022]

[Chemical 12]

[0023]

[Chemical 13]

[0024]

[Chemical 14]

[0025]

[Chemical 15]

[0026]

[Chemical 16]

[0027]

[Chemical 17]

[0028]

[Chemical 18]

[0029]

[Chemical 19]

[0030]

[Chemical 20]

[0031]

[Chemical 21]

[0032]

[Chemical formula 22]

[0033]

[Chemical formula 23]

[0034]

[Chemical formula 24]

[0035]

[Chemical 25]

[0036]

[Chemical formula 26]

[0037]

[Chemical 27]

[0038]

[Chemical 28]

The compounding ratio of the organic sulfur compound 1 is 5 to 95% by weight, preferably 30 to 9% by weight based on the whole composition.
The amount may be 5% by weight, particularly preferably 35 to 70% by weight. If the blending ratio exceeds 95% by weight, sufficient mechanical strength and heat resistance cannot be obtained, and if less than 5% by weight, a sufficient refractive index cannot be obtained, which is not preferable.

To prepare the organic sulfur compound 1, specifically, for example, 4-chlorothiophenol 1
Mol and 1 mol of chloromethylstyrene in the presence of a base such as sodium hydroxide, preferably at a reaction temperature of 0 to
It can be obtained by a method of reacting at 50 ° C. for 5 to 48 hours.

As the organic sulfur compound 2 used in the composition for optical materials of the present invention, specifically, the following chemical formulas 29 to 40 can be preferably mentioned, and when used, they can be used alone or as a mixture. ..

[0042]

[Chemical 29]

[0043]

[Chemical 30]

[0044]

[Chemical 31]

[0045]

[Chemical 32]

[0046]

[Chemical 33]

[0047]

[Chemical 34]

[0048]

[Chemical 35]

[0049]

[Chemical 36]

[0050]

[Chemical 37]

[0051]

[Chemical 38]

[0052]

[Chemical Formula 39]

[0053]

[Chemical 40]

The organic sulfur compound 2 is incorporated in the composition in an amount of 5 to 95% by weight, preferably 10 to 7% by weight, based on the whole composition.
It may be added in an amount of 0% by weight, particularly preferably 20 to 50% by weight. If the blending ratio exceeds 95% by weight, sufficient impact resistance and high Abbe number cannot be obtained, and if less than 5% by weight, sufficient heat resistance cannot be obtained, which is not preferable.

To prepare the organic sulfur compound 2, specifically, for example, 1 mol of a dihydric alcohol or divalent thiol represented by the following general formula 41 and 1 to 4 mol of (meth) acrylic acid chloride are used. Can be obtained by a method of reacting in the presence of a base such as triethylamine or pyridine as a dehydrochlorinating agent, preferably at a reaction temperature of 0 to 50 ° C. for 1 to 48 hours.

[0056]

[Chemical 41]

The composition for optical materials of the present invention may contain a polymerizable monomer as another raw material monomer component.
Examples of the polymerizable monomer include styrene; α-
Α-substituted styrene such as methyl styrene, α-ethyl styrene and α-chlorostyrene, halogen nucleus substituted styrene,
Alkyl nucleus-substituted styrene; divinylbenzene, chloromethylstyrene, diethylene glycol bisallyl carbonate, (meth) acrylic acid, allyl acetate, diallyl isophthalate, (meth) acrylonitrile, vinyl benzoate, alkyl (meth) acrylate, alkenyl ( (Meth) acrylate, alkoxy polyethylene glycol (meth) acrylate, 2-hydroxyethyl (meth)
Acrylate, 2-hydroxybutyl (meth) acrylate, dialkylaminoethyl (meth) acrylate,
Ethylene glycol bis (meth) acrylate, polyethylene glycol bis (meth) acrylate, propylene glycol bis (meth) acrylate, polypropylene glycol bis (meth) acrylate, bisphenol A bis (meth) acrylate, 1, ω-alkanediol di (meth) ) Acrylate, glycidyl (meth) acrylate, glycerol (meth) acrylate, dibromoneopentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, benzyl vinylbenzyl sulfide, pentaerythritol (Meth) acrylate, dipentaerythritol (meth) acrylate, tetramethylolmethane (meth) acrylate, 2,2-bis (4- (meth) acryloxy Tokishifeniru) propane, 2,2-bis (4- (meth) acryloxy ethoxy-dibromophenyl) propane, 2,2-bis (4-
(Meth) acryloxypolyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypropoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolypropoxyphenyl) propane, etc. (Meth) acrylic acid ester; 2- (meth) acryloyloxyethyl phosphate and the like can be preferably mentioned, and when used, they can be used alone or as a mixture.

In addition, the composition for optical materials of the present invention may further contain additives such as UV absorbers, anti-coloring agents, chain transfer agents, antioxidants, fragrances, organic dyes and inorganic pigments, if necessary. It can also be added.

The optical material of the present invention is a material having a refractive index of 1.55 or more obtained by polymerizing and curing the composition for optical material. The optical material can be prepared, for example, by heat-polymerizing the composition for optical material 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, and specific examples thereof include cumyl peroxyneodecanoate and diisopropyl peroxydicarbonate. , Tert-butyl peroxypivalate, lauroyl peroxide, tert-butyl peroxy-2-ethylhexanoate, benzoyl peroxide, 1,1-bis (tert-butyl peroxy) 3,3,5-trimethylcyclohexane, azobis Examples include isobutyronitrile and the like, which can be used alone or as a mixture when used. The radical polymerization initiator is used in an amount of 10 parts by weight or less, particularly preferably 5 parts by weight or less, based on 100 parts by weight of all raw material monomer components of the composition for optical materials.

To carry out the heat polymerization, for example, the composition for optical material and the radical polymerization initiator are directly charged into a desired mold and the mixture is heated preferably at 0 to 200 ° C. for 1 to 48 hours. Can be made At this time, the polymerization system is preferably carried out in an atmosphere of an inert gas such as nitrogen, carbon dioxide or helium. In addition, the composition for optical materials is, for example, 0 to 200 before the heat polymerization.
After preliminarily polymerizing at 0.5 ° C. for 0.5 to 48 hours, it can be charged in a desired mold and post-polymerized.

Further, for the purpose of improving the surface properties of the obtained optical material, various surface treatments such as hard coating, multi coating, antireflection coating, UV absorption coating and post-dyeing can be carried out after curing.

[0062]

EFFECTS OF THE INVENTION The composition for optical materials of the present invention has no bad odor peculiar to sulfur compounds and has a low viscosity, so that it has excellent handleability, and the reaction control and molding during curing and polymerization are easy. Further, the optical material of the present invention has a refractive index of 1.55 or more and a high Abbe number, has small chromatic aberration and optical distortion, and is excellent in optical transparency, heat resistance, solvent resistance and impact resistance. Moreover, since it has a small specific gravity and can be made lightweight, it is useful as a plastic lens such as a lens for glasses, a camera lens, an optical material, or other optical resin material.

[0063]

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

[0064]

Example 1 6 g of chlorophenylvinylbenzyl sulfide (meta form: para form = 2: 3, weight ratio) and 4,4 ′
-0.05 g of tert-butyl peroxy-2-ethylhexanoate was added to and mixed with the composition for optical materials consisting of 4 g of dimercaptodiphenyl sulfide dimethacrylate. Then, after charging in two glass molds, 40
The mixture was placed in a constant temperature bath at 0 ° C, heated to 70 ° C in 12 hours, then heated to 110 ° C in 4 hours, and finally heated to 100 ° C for 2 hours. Subsequently, annealing treatment was performed at 100 ° 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. The results are shown in Table 1. -Refractive index and Abbe number: Abbe refractometer (manufactured by Atago Co., Ltd.) was used, and methylene iodide was used as an intermediate solution for measurement. B * value (yellowness): measured using a photometer model 1001 manufactured by Nippon Denshoku Industries Co., Ltd. The smaller this value, the smaller the yellowness and the better. -Heat resistance: A sample having no deformation or discoloration in an oil bath at 130 ° C was rated as ◯, and a sample having deformation or discoloration was rated as x.

[0065]

Examples 2 to 14 Cured resins were prepared in the same manner as in Example 1 except that the compositions for optical materials composed of the raw material monomers shown in Table 1 were used, and each measurement was performed. The results are shown in Table 1.

[0066]

[Table 1]

[0067]

Comparative Examples 1 to 5 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. The results are shown in Table 2.

[0068]

[Table 2]

As is clear from Tables 1 and 2, the optical material of the present invention is superior in optical characteristics such as refractive index, heat resistance and yellowness, as compared with the comparative examples.

Claims (2)

[Claims] 1. A composition for an optical material, which contains an organic sulfur compound represented by the following general formulas 1 and 2 as a main component. [Chemical 1] [Chemical 2] 2. An optical material having a refractive index of 1.55 or more, which is obtained by polymerizing and curing the composition for optical materials according to claim 1.