JPH0463301A - Optical resin - Google Patents

Abstract

PURPOSE:To provide the optical resin which has excellent characteristics, such as transparency, refractive index, chromatic aberration, optical distortion, has slight smells and has a good handling characteristic at the time of curing by polymerizing a raw material monomer contg. a specific org. sulfur compd. CONSTITUTION:The optical resin is formed by polymerizing the raw material monomer contg. the org. sulfur compd. expressed by formula I [where A denotes formula II. (In the formula, R3 denotes a hydrogen atom or methyl group); R1 and R2 denote 1 to 6C alkyl groups which are the same or different groups; X denotes a chlorine atom, bromine atom or iodine atom. Further, l, m and n respectively denote 0 to 2.]. This org. sulfur compd. is easily prepd. by the reaction of, for example, 1mol equiv. 2-mercaptobenzothiazole and 1mol equil. 2-hydroxy-3-chloropropyl methacrylate, etc. The compounding ratio of the above- mentioned org. sulfur compd. with the entire part of the raw material monomer is not particularly limited and is preferably in a 1 to 100wt.% range, more particularly preferably in a 50 to 100wt.% range.

Description

Detailed Description of the Invention <Field of Industrial Application> The present invention relates to an optical resin useful for plastic lenses for eyeglasses, etc., which has excellent optical properties such as refractive index, chromatic aberration, and transparency, and various mechanical properties. .

<Prior Art> In recent years, synthetic resin materials that are lightweight, easy to mold, have excellent impact resistance, dyeability, etc. have been used as plastic lens materials in place of inorganic glass. As the synthetic resin material, for example, polymethyl methacrylate, polydiethylene glycol bisallyl carbonate, polystyrene, and polycarbonate are known. However, although the polymethyl methacrylate and polydiethylene glycol bisallyl carbonate themselves are lightweight and have excellent impact resistance, they have a refractive index of 1.49.
When used as a lens, it requires a thicker lens than inorganic glass, and has the drawback of being unsuitable for high magnification and weight reduction.

Furthermore, although the refractive index of polystyrene and polycarbonate is high at about 1.58 to 1.59, since these resins are thermoplastic resins, there is a problem that optical distortion due to birefringence is likely to occur during injection molding. Other drawbacks include poor solvent resistance and scratch resistance.

Recently, various technical proposals have been made to improve these conventional drawbacks. for example.

JP-A-1-309002 discloses a plastic lens made by curing a distyryl-type organic sulfur compound and a trivalent or tetravalent thiol compound.
Publication No. 315701 discloses that a compound having 1.3 or more vinyl groups on a molar average and a compound having 1.1 or more thiol groups on a molar average in the molecule are mixed in a specific ratio and cured. A sulfur-containing plastic lens is also disclosed in Japanese Unexamined Patent Publication No. 2-58001, which is a high refractive plastic lens obtained by reacting a dimercaptobenzene nuclear substitute with a compound having at least two reactive unsaturated groups per molecule. Various resins for optical efficiency have been proposed. However, although the optical resin proposed above achieves a high refractive index, it has poor monochromatic aberration, and when the raw material is placed into a lens mold or heated for curing, it produces a bad odor due to the thiol compound in the raw material. It is strong, has poor handling properties during resin production, and also poses problems in the working environment.

<Problem that the invention seeks to solve> Therefore, the object of the present invention is to improve transparency and refractive index.

The object of the present invention is to provide an optical resin that has excellent optical properties such as chromatic aberration and optical distortion, and various mechanical properties, has little odor, and has good handling properties during curing.

According to the present invention, the following general formula (1) (wherein R3 represents a hydrogen atom or a methyl group) and R and R2 are the same or different groups; , carbon number 1
~6 alkylene group, and X represents a chlorine atom, a bromine atom, or an iodine atom. Further Q.

An optical resin obtained by polymerizing a raw material monomer containing an organic sulfur compound represented by m and n each represent an integer of O to 2 is provided.

The present invention will be explained in more detail below.

The optical resin of the present invention is characterized in that it is formed by polymerizing a specific organic sulfur compound as an essential raw material monomer.

The organic sulfur compound can be represented by the following general formula (1).

m and n each represent an integer of 0 to 2. This 11R
and R2 are alkylene groups having 7 or more carbon atoms, Q.

When m and n exceed 3, manufacturing is difficult.

Examples of the organic sulfur compound represented by the general formula (I) include (wherein, R3 represents a hydrogen atom or a methyl group), and R1 and R2 are the same or different groups, and have a carbon number of 1
~6 alkylene group, and X represents a chlorine atom, a bromine atom, or an iodine atom. Further Q.

etc., and can be used alone or as a mixture.

To prepare the organosulfur compound, for example, one molar equivalent of 2-mercaptobenzothiazole and 2-hydroxy-
It can be easily obtained by reaction with 1 molar equivalent of 3-chloropropyl methacrylate.

Further, the blending ratio of the organic sulfur compound to the entire raw material monomer is not particularly limited, but is preferably in the range of 1 to 100% by weight, particularly preferably 50% by weight.
-100% by weight.

Furthermore, when the organic sulfur compound is blended in an amount of 1 to 30% by weight, it can also be used as a high-performance crosslinking agent having a high refractive index.

In the present invention, monomers other than the organic sulfur compound that can be used as raw material monomer components include, for example, styrene, p-methylstyrene, P-chlorostyrene, and 0-chlorostyrene.

p-bromustyrene, 0-bromustyrene, vinyl acetate, vinyl propionate, methyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate, benzyl methacrylate, bromphenyl methacrylate, acrylonitrile, methacrylaterile, 2,2-bis(4-methacryloyloxyethoxyphenyl)propane, 2,2-bis(4-
Acryloyloxyethoxyphenyl)propane, diethylene glycol bisallyl carbonate 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 tetrachlorphthalate, diallyl isophthalate, allyl methacrylate, propylene glycol bisacrylate, hexaethylene glycol bisacrylate, Preferred examples include octaethylene glycol bisacrylate, decane ethylene glycol bisacrylate, neopentyl glycol dimethacrylate, and polyethylene glycol #200 dimethacrylate.

To prepare the high refractive index optical resin of the present invention.

For example, it can be obtained by heating and polymerizing the above-mentioned raw material monomers in the presence of a radical polymerization initiator. The radical polymerization initiator has a 10-hour half-life temperature of 160°C.
The following organic peroxides or azo compounds can be used, specifically, for example, benzoyl peroxide, diisopropyl peroxydicarbonate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy pivalate. , tert-butylperoxydiisobutyrate, lauroyl peroxide, 1-butylperoxyacetate, tert-peroxyoctoate, tert-butylperoxybenzoate, azobisisobutyronitrile, mixtures thereof, and the like. Polymerization initiators can be mentioned. The amount of the radical polymerization initiator used is 100% of the total monomers charged.
It is preferably 10 parts by weight or less, particularly preferably 5 parts by weight or less.

To carry out the heating polymerization, for example, the raw material monomer and the radical polymerization initiator can be directly charged into a desired mold, and the polymerization can be carried out by heating preferably at a temperature of 0 to 200°C for 1 to 48 hours. . In this case, the polymerization system is, for example, nitrogen or carbon dioxide.

It is preferable to use an atmosphere of an inert gas such as helium. In addition, before the polymerization, the raw material monomer may be added to, for example, 0
After prepolymerizing at ~200°C for 0.5 to 48 hours, it can also be charged into a desired mold and post-polymerized.

Moreover, additives such as a UV absorber and a coloring inhibitor can be added to the raw material monomer as necessary. Furthermore, various surface treatments can be performed after curing in order to improve the surface properties of the cured product.

<Effects of the Invention> The optical resin of the present invention has a refractive index of 1.53 or more,
Low chromatic aberration and optical distortion, optical transparency, heat resistance,
It has excellent solvent resistance and impact resistance, and has a low specific gravity, allowing for weight reduction. In addition, there is no bad odor characteristic of sulfur compounds during curing preparation or curing, and reaction control and molding during curing polymerization are easy. It is useful as an optical resin material.

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

Last 1111 and 7.5 g of an organic sulfur compound having the following structural formula.

A raw material monomer composition was prepared by mixing 0.05 g of tert-butyl peroxybenzoate with 2.5 g of polyethylene glycol #200 dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.). Next, after charging the monomer composition into two glass molds, they were placed in a constant temperature bath at 80°C, heated at a curing temperature of 80°C for 6 hours, and further heated to 100°C for 3 hours. It was heated at 100°C for 3 hours. Finally, an annealing treatment was performed at 100° C. for 2 hours to obtain a cured resin. The obtained cured resin was taken out from the mold, and its refractive index, Abe's number, 5-point value, and heat resistance were measured according to the following methods. The results are shown in Table 1.

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

5 values...Product name "Photometer Model 1001"
(manufactured by Nippon Denshoku Kogyo Co., Ltd.). still,
The smaller this value is, the lower the degree of yellowness is.

Heat resistance: Those with no deformation or discoloration in an oil bath at 130°C were rated 0, and those with deformation or discoloration were rated ×.

A cured resin was prepared in the same manner as in Example 1, except that the raw material monomers shown in Table 1 were used, and each measurement was performed.

The results are shown in Table 1.

A cured resin was prepared in the same manner as in Example 1, except that the raw materials shown in Table 2 were used, and various measurements were carried out as a comparative example. The results are shown in Table 2. "Thank you for your greeting"
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Claims (1)

[Claims] The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) [In the formula, A is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas, There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼. (However, R_3 represents a hydrogen atom or a methyl group) R_1 and R_2 are the same or different groups and represent an alkylene group having 1 to 6 carbon atoms, and X represents a chlorine atom, a bromine atom, or an iodine atom. show. Furthermore, 1, m and n each represent an integer of 0 to 2.] An optical resin obtained by polymerizing a raw material monomer containing an organic sulfur compound represented by the following formula.