JPH0463303A - Optical resin - Google Patents

Abstract

PURPOSE:To provide the optical resin which has excellent transparency, refractive index, chromatic aberration, optical distortion, etc., 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 R denotes formula II (where A denotes an oxygen atom or sulfur atom and m denotes 1 to 6 integer and n1 and n2 denote 0 to 2 integer); X denotes a chlorine atom, bromine atom or iodine atom and l1 and l2 denote 0 to 2 integer]. This org. sulfur compd. is easily prepd. by the reaction of, for example, the compd. obtd. by the reaction of 1mol equiv. benzyl chloride and 1mol equiv. 1,2- dimercaptoethane and 1mol equiv. chloromethyl styrene, 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 <Industrial Application Field> The present invention has excellent optical properties such as refractive index, chromatic aberration, and transparency, and various mechanical properties. This invention relates to optical resins useful for plastic lenses for glasses.

<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.

Similarly, JP-A-1-315701 discloses a compound having 1.3 or more vinyl groups in the molecule on a molar average;
JP-A-2-58001 also discloses a sulfur-containing plastic lens obtained by mixing and curing a compound having 1.1 or more thiol groups on a molar average in a specific ratio. A high refractive index optical resin obtained by reacting a compound having at least two reactive unsaturated groups per molecule has been proposed. However, although the optical resin proposed above achieves a high refractive index, it has poor chromatic 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 to be solved by the invention> Therefore, the purpose of the present invention is to improve transparency, refractive index, chromatic aberration,
The object of the present invention is to provide an optical resin that has excellent optical properties such as optical distortion and various mechanical properties, has little odor, and has good handling properties during curing.

〈Means for solving problems〉 According to the present invention, the following general formula (I) [In the formula, R is -E+CH2+II-A probe CH.

(However, A represents an oxygen atom or a sulfur atom. Also, m represents an integer of 1 to 6, and n□ and n represent an integer of 0 to 2.) X represents a chlorine atom, a bromine atom, or an iodine atom. Indicates an atom. Further, there is provided an optical resin obtained by polymerizing a raw material containing an organic sulfur compound, in which al and ρ3 are integers of O to 2.

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 (I).

In the formula, R is -++CH2→y-A+vtr+CHz+m
s, (where A represents an oxygen atom or a sulfur atom, m represents an integer of 1 to 6, and n□ and n2 represent 0 to 2.
) X represents a chlorine atom, bromine atom, or iodine atom, and Q and Ω2 represent integers from O to 2, where m is 6, and n, n2゜ρ, and a2 are If it exceeds 2, manufacturing is difficult. Examples of the organic sulfur compound represented by the general formula (I) include 012-C) 1-C and 2S+CH2 complex 2M box-〇CH2
=CH-min-CH-5-O5CH2@\-/cH, =cH-(〉CHz s-(〉5-eSGHz-
Preferable examples include O and the like, and when used, they can be used alone or as a mixture.

To prepare the organic sulfur compound 1. For example, it can be easily obtained by reacting a compound obtained by reacting 1 molar equivalent of benzyl chloride and 1 molar equivalent of 1,2-dimercaptoethane with 1 molar equivalent of chloromethylstyrene. be able to. In this case, when the chloromethylstyrene used is pure para-isomer, the organic sulfur compound obtained is solid at room temperature, and when it is a meta-para-isomer mixture, the organic sulfur compound obtained is liquid at room temperature or glycerol. It is in a state of

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 components include, for example, styrene, P-methylstyrene, P-chlorostyrene, 0-chlorostyrene, p-bromstyrene, 0-
Bromstyrene, vinyl acetate, vinyl propionate, methyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, phenyl methacrylate, phenyl acrylate, benzyl acrylate,
Benzyl methacrylate, bromphenyl methacrylate, acrylonitrile, methacrylate trile, 2,2-
Bis(4-methacryloyloxyethoxyphenyl)propane, 2,2-bis(4-acryloyloxyethoxyphenyl)propane, diethylene glycol bisallyl carbonate, diallyl tetrachlorophthalate, diallyl phthalate, p-divinylbenzene, □-divinylbenzene, Divinylbiphenyl, 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 bis methacrylate, Diallyl tetrachlorophthalate, diallyl isophthalate, allyl methacrylate,
Preferred examples include propylene glycol bisacrylate, hexaethylene glycol bisacrylate, octaethylene glycol bisacrylate, decaneethylene glycol bisacrylate, neopentyl glycol dimethacrylate, and 200 dimethacrylate with polyethylene glycol.

In order to prepare the high refractive index optical resin of the present invention, it can be obtained, for example, by heating and polymerizing the above-mentioned raw material monomers 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 less can be used, and specifically, for example, benzoyl peroxide, diisopropyl peroxydicarbonate, tert-butyl Peroxy-2-ethylhexanoate, tert-butyl peroxypivalate, tert-butyl peroxydiisobutyrate, lauroyl peroxide, 1-butyl peroxyacetate, tert-peroxyoctoate, t-butyl peroxybenzoate, azobisiso Polymerization initiators selected from the group consisting of butyronitrile, mixtures thereof, and the like can be mentioned. The amount of the radical polymerization initiator used is preferably 10 parts by weight or less, particularly preferably 5 parts by weight or less, based on 100 parts by weight of the total monomers charged.

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. . At this time, the polymerization system is preferably under an inert gas atmosphere such as nitrogen, carbon dioxide, or helium. Furthermore, before the polymerization, the raw material monomers may be prepolymerized, for example, at 0 to 200°C for 0.5 to 48 hours, and then placed in a desired mold for post-polymerization.

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 1.55 or more and 1.
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.

1st 1Y 0.05g of tert-butyl peroxybenzoate is added to a raw material monomer consisting of 8.0g of an organic sulfur compound having the following structural formula and 2.0g of diethylene glycol dimethacrylate (para form: meta form = 3:2). The raw material monomer composition was prepared by mixing. Next, the monomer composition was poured into two glass molds, placed in a constant temperature bath at 80°C, and cured at a curing temperature of 80°C.
The mixture was heated at 100°C for 6 hours, then raised to 100°C over 3 hours, and then heated at 100°C for 3 hours. Finally, at 100℃ 2
A cured resin was obtained by performing a time annealing treatment. The obtained cured resin was taken out from the mold, and the refractive index, Atsube number,
The five-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 solution of methyl iodide as the opening solution.

5 values...Product name "Photometer Model 1001J"
(manufactured by Nippon Denshoku Kogyo Co., Ltd.). Note that 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 ×.

1J1[-1 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.

Comparative examples 1 to 3

Claims (1)

[Claims] The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R is ■CH_2■_mA■_m■CH_2■_
m, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲mathematical formulas,
There are chemical formulas, tables, etc.
X represents a chlorine atom, a bromine atom, or an iodine atom. In addition, l_1 and l_2 represent integers from 0 to 2]
Optical resin obtained by polymerizing raw material monomers containing organic sulfur compounds represented by: