TW200848396A - Radically polymerizable compound having a dithiocarbonate structure and a sulfur-containing allylcarbonate - Google Patents

Abstract

The invention provides a radically polymerizable compound having a dithiocarbonate structure represented by formula (1) and a sulfur-containing allylcarbonate group which can give an optical material stable and little colored at the time of thermal curing reaction, having a high refractive index and an excellent transparency, production method thereof, (co) polymer of the compound, composition containing the compound and cured product thereof, andmolded product for optical material comprising the cured product. (In the formula, R<1> and R<2> each independently represents a hydrogen atom or methyl group, and X and Y each independently represents a divalent group selected from group consisting of an alkylene group having 1 to 10 carbon atoms which may be branched, an arylene group and a cycloalkylene group.)

Description

200848396 IX. OBJECT OF THE INVENTION [Technical Field] The present invention relates to a radically polymerizable compound having a specific dithiocarbonate structure and a thioallyl carbonate group, and a use of the radical polymerizable compound High refractive index optical material. [Prior Art] Compared with inorganic glass, plexiglass is more lightweight, and has excellent impact resistance, thermoplastic formation and easy coloring. Therefore, it is used as a substitute for inorganic glass for window materials and lighting of buildings or vehicles. Machine tools, billboards, daily necessities, etc. Such a plexiglass is preferably represented by a diethylene glycol bis(allyl carbonate) polymer represented by CR-3 9 (trade name: manufactured by PPG Corporation) or a methyl methacrylate polymer. When a lens for glasses is made of glass, the higher the refractive index of the glass, the thinner the thickness of the lens, but the refractive index of the organic glass is 1.49 to 1.50, compared with inorganic glass (1.523 for white crown glass). Therefore, when a lens is produced using plexiglass, the edge becomes thicker and the weight is lost, compared with when a lens is produced using inorganic glass. In addition, when a lens for vision correction is produced using plexiglass, the appearance is deteriorated, and the appearance is deteriorated. Therefore, in the above-described situation, a resin for an optical material which can impart a polymer having a high refractive index is desired. In order to increase the refractive index of plexiglass, many methods have been tried so far. For example, in the thiourea system obtained by reacting an isocyanate compound with a mercapto compound, Patent Document 1 (Patent Document 1) discloses a thiourethane system obtained by reacting an isocyanate compound with a mercapto compound. The resin is a high-refractive-index optical resin, but the thiourethane-based resin is toxic by the isocyanate compound as a raw material, and the extremely unpleasant odor characteristic of the thiol compound of the raw material is a problem. Japanese Patent Publication No. 3-217412 (Patent Document 2) discloses an optical resin material having a high refractive index as a (meth) acrylate compound containing a sulfur atom. However, most of these materials become high viscosity. However, since the reactivity is too high, many methods are required as a method of preserving the lens material, and it is not a material that is easy to handle. In Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The radical polymerizable compound having a thioallyl carbonate group is used as an optical resin material for imparting a high refractive index. These compounds have a high refractive index and are excellent in hardenability due to light, and vice versa. When a peroxide is used as a polymerization initiator for a thermosetting reaction, problems such as oxidation and coloration are likely to occur in the sulfide structure portion in the molecule, and control of polymerization is also difficult. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Problem to be Solved by the Invention] An object of the present invention is to provide a thermosetting reaction that can be stably carried out. Further, a radically polymerizable compound having less coloration and an optical material having high refractive index and excellent transparency are used. [Means for Solving the Problem] The inventors of the present invention have found that a specific dithiocarbonate structure and a thioallyl carbonate-containing radical polymerizable property have been repeatedly studied in order to solve the above problems. The compound is stable in the heat-hardening reaction and has little coloration, and an optical material having a high refractive index and excellent transparency is supplied, and the present invention has been completed. That is, the present invention relates to the following [1] to [1 6 ]. [1] A radically polymerizable compound represented by the general formula (1), [Chemical Formula 1]

(wherein R1 and R2 each independently represent a hydrogen atom or a methyl group, and X and γ each independently form a group of a branching group, an exoaryl group and a cycloalkyl group having a carbon number of 1 to 10; The selected two-valent base). [2] The radically polymerizable compound according to the above 1, wherein X and Y in the above general formula (1) are a methyl group, an ethyl group, a 1,2-propyl group or a 200848396 1,3-propane group. base. [3] The radically polymerizable compound according to the above 1 or 2, wherein R1 and R2 in the above general formula (1) are a hydrogen atom. [4] A method for producing a radically polymerizable compound represented by the general formula (1), characterized in that the dithiol represented by the general formula (2) is represented by a general formula (3) in the presence of a base The (meth)allyl halide is reacted to obtain a thiol compound represented by the general formula (4), and then reacted with n,N,-carbonyldiimidazole, [Chemical 2] HS/^SH ( 2) (wherein, L represents a divalent group selected from the group consisting of a branched alkyl group, an extended aryl group and a ring-forming group of carbon atoms 1 to ι〇)

(wherein R4 represents no hydrogen atom or methyl group, and Z represents a chlorine atom or a bromine atom)

(4) 200848396 (the mark in the formula is the same as above) [5] R1

(1) (Formula, R1 and R2 each independently represent a hydrogen atom or a methyl group, and X and Y each independently represent a branched alkyl group, an extended aryl group and a cycloalkyl group having a carbon number of 1 to 10 The selected two-valent group in the group). [5] The method for producing a radically polymerizable compound according to the above 4, wherein X and Y in the above general formula (1) are a methyl group, an ethyl group, a 1,2-propyl group or a 1,3- Prolonged propyl. [6] The method for producing a radically polymerizable compound according to the above 4 or 5, wherein R1 and R2 in the above general formula (1) are a hydrogen atom. [7] A polymer or a copolymer, which is characterized in that the radical polymerizable compound according to any one of the above 1 to 3 is used as a raw material monomer. [8] The copolymer according to any one of the above 1 to 3, which is a copolymer of a radically polymerizable compound according to any one of the above 1 to 3, and another radical polymerizable compound. [9] The copolymer according to any one of the above 1 to 3, which is a copolymer of a radical polymerizable compound according to any one of the above 1 to 3, and a copolymer of allyl methacrylate and/or diallyl maleate. . [10] A polymerizable composition for an optical material, which comprises the radical polymerizable compound according to any one of the above 1 to 3. -9-200848396 [1 1] The polymerizable composition for an optical material according to the above 1st, which further contains another radical polymerizable compound. (2) The polymerizable composition for an optical material according to the above, wherein the other radically polymerizable compound 'is at least allyl methacrylate and/or diallyl maleate. [13] The cured product of the polymerizable composition for an optical material according to any one of the above items 10 to 12. [14] A molded article for an optical material, characterized in that the cured product described in the above 13 is contained. [1] The molded article for an optical material according to the above-mentioned item 14, which is selected from the group consisting of a lens, an optical waveguide, a film, a prism, a flat plate, or a fiber. [16] A type of lens is characterized in that the optical material contained in any of the above-mentioned 1 〇 to 1 2 is cured by a polymerizable composition. [Effects of the Invention] The composition for an optical material using the radical polymerizable compound of the present invention has a high refractive index and excellent transparency, and has less coloration during the thermosetting reaction. Therefore, it is particularly suitable for use in a spectacle lens. An optical lens such as a camera lens, an optical waveguide, an optical sealant, an optical adhesive, an optical film, a prism, a light guide plate for a liquid crystal panel, or an optical material such as an optical fiber. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. -10- 200848396 [Free radically polymerizable compound having a dithiocarbonate structure and a thioallyl carbonate group] The present invention has a dithiocarbonate structure and a radical containing a thioallyl carbonate group The polymerizable compound is the following general formula (1) [Chemical 6]

The compound represented by the above is also referred to as "the radical polymerizable compound of the present invention" hereinafter. Further, in the present specification, if the chemical formula does not match the compound name, the chemical formula is preferred. In the general formula (1), R1 and R2 each independently represent a hydrogen atom or a methyl group, and among them, a hydrogen atom is preferred from the viewpoint of increasing the refractive index. In the general formula (1), X and Y each independently represent a divalent group selected from the group consisting of a branched alkyl group, an extended aryl group and a cycloalkyl group having 1 to 10 carbon atoms. Specific examples of the alkylene group include a methyl group, an ethyl group, a 1,2-propyl group, a 1,3 -propyl group, a butyl group, a pentyl group and a hexyl group. Examples of the aryl group include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a tolyl group, an anthranyl group, and a biphenyl group. Examples of the cycloalkyl group include a 1,3-cyclopentanyl group, a 1,2-cyclopentyl group, a 1,1-cyclopentenyl group, a 1,4-cyclohexylene group, a 1,3-cyclohexylene group, and i, 2-extension ring -11 - 200848396 base, ι, ι-extension cyclohexyl and the like. X and Y in these are preferably an alkylene group having a carbon number of 1 to 4 and a stretching ring having a carbon number of 6 to 10, from the viewpoint of having both a refractive index and an Abbe number. Methyl, ethyl, 1,2-propenyl, iota, 3-propyl are particularly preferred. The radically polymerizable compound represented by the general formula (1) is particularly preferably S,S '-bis[2-(allyloxycarbonylthio)ethyl]dithiocarbonate. The radically polymerizable compound for an optical material described in the above-mentioned prior art contains a sulfur atom-containing sulfide skeleton (-CH2-S-CH2-) for the purpose of increasing the refractive index. However, since this sulfur structure is easily oxidized, it causes coloring during polymerization or hardening reaction, and the stability of the polymerization initiator is incomplete due to deactivation of the polymerization initiator. . On the other hand, the radically polymerizable compound of the present invention contains a dithiocarbonate structure as a sulfur-containing group (-3-((:: 0)-8-) and a thio-allyl carbonate-containing structure (CH2) = CR3-CH2-0-(C = 0)-S-(R3 represents the above R1 or R2). This structure is because the sulfur atom is not easily oxidized by providing an electron-attracting carbonyl group beside the sulfur atom. In the case of the polymerization or the hardening reaction, the coloring is not caused, and it is stable. [Production Method] Next, the structure having the dithiocarbonate and the thioallyl carbonate group represented by the general formula (1) of the present invention will be described. A method for producing a radically polymerizable compound. The radically polymerizable compound having a dithiocarbonate structure and a thioene-12-200848396 propyl carbonate group represented by the general formula (1) can be obtained by The dithiol is produced by reacting with a (meth)allyl halide of formic acid in the presence of a base, and 2. reacting it with N,N'-carbonyldiimidazole. Further, in the present specification, "(methyl "Allyl" is "methallyl and/or allyl" and "(meth)acrylate" is " Base acrylate and/or acrylate". 1. Reaction of dithiol with halogenated formic acid (meth)allyl ester in the presence of a base The dithiol used in the present invention is the following general formula (2) [ 7) HS/(2) (wherein, L represents a divalent group selected from the group consisting of a branching group of a carbon number of 1 to 1 〇, a aryl group and a cycloalkyl group) The compound represented by the (meth)allyl carboxamide is the following general formula (3) [Chemical 8]

(3) (wherein R4 represents a hydrogen atom or a methyl group, and Z represents a chlorine atom or a bromine atom). The two compounds are reacted in the presence of the test to obtain the general formula (4) -13 - 200848396.

(4) A thiol compound (hereinafter also referred to as "thiol compound (4)") represented by (the symbol in the formula is the same as above). In the general formula (3), Z is preferably a chlorine atom from the viewpoint of having both reactivity and economy, and is generally L in the formula (4), corresponding to the general formula (1) of the purpose. X and Y in the indicated compounds are selected. The amount of the dithiol represented by the general formula (2) and the (meth)allyl halide of the general formula (3) is not particularly limited, but usually it is usually relative to the dithiol 1 mol. The halogenated formic acid (meth)allyl ester is preferably used in 0 · 1 to 1 · 5 moles of 'use 0 · 5 to 1 · 1 mole is particularly good. When the (meth)allyl carboxamide is less than 〇·1 mol, the reaction yield with respect to the dithiol becomes low, and when it exceeds 1.5 m, the amount of by-product formation increases. This reaction can be carried out by a method in which the hydrogen halide of the by-product is removed to the outside of the reaction system, and a method of adding a hydrogen halide trapping agent. Examples of the hydrogen halide scavenger include pyridine, triethylamine, picoline, dimethylaniline, diethylaniline, 1,4-diazabicyclo[2.2.2]octane, and 1,8-diaza. Inorganic alkali such as heterobicyclo[5.4.0]undec-7-ene, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, carbonated carbonate, lithium carbonate, sodium hydrogencarbonate, etc. Test. The amount of the hydrogen halide scavenger to be used is not particularly limited, but it is preferably 0.1 to 1.5 moles per mole of the above-mentioned dithiol, and particularly preferably 〇 5 to 1.1 moles. Further, the reaction may be carried out without a solvent, or a solvent which does not react with the substrate, and may be carried out without any problem in the presence of water. Examples of the solvent include a hydrocarbon solvent such as η-hexane, toluene, xylene or benzene, a ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone, or an ester of ethyl acetate or butyl acetate. a solvent, an ether solvent such as diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or tetrahydropyran, a halogen solvent such as dichloromethane, dichloroethane, chloroform or chlorobenzene, acetonitrile, hydrazine, hydrazine. - a polar solvent such as dimethylformamide or dimethyl hydrazine. These solvents may be used singly or in combination of two or more. The reaction temperature is not particularly limited, but is usually in the range of -30 to 100 ° C, preferably 〇 5 (TC is particularly preferred, and below -30 ° C, the reaction is extremely slow, exceeding 1 〇〇 ° C, a side reaction which is easy to cause a thiol compound of an intermediate to be polymerized by an ene-thiol reaction, etc. Further, a polymerization inhibitor for suppressing polymerization may be added to the reaction. The polymerization inhibitor may, for example, be P-benzoquinone. , naphthoquinone, 2,5-diphenyl-P-benzoquinone, etc., hydroquinone, P-bubutyl catechol, 2,5-di-t-butyl hydrogen flooding, etc. a phenol such as hydroquinone monomethyl ether, di-t-butyl p-formamidine or α-naphthol. The thiol compound (4) obtained by such a method can be recrystallized, chromatographed or activated carbon, Purification of activated clay, synthetic adsorbent, etc. -15- 200848396 2. Reaction of thiol compound (4) and N,N'-carbonyldiimidazole formed by the reaction of 1. above, The resulting thiol compound (4) is reacted with N,N'-carbonyldiimidazole to produce a radical polymerizable compound represented by the general formula (1) of the present invention. The amount of the thiol compound (4) to be reacted with N,N'-carbonyldiimidazole is not particularly limited, but usually, relative to the thiol compound 1 mole, ruthenium, osmium, carbonyl diimidazole is used. 0.1 to 0.7 mol is preferred, and 〇·3 to 〇.5 mol is particularly preferred. When Ν, Ν5-carbonyldiimidazole is less than 0.1 mol, the reaction yield relative to the thiol compound (4) is low. When the amount exceeds 0.7 mol, the amount of by-product formation increases. The reaction can be carried out in the presence of a base or in the absence of a base. When the reaction is carried out in the presence of a base, the base to be used may, for example, be mentioned. Shenjiamine, dimethylamine, triethylamine, pyridine, picoline, aniline, dimethylaniline, diethylaniline, toluidine, methoxyaniline, ;!, 4_diazabicyclo[2 ·2·2] an organic base such as octane (DABCO), 1,8-diazabicyclo[5·4·0; Η-red-7-ene (DBU), or sodium hydrogencarbonate or sodium carbonate, An inorganic base such as barium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide or magnesium oxide. The amount of the base used is not particularly limited, but The above thiol compound (4) 1 旲 ear ' is preferably 0.1 to 5 moles, more preferably 〇 5 to 3 moles, and particularly preferably 0 · 8 to 1 · 2 旲 ears. The solvent is used in an inert solvent. -16-200848396 The solvent is not particularly limited as long as it is inert to the reaction, and specific examples thereof include hydrocarbons such as η-hexane, benzene, toluene, and xylene. Solvent, methanol, ethanol, isopropanol, η-butanol, methoxyethanol, ethoxyethanol, butoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol An alcohol solvent such as monobutyl ether; a ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone; an ester solvent such as ethyl acetate or butyl acetate; diethyl ether or diethylene glycol An ether solvent such as methyl ether, tetrahydrofuran or dioxane, or a halogen such as dichloromethane, chloroform, carbon tetrachloride, 1,2-chloroethane, tetrachloroethylene, chlorobenzene or hydrazine-dichlorobenzene. Solvent, acetonitrile, hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, hydrazine, hydrazine-dimethylimidazolidinone, dimethyl hydrazine, cycline A polar solvent such as hydrazine. These solvents may be used singly or in combination of two or more. The reaction temperature is not particularly limited, but is usually in the range of -7 8 to 150 ° C, more preferably in the range of -20 to 120 ° C, and particularly preferably 0 to 100 ° C. The above-mentioned reaction of the thiol compound (4) with N,N'-carbonyldiimidazole to form an intermediate intermediate thiol formed by the reaction of the first stage dithiol with the halogenated formic acid (meth)allyl ester After the compound (4) is once taken out, the step of the second stage carbonylation reaction may be carried out, or the thiol compound (4) may not be taken out in the middle, and the next carbonylation reaction may be carried out in one stage. When the stepwise method is employed, the thiol compound (4) of the intermediate of the first stage reaction may be further subjected to a conventional method (for example, distillation, recrystallization, chromatography or activated carbon treatment, etc.) if necessary. Separation and purification, -17- 200848396 can also be isolated from higher purity compounds. In the production of the radically polymerizable compound of the present invention, a polymerization inhibitor may be used in order to prevent polymerization of the thiol compound (4) of the intermediate to cause an ene-thiol reaction. The polymerization inhibitor which can be used may, for example, be a conventional compound such as 4-methoxyphenol, 2,6-di-tert-butyl cresol, hydroquinone or phenothiazine. The amount of the polymerization inhibitor to be used is not particularly limited, but is preferably 0.001 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, per 100 parts by mass of the raw material mixture or the reaction product in the reaction system. It is particularly preferable to be 0.01 to 1 part by mass. After the completion of the reaction, the radically polymerizable compound represented by the general formula (1) of the present invention is subjected to a conventional operation and treatment method (for example, neutralization, solvent extraction, water washing, liquid separation, solvent distillation removal, etc.). ) is post-processed and isolated. [Polymer polymerizable compound of the general formula (1)] The radically polymerizable compound represented by the general formula (1) of the present invention is easily radically polymerized by heat, ultraviolet rays, electron beams or the like. It can also be copolymerized with other radical polymerizable compounds. The radically polymerizable compound represented by the general formula (1) means that two polymerizable double bonds are difunctional, and a single polymerization (hardening reaction) can also form a crosslinked structure, but the physical properties of the individual polymers. For example, when it is possible to copolymerize with other radical polymerizable -18-200848396 compounds for the purpose of improving the balance between the refractive index and the Abbe number, and the copolymerizable radical polymerizable compound has polyfunctional radical polymerizability, It can be made into a cured product with a higher crosslinking density. Further, a monofunctional radical polymerizable monomer can also be used for the purpose of lowering the viscosity of the polymer and improving the moldability. The radically polymerizable compound to be copolymerized with the radically polymerizable compound of the present invention is not particularly limited as long as it is a compound copolymerizable with the radically polymerizable compound of the general formula (1), and specific examples thereof are Examples thereof include di(meth)allyl phthalate, di(meth)allyl isophthalate, di(meth)allyl terephthalate, (methyl) Allyl benzoate, α-naphthoic acid (meth)allyl ester, 10,000-naphthoic acid (meth)allyl ester, 2-phenylbenzoic acid (meth)allyl ester, 3-benzene (meth)allyl benzoate, (meth)allyl 4-phenylbenzoate, (meth)allyl 〇-chlorobenzoate, (meth)allyl m-chlorobenzoate , (meth)allyl p-chlorobenzoate, (meth)allyl bromo-bromobenzoate, (meth)allyl m-bromobenzoate, (methyl) ene P-bromobenzoate Propyl ester, (meth)allyl 2,6-dichlorobenzoate, (meth)allyl 2,4-dichlorobenzoate, (meth)ene 2,4,6-tribromobenzoate Propyl ester, 1,4-cyclohexanedicarboxylic acid di(a) Allyl ester, u-cyclohexyl dicarboxylic acid di(methyl) propyl acrylate, 1,2-cyclohexane dicapric acid di(methyl) allyl ester, 1-cyclohexane-1 5 Di(methyl)allyl 2-dicarboxylate, di(methyl)allyl 3-methyl-1,2-cyclohexanedicarboxylate, 4-methyl-12-cyclohexanedicarboxylate Di(meth)allyl ester, endic acid di(methyl)propanate, di(methyl)allyl chlorate, 3,6·methyl-1,2-cyclohexanedicarboxylate Di(meth)allyl acid, tris(meth)allyl trimellitate, tetrakis(meth)-19-200848396 allyl ester, di(meth)allyl of biphenylate Allyl esters such as ester, di(meth)allyl succinate, di(meth)allyl adipate; dibenzyl maleate, dibenzyl fumarate, diphenyl Maleate, diphenyl fumarate, dibutyl maleate, dibutyl fumarate, dimethoxyethyl maleate, dimethoxyethyl fumarate Maleic acid diester/fumaric acid diester; methyl (meth) acrylate, ethyl (meth) acrylate, η-butyl (a Acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, stearin Base (meth) acrylate, lauryl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, B Diol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, anthracene, 6-hexanediol di(meth)acrylate, 1,9-nonanediol di(a) Acrylate, neopentyl glycol di(meth) acrylate, polyethylene glycol di(meth) acrylate, pentaerythritol tetra(meth) acrylate, di-trimethylolpropane tetra(methyl) Acrylate, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentene Hydroxyethyl (meth) acrylate, tricyclodecane dimethanol di(meth) acrylate, B (meth) acrylate such as oxycyclohexane dimethanol dimercapto acrylate or adamantyl (meth) acrylate; styrene, α-methyl styrene, methoxy styrene, diethylene An aromatic vinyl compound such as phenylbenzene; a vinyl ester of an aliphatic carboxy ester such as vinyl acetate, vinyl propionate, vinyl butyrate, trimethyl vinyl acetate, vinyl stearate or vinyl hexanoate An alicyclic ethyl -20-200848396 olefin ester such as cyclohexanecarboxylic acid vinyl ester; an aromatic vinyl ester such as vinyl benzoate or vinyl t-butyl benzoate; diallyl carbonate, diethyl a diol bisallyl carbonate, an allyl carbonate compound such as polyethylene glycol bis(allyl) carbonate typified by PPG Corporation under the trade name CR-39; (meth)acrylic acid having a terminal (meth)acrylic acid An ester group having an oligomer formed by an ester structure derived from a polyvalent carboxylic acid and a polyhydric alcohol; (meth)acrylic acid (meth) allyl ester having a polymerizable double bond having different reactivity in the molecule; Methyl)vinyl acrylate and di(meth)allyl maleate Thereof; triallyl isocyanurate and tri allyl cyanurate, etc. nitrogen-containing polyfunctional allyl compounds. However, these radically polymerizable compounds are not limited to the above, and are not limited to the above. Further, these radically polymerizable compounds may be used in combination of two or more kinds in order to obtain the desired physical properties. Among these radically polymerizable compounds, from the viewpoint of having both a refractive index and an Abbe number, di(methyl)allyl 1,4-cyclohexanedicarboxylate or trimethylol is preferred. Propane tri(meth)acrylate, di(meth)allyl isophthalate, di(meth)allyl terephthalate, tris(meth)allyl trimellitate The ester, tetrakis(meth)allyl ester of pyromellitic acid, an oligomer having a (meth) acrylate group at the terminal and an ester structure derived from a polyvalent carboxylic acid and a polyol. Further, a (meth)acrylic acid (meth) allyl ester, a vinyl (meth) acrylate, and a di(methyl) allyl maleate have a radically polymerizable double bond having different reactivity in a molecule. Compounds are also preferred, and such compounds are useful in controlling the degree of hardening at the time of hardening formation by radical polymerization from the difference in reactivity. -21 - 200848396 When the radically polymerizable compound of the present invention is polymerized, it may be thermally polymerized without using an initiator, but a radical polymerization initiator is preferably used as a radical polymerization initiator, as long as it is Any one of radicals generated by heat, ultraviolet rays, electron beams, radiation, or the like may be used, and a thermal radical polymerization initiator and a polymerization initiator by radiation may be used. Examples of the thermal radical polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobisisovaleronitrile, and dimethyl-2,2'-azobisisobutyrate. An azo compound; a ketone peroxide such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide or cyclohexanone peroxide; benzamidine peroxide, hydrazine a sulfhydryl peroxide such as a base peroxide or a lauryl peroxide; a di- lysyl peroxide, a tributyl cumyl peroxide, a di-tert-butyl peroxide, etc. Dialkyl peroxide; 1,1_bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(p-hexylperoxy)cyclohexane, 1, a peroxy ketal such as 1-di-t-butylperoxycyclohexane or 2,2-bis(t-butylperoxy)butane; t-butylperoxytrimethylacetate, T-butylperoxy-2-ethylhexanoate, t-butyl peroxyisobutyrate, di-t-butylperoxy hexahydroterephthalic acid, dibutyl peroxyperoxide , t-butylperoxy-3,5,5-trimethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1,3 , 3-tetramethylbutylperoxy-2-ethylhexanoate, t-butyl peroxyacetate, t-butyl peroxybenzoate, di-t-butylperoxytrimethyl peroxide a hospital-based peroxyester such as adipate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxylaurate, t-hexylperoxybenzoate; diisopropyl Peroxycarbonate -22-200848396, etc., such as oxydicarbonate, di-sec-butyl peroxydicarbonate, t-butylperoxy isopropyl carbonate, etc., but is not limited thereto. Further, these thermal radical polymerization initiators may be used in combination of two or more kinds. The radical polymerization initiator of ultraviolet rays, electron beams, and radiation' can be exemplified by, for example, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, and 1- Hydroxy-cyclohexyl-phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1, 2-benzyl-2-dimethylamino Acetophenone derivatives such as 1-(4-?B-linylphenyl)-butanone-1, 2-hydroxy-2-methyl-1-phenyl-propan-1-one; benzophenone , 4,4,-bis(dimethylamino)benzophenone, 4-trimethyldecyl benzophenone, 4-benzylidene-4,-methyl-diphenyl sulfide, etc. Benzophenone derivatives; benzoin derivatives such as benzoin, benzoin ether, benzoin propyl ether, benzoin isobutyl ether, benzoin isopropyl ether; methylphenylglyoxylic acid The ester, the benzoin dimethyl ketal, the 2,4,6-trimethylbenzhydryldiphenylphosphine oxide, and the like are not limited thereto. Further, these ultraviolet rays, electron beams, and radiation radical polymerization initiators may be used in combination of two or more kinds. The amount of the polymerization initiator to be added differs depending on the curing temperature or the composition ratio of the radical polymerizable composition, the type and amount of the additive, and thus cannot be uniformly defined, but is relative to the general formula of the present invention ( The total amount of the radically polymerizable compound of 1) and the other radically polymerizable compound copolymerized as necessary is 100 parts by mass, preferably 1 to 15 parts by mass, preferably 〇·1~ 10 parts by mass is particularly preferred. When the amount of the radical polymerization initiator added is less than the parts by mass, polymerization and hardening may be insufficient, and addition of more than 15 parts by mass is economically unfavorable. The polymerization temperature (hardening temperature) may be appropriately selected according to the type of the polymerization initiator, and may be selected from 23 to 200848396. If it is polymerized by ultraviolet light or the like, it may be at room temperature, and it is desirable to correspond to the decomposition temperature of the initiator at the time of thermal polymerization. As appropriate, it is generally 30 to 13 (TC, and it is also possible to change the temperature stepwise to polymerize (harden), and an inert solvent can be used for the polymerization. By the general formula (1) of the present invention The resin obtained by the polymerization of the radically polymerizable compound is suitable as a resin for an optical material having high transparency and high refraction. [A composition for an optical material] The composition for an optical material of the present invention and a cured product thereof contain the above-mentioned In the case of the radically polymerizable compound represented by the formula (1), the compound of the general formula (1) is polymerized alone, or the composition copolymerized with another radically polymerizable compound is cured to form a cured product. If necessary, a radical polymerization initiator or the like may be contained. When the copolymerized radical polymerizable compound is polyfunctional, the crosslinking density can be adjusted. The base polymerizable compound, the radical polymerization initiator, and the polymerization (hardening) method are as described above, but since there is a problem of removal from the cured product, it is preferred not to use a solvent. The radical polymerizable compound of the present invention is The blending amount of the composition in the case where the other radically polymerizable compound is copolymerized is not particularly limited, but is preferably 60% by mass or more of the radical polymerizable compound of the present invention, and more preferably 75 mass% or more. Further, any one of the polymerization or the copolymerization alone may be suitably blended with a monofunctional radical polymerization in the case of casting hardening in the case of hardening, in the case of casting hardening, in order to reduce the viscosity and easily inject into the mold. The viscosity of the monomer is used as a reactive diluent. The viscosity is preferably 600 mPa·s or less in the temperature when flowing into the model, preferably less than 30 OmP a · s, and particularly preferably below 20 OmP a · s. Further, the viscosity is 値 measured according to ns Z8 8 03, and the monofunctional radical polymerizable monomer may be exemplified as the copolymerization with the radical polymerizable compound of the present invention. A monofunctional one of the compounds exemplified by the radically polymerizable compound. Further, the composition for an optical material of the present invention may be an ultraviolet absorber, an antioxidant, a release agent, a colorant (pigment, dye). Various additives such as a flow regulator, a leveling agent, an inorganic chelating agent, etc. Specific examples of the ultraviolet absorber include 2-(2'-hydroxy-tert-butylphenyl)benzotriazole Such as triazoles, benzophenones such as 2,4-dihydroxybenzophenone, salicylates such as 4-tert-butylphenylsalicylate, and double-(2,2 a hindered amine such as 6,6-tetramethyl-4-piperidine) sebacate, but is not limited thereto. The blending amount of the ultraviolet absorber may be depending on the type of other blend, The amount of the total radical polymerizable component in the composition for an optical material is preferably 0.01 to 2 parts by mass, and more preferably 〇. 3 to 1.7 parts by mass. 0.05 to 1.4 parts by mass is the best. When the ultraviolet absorber is less than 0.01 parts by mass, sufficient effects cannot be expected, and more than 2 parts by mass are economically unsatisfactory. As the antioxidant, 2,6·di-tert-butyl-4-methylphenol, -25-200848396 肆·[methyl-3-(3,5,-di-tert-butyl-) 4-hydroxyphenyl)propionate] a phenol type such as methane, a sulfur-based compound such as dilauryl-3,3'-thiodipropionate, or a phosphorus-based antioxidant such as decyl phenyl phosphate Wait. The blending amount of the antioxidant may vary depending on the type, amount, and the like of the other blend, but generally, the amount of the total radical polymerizable component in the composition for an optical material is 〇〇. 1 to 5 parts by mass is more preferable, and 〇·〇 5 to 4 parts by mass is more preferable, and 1 to 3 parts by mass is most preferable. If the antioxidant is less than 质量·〇1 by mass, sufficient effect cannot be expected, and if it is more than 5 parts by mass, it is economically unsatisfactory. The release agent may, for example, be stearic acid, butyl stearate, zinc stearate, decylamine stearate, a fluorine compound or an anthraquinone compound, but is not limited thereto. The blending amount of the release agent may vary depending on the type, amount, and the like of the other blend, but is generally 0.01 to 2 by mass based on 100 parts by mass of the total radical polymerizable component in the composition for an optical material. The portion is preferably 0.03 to 1.7 parts by mass, more preferably 0.05 to 1.4 parts by mass. When the release agent is less than 0.01 parts by mass, sufficient effects cannot be expected, and if it exceeds 2 parts by mass, it is economically unfavorable, and there is a problem that the surface of the cured product is sticky or the like. Examples of the coloring agent include organic pigments such as anthraquinone, azo, cation, quinolin, quinone, anthraquinone, and phthalocyanine, and organic dyes such as ice dyes and sulfur dyes. , inorganic pigments such as tian yellow, yellow iron oxide, zinc yellow, chrome orange, molybdenum red, cobalt violet, cobalt blue, cobalt green, chromium oxide, titanium oxide, zinc sulfide, carbon black, etc., but not The amount of the blending is not particularly limited. -26- 200848396 When the composition for an optical material of the present invention is formed into an optical material such as a plastic lens, casting molding is suitable, and specifically, a radical polymerization initiator is added to the composition, and a hose or a catheter is used. Injecting into a mold in which an elastomer pad and a liner are fixed, a method of hardening it in an oven by heat, or the like. As the model to be used, it is preferable to use metal or inorganic glass. The model after casting the plastic lens must be washed with strong acid or alkali, so it is not easy to be deteriorated due to washing, and it is easy to be honed. For the reason of obtaining a flat surface, it is preferable to use a model made of inorganic glass. The curing temperature of the composition for an optical material of the present invention when molded into a plastic lens or the like varies depending on the composition ratio of the composition and the type and amount of the additive, but is generally about 20 to 150 ° C, preferably 30 to 120. °C. Further, in the operation of the hardening temperature, it is preferable to consider the shrinkage or the skew at the time of hardening to slowly harden while raising the temperature. Generally, it takes from 0. 5 to 100 hours, preferably from 3 to 50 hours, and more preferably from 10 to 30 hours. In addition, the molded article for an optical material obtained by curing the composition for an optical material of the present invention may be subjected to various coating treatments if necessary, and for example, an organic antimony compound for improving scratch resistance and tin oxide may be used. A coating liquid of a fine particulate inorganic substance such as cerium oxide, chromium oxide or titanium oxide can form a high hardness film on the molded body. In addition, in order to improve the impact resistance, an undercoat layer mainly composed of polyurethane or polyester may be provided, and in order to impart anti-reflection properties, cerium oxide, oxidized cerium, chromium oxide, or the like may be used. Oxidation giants form an anti-reflection film, and in addition, in order to repel water -27-200848396, an organic ruthenium compound having a fluorine atom can be used to form a water-repellent film on the anti-reflection film. [Optical material] The cured product of the composition for an optical material of the present invention can be used as an optical lens such as a spectacle lens or a camera lens, an optical waveguide, an optical sealant, an optical adhesive, an optical film, a prism, or a guide for a liquid crystal panel. Optical materials such as light plates, optical fibers, transparent panels, transparent films, transparent plates, and the like. [Embodiment] [Examples] Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, and the invention is not limited by the description. The physical properties of the materials synthesized in the examples and comparative examples were measured as follows. 1·Refractive index (η〇) and Abbe number (Vd) Model: Abbe refractometer IT type (made by ATAGO Co., Ltd.), measurement method: Produce a test piece of 9 mm X 1 6 mm X 4 mm, using " The Abbe refractometer 1T" measures the refractive index (nD) at 25 ° C and the Abbe number (&gt; D), and the contact liquid uses diiodomethane.

2. ^-NMR/^-NMR Model: JEOL EX-400 (400 MHz, manufactured by JEOL Ltd.), measurement method: Dissolved in heavy hydrogenated chloroform, and internal standard was measured using tetramethyl -28-200848396 decane.

3. FT-IR model: Spectrum GX (manufactured by Perkin Elmer Co., Ltd.), measurement method: using a KBr plate, measured by a liquid membrane method. 4. Barcol hardness According to JIS K6911, the GYZJ93 4-1 type manufactured by BARBER COLMAN is used. Example 1: Synthesis of S,S'-bis[2-(allyloxycarbonylthio)ethyl]dithiocarbonate (abbreviated as BADTC) [Chemical 10] + HS^/^sh NaOH 〇Ο (7) 1/2 1/2 03⁄4 (8) S人 S 八/丫0—^ ο ο (9) In a three-necked flask equipped with a thermometer, a dropping funnel, and a stirrer, add sodium hydroxide (8.07§ 'OJOmol) to 80.7 g of pure water was completely dissolved, and then toluene 2 4 · 0 m 1 ' was added to the ice bath to make the temperature in the system 10 ° C or less. (6) 'Ishi 化g, 0.20 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), stirred for 2 minutes, and then added to the dropping funnel, toluene-29-200848396 24.0 ml diluted with allyl chloroformate (chemical formula (5) ), a solution of Tokyo Chemical Co., Ltd., 24.3 g, 0.20 mol), which was added to a solution of ethylenedithiol in 1 hour. After the completion of the dropwise addition, the temperature in the system was stirred for 1 hour or less, and the reaction liquid was transferred to a separatory funnel liquid operation, and the water layer of the toluene layer was further washed to obtain a water layer of 7, and the obtained water was obtained. The toluene layer is subjected to sodium sulfate removal by filtration to obtain a toluene of dehydrated decyl-allyl 3-ethylethyl thiocarbonate (a compound of the formula (7)), and a thermometer and a drop are provided. a three-necked flask of a funnel, a Dimroth condenser, and a stirrer was placed therein to carry nitrogen into the previously obtained toluene solution, and then, in an ice-baked bath, the temperature of the contents was set at 1 (TC or less, by using A solution of N,N'-carbonyldiimidazole (chemical formula (8), 16.4 g, 0.1 mol) prepared by dissolving N,N-diamine (DMF) 1 in 15.0 ml was added dropwise thereto for 1 hour. When the temperature in the system is maintained at 10 ° C or lower H, pure water 50 m 1 is added to the reaction solution, and the mixture is transferred to a separatory funnel liquid, and the obtained organic layer is further 5% aqueous sodium hydroxide solution 5 The treatment of 0 ml, 5% hydrochloric acid 15 ml was carried out in sequence, and finally the heavy water was washed until The layer was made neutral, and the recovered organic sodium sulfate was dried, filtered, and the sodium sulfate was removed, and the crude product was evaporated under reduced pressure to give a crude product (37.6 g). Further, the crude product was mixed with hexane and ethyl acetate. The solvent was purified as a solvent to obtain a colorless transparent liquid (yield: 21.4 g of the industrial company was added to the above-mentioned degree to maintain the pH of the fraction to be dried, by S-S-(2 - dredging liquid. Displacement, the bottle is immersed in the dropping funnel, the soil is stabilized, the methyl methacrylate is mixed with 3 small, and the mixture is divided into 15 ml, and the pure layer is purified. The pure layer is removed by anhydrous distillation to remove the low-mass by column chromatography. Yield: -30- 200848396 5 6.0%). The W-NMR, 13C-NMR and IR of the liquid were measured to confirm that the target compound was S,S'-bis[2-(allyloxycarbonylthio)ethyl]dithiocarbonate. The results of (chemical formula (9)), W-NMR, 13C-NMR and IR are shown in Figures 1 to 3. Example 2: Hardening reaction of BAD TC The BAD TC (2.5 00 g) obtained in Example 1 In the addition of 1,1-di(1&gt;hexylperoxy)-3,3,5-dimethylcyclohexanide as a radical polymerization initiator ( Made by Nippon Oil & Fat Co., Ltd., trade name: PERHEXA TMH, O.OlOg), flowing into a 4mm thick model made of 2 pieces of glass and a lining hose as a liner, placed in an oven at 70 °C After heating for 7 hours, the temperature was raised to 90 ° C for 10 hours, and the temperature was raised to 120 ° C over 3 hours, and in this state, the so-called hardening temperature was heated at 1 20 ° C for 2 hours to thermally harden it. The colorless and transparent curable physical properties (refractive index, Abbe number, and Bacol hardness) obtained by the results were measured, and the resin compositions are shown in Table 1. The physical properties of the measurement results are shown in Table 2. Example 3: Hardening of a copolymer composition of BADTC and trimethylolpropane trimethacrylate. BAD TC (2.375 g) obtained in Example 1 and trimethylolpropane trimethacrylate (Tokyo Chemical Co., Ltd.) Industrial Co., Ltd., 0.1 25 g) of a mixture of t-hexylperoxy-2-ethylhexanoic acid-31 - 200848396 ester added to a radical polymerization initiator (trade name: PERHEXYL®, 〇. 〇75g) and PERHEXA TMH (0.025g) were thermally hardened using the same model and hardening temperature process as in Example 1. The colorless and transparent curable physical properties obtained by this result were measured, the resin composition is shown in Table 1, and the physical property measurement results are shown in Table 2. Example 4: Copolymerization of BADTC with diallyl isophthalate

In the mixture of BADTC (1·80 3 g) obtained in Example 1 and diallyl isophthalate (0.203 g), 1, 1, 3, 3 - 4 of a radical polymerization initiator was added. Methyl butyl peroxy-2-ethylhexanoate (manufactured by Nippon Oil & Fats Co., Ltd., trade name: PEROCTA®, 0.061 g) and PERHEXA TMH (0.020 g) were passed through two sheets of glass and a crucible The model of the thickness of 4 mm made of the hose was placed in an oven and heated from 60 ° C to 120 ° C for 16 hours. In this state, the so-called hardening temperature process was heated for 2 hours to make it hot. hardening. The colorless and transparent curable physical properties obtained by this result were measured, the resin composition is shown in Table 1, and the physical property measurement results are shown in Table 2. Example 5: Hardening of a copolymer composition of BADTC and diallyl 1,4-cyclohexanedicarboxylate BADTC ( 1.807 g) obtained in Example 1 and 1,4-cyclohexanedicarboxylic acid In a mixture of allyl ester (〇·〇2 Og), a free radical polymerization initiator PEROCTA 0 (0.066 g) and PERHEXA Τ Μ Η (0 · 0 2 0 g) were added, and -32-200848396 Example 4 The same model and hardening temperature process were used to thermally harden it. The colorless and transparent curable physical properties obtained by this result were measured, the resin composition is shown in Table 1, and the physical property measurement results are shown in Table 2. Example 6: Hardening of a copolymer composition of BADTC and isobornyl methacrylate. The BAD TC ( 1.90 7 g) obtained in Example 1 and isobornyl methacrylate (manufactured by Kyoei Chemical Co., Ltd., PEROCTA 0 (0.065 g) and PERHEXA TMH (0.023 g) were added to a mixture of LIGHT-ESTER IB-X, 0.105 g, and thermally hardened by the same model and hardening temperature process as in Example 4. The colorless and transparent curable physical properties obtained by this result were measured, the resin composition is shown in Table 1, and the physical property measurement results are shown in Table 2. Example 7: Hardening of a copolymer composition of BADTC and dicyclopentyl methacrylate BADTC (1.900 g) obtained in Example 1 and dicyclopentyl methacrylate (trade name: Hitachi Chemical Co., Ltd.: To a mixture of FA-513M, O.lOlg), PEROCTA 0 (0.064 g) and PERHEXA TMH (0.023 g) were added, and the same model and hardening temperature process as in Example 4 were used to thermally harden. The colorless transparent curable physical property 'resin composition obtained by measuring this result is shown in Table 1, and the physical property measurement results are shown in Table 2 ° -33 - 200848396. Example 8: BADTC and allyl ester oligomer-1 Hardening of the copolymer composition in the mixture of BADTC (1.801 g) obtained in Example 1 and allyl ester oligomer_1 (the following chemical formula (10), n = 0 (monomer) was 40% by mass, n Above =1 is 60 mass. PEROCTA 0 (0.064 g) and PERHEXA TMH (0.029 g) were added to the mixture of 〇 206 (206 g), and the same model and hardening temperature process as in Example 4 was used to thermally harden it. The colorless and transparent curable physical properties obtained by this result were measured, the resin composition is shown in Table 1, and the physical property measurement results are shown in Table 2. [1 1]

Further, allyl ester oligomer-1 was produced as follows. A 3 liter three-necked flask equipped with a distillation apparatus was charged with 1500.0 g (6.09 mol) of diallyl meta-formate, 154.5 g (2.03 mol) of propylene glycol, and 150 kg of dibutyltin oxide under a nitrogen stream. After heating at 180 ° C, the resulting allyl alcohol was removed. When the allyl alcohol was distilled off to a degree of about 140 g, the pressure in the reaction system was reduced to 1.33 kPa to accelerate the distillation removal rate of allyl alcohol, and the theoretical amount (23 5.9 g) of allyl alcohol was distilled off, and then 180 C / 0. · 1 3 k P a was maintained for 1 hour and 'cooling reaction benefit' to obtain 1 4 2 0 · 1 g of allyl ester oligomer-1. -34- 200848396 Example 9: Hardening of a copolymer composition of BADTC and allyl ester oligomer-2 BADTC ( 1.802 g) and allyl ester oligomer-2 obtained in Example 1 {The following chemical formula ( PEROCTA 0 (0.064 g) and PERHEXA TMH (0.021 g) were added to a mixture of 1 1), η = 0 (monomer) of 45 mass%, and η = 1 or more of 55 mass%} (0.203 g). It was thermally hardened by the same model and hardening temperature process as in Example 4. The colorless transparent curable physical property of the resin obtained by measuring the results is shown in Table 1, and the measurement results of the physical properties are shown in Table 2. [1 2]

Further, allyl ester oligomer-2 was produced as follows. A 3 liter three-necked flask equipped with a distillation apparatus was charged with diallyl 1,4-cyclohexanedicarboxylate 1 500.0 g (5.95 mol), trimethylolpropane 177.3 g (1.32 mol), dibutyltin. 1.50 g of an oxide was heated at 180 ° C under a nitrogen stream to remove the allyl alcohol formed. When the allyl alcohol was distilled off to a degree of 138 g, the pressure in the reaction system was reduced to 1.33 kPa to accelerate the distillation removal rate of allyl alcohol. After the theoretical amount (2 3 0.2 g) of allyl alcohol was distilled off, After maintaining at 180 ° C /0 · 1 3 kP a for 1 hour, the reactor was cooled to obtain I 448.5 g of allyl ester oligomer-2. -35- 200848396 Example 10: Hardening of a copolymer composition of BADTC and allyl ester oligomer-3 BADTC ( 1.808 g) and allyl ester oligomer-3 obtained in Example 1 {The following chemical formula ( PEROCTA 0 (0.061 g) and PERHEXA TMH (0.022 g) were added to a mixture of 12), a mixture of n = 0 (monomer) of 40% by mass, and n = 1 or more of 60% by mass} (〇.212 g). The same model and the hardening temperature process as in Example 4 were used to thermally harden it. The colorless and transparent curable physical properties obtained by this result were measured, the resin composition is shown in Table 1, and the physical property measurement results are shown in Table 2. 【化1 3】

Further, allyl ester oligomer-3 was produced as follows. A 3 liter three-necked flask equipped with a distillation apparatus was charged with diallyl isophthalate 1500. (^(6.09111〇1), 2,2-bis[4-(2-hydroxyethoxy)-3, 5-Bybromophenyl]propane 5 54.7g (〇.88mol), dibutyltin oxide 1 · 50g, heated under the nitrogen stream at 180 ° C, 'removed the allyl alcohol produced, in the ene When the propanol is distilled off to a degree of 6 1 g, the pressure in the reaction system is reduced to 1.33 kPa to accelerate the distillation removal rate of the allyl alcohol. The theoretical amount (10 g 2.0 g) of the allyl alcohol is distilled off, and then 180 °. After maintaining C / 0.13 kPa for 1 hour, the reactor was cooled to obtain 1 954.2 g of allyl ester oligomer-1 - 36 - 200848396 Example 1 1 : copolymerization composition of BADTC and triallyl trimellitate The hardening was carried out in a mixture of BADTC ( 1.907 g) obtained in Example 1 and triallyl trimellitate (manufactured by Wako Pure Chemical Industries, Ltd., 〇·1 03 §). 'Add PEROCTA 〇 (〇.〇61g) It was thermally hardened with PERHEXA TMH (0.022 g) in the same manner as in Example 4 and a hardening temperature process. The colorless transparent hardenable physical property of the resin obtained by measuring the results is shown in 1. The measurement results of the physical properties are shown in Table 2. Example 12: Hardening of the copolymer composition of BADTC and triallyl isocyanate, BADTC (1.803 g) obtained in Example 1 and trimerization PEROCTA 0 (0.061 g) and PERHEXA TMH (0.025 g) were added to a mixture of triallyl cyanate (0.201 g, manufactured by Wako Pure Chemical Industries, Ltd.), and the same model and hardening temperature process as in Example 4 were used. Thermal hardening. The colorless and transparent hardenability property obtained by this result was measured, the resin composition is shown in Table 1, and the physical property measurement result is shown in Table 2. Example 13: Copolymerization of BADTC and diallyl maleate The composition was hardened in a mixture of BADTC (1.806 g) obtained in Example 1 and diallyl maleate (0.202 g), and was forced into PEROCTA® (〇.062g) and PERHEXA TMH (0.023 g). The same model and the hard-37-200848396 temperature process were used to thermally harden the same method as in Example 4. The colorless and transparent hardenability property obtained by measuring the results was measured, and the resin composition is shown in Table 1, and the physical property measurement results are listed. Shown in Table 2. Example 14: A total of BADTC and allyl methacrylate Hardening of the poly-component was carried out in a mixture of BADTC (4.759 g) obtained in Example 1 and allyl methacrylate (0.256 g, manufactured by Wako Pure Chemical Industries, Ltd.), and PEROCTA 0 (0.150 g) and PERHEXA TMH were added. (0.05 3 g), which was thermally hardened in the same manner as in Example 4 and a hardening temperature process. The colorless and transparent curable physical properties obtained by this result were measured, the resin composition is shown in Table 1, and the physical property measurement results are shown in Table 2. Example 15: Hardening of a copolymer composition of BAD TC, allyl ester oligomer-2, and allyl methacrylate. The BADTC (4.251 g) obtained in Example 1 and allyl ester oligomer-2 ( PEROCTA® (0.151 g) and PERHEXA® Μ Η (0.06 0 g) were added to a mixture of 0.509 g) and allyl methacrylate (0.251 g), and the same model and hardening temperature process as in Example 4 were used. It is thermally hardened. The colorless and transparent curable physical properties obtained by this result were measured, the resin composition is shown in Table 1, and the physical property measurement results are shown in Table 2. Example 16: Hardening of a copolymer composition of BADTC, allyl ester oligomer-1, allyl methacrylate-38-200848396 BADTC (4.251 g) and allyl ester oligomer obtained in Example 1 PEROCTA® (0.154 g) and PERHEXA TMH (0.05 3 g) were added to a mixture of l (0.501 g) and allyl methacrylate (〇.257 g), and the same model and hardening as in Example 4 was used. The temperature process heats it hard. The colorless and transparent curable physical properties obtained by this result were measured, the resin composition is shown in Table 1, and the physical property measurement results are shown in Table 2. Example 17: Hardening of a copolymer composition of BADTC, diallyl 1,4-cyclohexanedicarboxylate, and allyl methacrylate, BADTC (4.259 g) obtained in Example 1 and 1,4- PEROCTA O (0.155 g) and PERHEXA TMH (0.05 7 g) were added to a mixture of diallyl cyclohexanedicarboxylate (0.25 2 g) and allyl methacrylate (〇.264 g), and used in Example 4 The same model and hardening temperature process make it thermally hard. The colorless and transparent curable physical properties obtained by this result were measured, the resin composition is shown in Table 1, and the physical property measurement results are shown in Table 2. Example 18: Hardening of a copolymer composition of BAD TC, allyl ester oligomer-2, diallyl maleate, BADTC (4.504 g) and allyl ester oligomer-2 obtained in Example 1. PEROCTA® (0.151 g) and PERHEXA TMH (0.05 3 g) were added to a mixture of (0.25 6 g) and diallyl maleate (〇.251 g), and the same model and hardening temperature process as in Example 4 was used. It is thermally hardened. The colorless and transparent hardenability property obtained by the measurement was measured, and the composition of the resin -39-200848396 is shown in Table 1, and the measurement results of the physical properties are shown in Table 2. Example 19: Hardening of a copolymer composition of BADTC and CR-39 In a mixture of BADTC (1.810 g) obtained in Example 1 and CR-39 (manufactured by PPG Co., Ltd., 〇_2〇lg), the force was broken into PEROCTA. 0 (0.065 g) and PERHEXA TMH (0.0 22 g) were thermally hardened in the same manner as in Example 4 and a hardening temperature process. The colorless and transparent curable physical properties obtained by this result were measured, the resin composition is shown in Table 1, and the physical property measurement results are shown in Table 2. Example 20: Hardening of a copolymer composition of BADTC, diallyl isophthalate, benzyl methacrylate, BAD TC ( 1. 802 g) obtained in Example 1, and diallyl isophthalate (〇·1 04g), a mixture of benzyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd., 0.102 g), PEROCTA 0 (0.062 g) and PERHEXA TMH (0.020 g) were used in the same manner as in Example 4. The model and the hardening temperature process make it thermally hardened. The colorless and transparent curable physical properties obtained by this result were measured, the resin composition is shown in Table 1, and the physical property measurement results are shown in Table 2. Example 21: Hardening of a copolymer composition of BAD TC, allyl ester oligomer-2, benzyl methacrylate BADTC ( 1.906 g) and allyl ester oligomer-2 (0) obtained in Example 1. .. 093 g), a mixture of benzyl methacrylate (〇.〇18g), adding -40-200848396 PEROCTA 0 (0.062g) and PERHEXA TMH (0.026g), using the same model and hardening as in Example 4. The temperature process heats it hard. The colorless and transparent curable physical properties obtained by this result were measured, the resin composition is shown in Table 1, and the physical property measurement results are shown in Table 2. Example 22: Hardening of a copolymer composition of BADTC, allyl ester oligomer-4, and allyl methacrylate, BADTC (2.250 g) and allyl ester oligomer-4 obtained in Example 1 The compound represented by the chemical formula (13), wherein n = 0 (monomer) is 40% by mass, and n = 1 or more is 60% by mass} (〇.60(^), allyl methacrylate (0.150 g) To the mixture, PEROCTA 0 (0.090 g) and PERHEXA TMH (0.03 0 g) were added, placed in the same model as in Example 4, and heated from 45 ° C to 1 20 ° C over 16 hours, in this state. The hardening temperature was heated for 2 hours to heat-harden. The colorless and transparent hardenability property obtained by this result was measured, the resin composition is shown in Table 1, and the physical property measurement result is shown in Table 2.

〇 ^0^^ 03) Further, allyl ester oligomer-4 was produced as follows. A 1 liter three-necked flask equipped with a distillation apparatus was charged with 400.04 g (1.664 mol) of diallyl terephthalate and 2,2-bis[4·(2-hydroxyethoxyl-41 - 200848396 base)- 3,5-dibromophenyl]propane I46.68g (0.23mol), dibutyl 0.127g' under the nitrogen stream, after 18 (^C heating, remove the allyl alcohol. The degree of allyl alcohol is 13.7g When distilling off, the pressure is reduced to 1.33 kPa, the distillation rate of allyl alcohol is accelerated, and (27.0 g) of allyl alcohol is distilled off, and then cooled at 13 Torr:/〇13 kPa. 5 1 9.0 g of allyl ester oligomer was obtained. Example 23: Hardening of BADTC (2.550 g) and trimer obtained from the compound of BADTC and triallyl isocyanate. PEROCTA 0 (0.090 g) and PERHEXA TMH (0.03 0 g) in a mixture of isoallyl ester (manufactured by Wako Pure Chemical Industries, Ltd., 0.450 g) were thermally cured in the same manner as in Example 22. The colorless and transparent obtained by measuring the results were measured. The composition of the physical properties of the hardening is shown in Table 1, and the measurement results of the physical properties are shown in Table 2. Example 24: Copolymer composition of BAD TC, triallyl isocyanurate, allyl olefinate Hardened in BADTC (2.5 50g) obtained in Example 1 and tripolyisoallyl ester (〇·300g) and allyl methacrylate (0.15 0g), PEROCTA O (〇.〇91g) PERHEXA(R) (0., which was thermally cured in the same manner as in Example 22. The physical properties of the colorless and transparent curable property obtained by measuring the results are shown in Table 1, and the measurement results of the physical properties are shown in Table 2. The theoretical amount of oxidation generated by the system is maintained at 1 J -4 ° copolymerization group cyanate III, added and implemented, resin methyl propyl cyanate three mixture, hydrazine 30g), resin -42- 200848396 Example 25: BAD TC, II Hardening of the copolymer composition of vinylbenzene and diallyl maleate in BADTC (1.500 g) obtained in Example 1 and divinylbenzene (manufactured by Wako Pure Chemical Industries, Ltd., O.100 g) and maleic acid In a mixture of diallyl ester (〇.3 99 g), PEROCTA 0 (0.060 g) and PERHEXA TMH (0.02 0 g) were force-injected, and the mixture was thermally cured in the same manner as in Example 22. The colorless transparency obtained by measuring the result was measured. The hardenability of the physical properties, the resin composition are shown in Table 1, and the measurement results of the physical properties are shown in Table 2. Example 26 : The copolymerization composition of BADTC, divinylbenzene, and allyl methacrylate was hardened in BADTC (1.700 g) obtained in Example 1 and divinylbenzene (0.10 g) and allyl methacrylate ( PEROCTA 0 (0.060 g) and PERHEXA TMH (0.019 g) were added to a mixture of 0.21 g), and the mixture was thermally cured in the same manner as in Example 22. The colorless and transparent curable physical properties obtained by this result were measured, the resin composition is shown in Table 1, and the physical property measurement results are shown in Table 2. Example 27: Hardening of a copolymer composition of BADTC, allyl methacrylate, diallyl maleate, BADTC (2.549 g) obtained in Example 1, and allyl methacrylate (0.015 g), To a mixture of diallyl maleate (0.310 g), PEROCTA 0 (0.090 g) and PERHEXA® (0·0 3 0 g) were added, and the mixture was thermally cured in the same manner as in Example 22 of No. 43-200848396. The colorless and transparent curable physical properties obtained by this result were measured, the resin composition is shown in Table 1, and the physical property measurement results are shown in Table 2. Example 28: Hardening of BADTC In B ADTC (2.000 g) obtained in Example 1, PEROCTA O (0.060 g) and PERHEXA TMH (0.020 g) were added, and the same model and hardening temperature process as in Example 4 were used. It is thermally hardened. The colorless and transparent curable physical properties obtained by this result were measured, the resin composition is shown in Table 1, and the physical property measurement results are shown in Table 2. Example 29: Lens formation of a copolymer composition of BAD TC, allyl ester oligomer-2, and allyl methacrylate. The BADTC (21.20 g) and allyl ester oligomer-2 obtained in Example 1 were formed. PEROCTA(R) (〇.75 0g) and PERHEXA TMH (0.25 0g) were added to a mixture of (2.550 g) and allyl methacrylate (1.250 g), and the mixture was stirred until uniform, and the obtained composition was poured into glass. The lens model of the model -2, which is formed of a resin-made gasket, was thermally cured by the same hardening temperature process as in Example 15, and after hardening, the lens mold was removed to obtain a lens-shaped molded body. Comparative Example 1: The hardening of bis(allyloxycarbonylthioethyl) sulfide is based on Example 1 of the paragraph [0025] of JP-A-10-357749 (Patent Document 4), Synthetic Chemical Formula (1 4 The compound represented by the formula: bis(ene-44-200848396 propoxythioethyl) sulfide. [Chemical 1 5 0 丫丫 0 (14) In this bis(storyloxythioethyl) sulfide (2.500 g), PERHEXA TMH (0.10 g) was added, and while heating, the flow was 2 The model of the thickness of 4 mm formed by the piece of glass and the enamel hose as a liner was placed in an oven, heated at 70 ° C for 7 hours, then heated at 90 ° C for 10 hours, and then heated for 3 hours. The so-called hardening temperature process was carried out at 120 ° C in this state at 120 ° C for 2 hours to thermally harden it. The yellow transparent hardenability property obtained by the above results was measured, and the resin composition is shown in Table 1, and the physical property measurement results are shown in Table 2. Comparative Example 2: Hardening of bis(allyloxycarbonylthioethyl) sulfide in bis(allyloxycarbonylthioethyl) sulfide (2.000 g) obtained in Comparative Example 1, PEROCTA 0 (0.060 g) and PERHEXA TMH (0.020 g) were thermally cured by the same model and hardening temperature process as in Example 4, and the obtained cured product was rubbery. The colorless and transparent curable physical properties obtained by this result were measured, the resin composition is shown in Table 1, and the physical property measurement results are shown in Table 2. -45 - 200848396 φ sl_ W 铤ACS |ιοο.ο| |ιοο.ο| DVB o tri o in TAC 15.0 10.0 AEO-4 I 20.0 BzMA tH in σ&gt; o CR - 39 I lo.o 1 ΑΜΑ ΙΛ ο in 1-4 in LO in o to 〇ΙΛ 10.0 ΙΛ DAM 10.0 S 20.0 10.5 TAIC 10.0 TAT 5 ss Μ AEO-3 ! 10.5 AEO-2 〇1.Λ0-2 1 2 AEO-1 10.3 | | lo.o | DCPMA 5 iBMA 6α ΙΛ H-DATP lo.o | CO io DAIP ιο.Γ] (M in TMPTMA S BADTC 100.0 1 95.0 1 89.9 1 90.0 1 94.8 1 94.9 | 89.7 | 89.9 | 89.5 | 94.9 | ί 90,0 1 1 90.0 ] 94.9 Ί 1 84.8 1 | 84.9 | "89.2 ] 89.9 | | 90.0 ! | 89.8 | 94.5 | 75.0 | 85.0 | 85.0 | 75.0 | 85.0 | 89.0 | loo.o C3 u CO Series u Grip in K 1 Example 6 | m Series n 00 Series "Example 9] 〇i 辑 rH i in ϊ 辑 W [Embodiment · 2 i IK in i series 2 £ Ϊ 辑 00 i series 2 i series sm key in m series K m series in 1 example 23 mm K m series in m. Example 27 "Example 28" Comparative Example 1 Plant Comparative Example 2 - 46 - 200848396 [Table 2] Hardening dose (% by mass) Optical physical hardness Appearance HO 00 TMH Refractive index (nD) (25° 〇 Abbe Number (vD) (25° 〇 Bakoer hardness Visual Example 2 4.0 1.6050 35.1 7 Colorless and transparent Example 3 3.0 1.0 1.6021 36.3 0 Colorless and transparent Example 4 3.0 1.0 1.6025 37.8 0 Colorless and transparent Example 5 3.3 1.0 1.5955 38.5 0 Colorless and transparent Example 6 3.2 1.1 1.5953 37.7 0 Colorless and transparent Example 7 3.2 1.1 1.5990 40.7 0 Colorless and transparent Example 8 3.2 1.4 1.5981 36.3 0 Colorless and transparent Example 9 3.2 1.0 1.5961 34.6 0 Colorless and transparent Example 10 3.0 1.1 1.6059 35.7 0 Colorless and transparent embodiment 11 3.0 1.1 1.6030 36.7 2 None Transparent Example 12 3.1 1.2 1.6010 36.5 4 Colorless and transparent Example 13 3.1 1.1 1.5998 37.5 7 Colorless and transparent Example 14 3.0 1.1 1.6030 36.6 0 Colorless and transparent Example 15 3.0 1.2 1.5940 37.5 4 Colorless and transparent Example 16 3.1 1.0 1.5970 37.4 8 Colorless Transparent Example 17 3.2 1.2 1.5950 38.5 2 Colorless and transparent Example 18 3.0 1.1 1.5967 38.6 0 Colorless and transparent Example 19 3.2 1.1 1.5971 39.5 0 Colorless and transparent Example 20 3.1 1.0 1.6020 39.0 0 Colorless and transparent Example 21 3.1 1.3 1.5995 41.0 0 Colorless Transparent Example 22 3.0 1.0 1.5959 36.1 0 Colorless and transparent Example 23 3.0 1.0 1.5975 37.8 6 Colorless and transparent Example 24 3.0 1.0 1.5962 38.2 3 Colorless and transparent Example 25 3.0 1.0 1.5930 37.5 24 Colorless and transparent Example 26 3.0 0.9 1.5971 38.8 10 Colorless Transparent Example 27 3.1 1.0 1.5901 37.7 5 Colorless and transparent Example 28 3.0 1.0 1.6050 36.7 0 Colorless and transparent Comparative Example 1 4.0 1.5875 42.6 0 Yellow transparent Comparative Example 2 3.0 1.0 1.5892 43.0 0 Colorless and transparent-47- 200848396 Table 1 and Table 2 The abbreviations used are as follows. BADTC : S,S'-bis[2-(allyloxycarbonylthio)ethyl]dithiocarbonate TMPTMA: trishydroxypropyl propyl trimethyl propyl acrylate DAIP : isophthalic acid II Allyl ester H-DATP : diallyl 1,4-cyclohexanedicarboxylate IBMA: isobornyl methacrylate DCPMA: dicyclopentyl methacrylate AEO-1~4: allyl ester oligo Polymer-1~4 TAT: Triallyl trimellitate TAIC ··Allyl isocyanate DAM: diallyl maleate ΑΜΑ : allyl methacrylate CR-39 : two Glycol bisallyl carbonate

BzMA: benzyl methacrylate TAC : triallyl isocyanurate DVB : divinylbenzene

ACS: bis(allyloxycarbonylthioethyl) sulfide HO: PERHEXYL Ο 00 : PEROCTA Ο TMH : PERHEXA TMH As shown in the results, the radically polymerizable compound of the present invention and the composition for chemical materials are obtained. The cured product is colorless and transparent, and has a high refractive index of -48-200848396, which is suitable as an optical material. On the other hand, in the cured product of Comparative Example 1, the refractive index is different from the Abbe number, and the coloring is observed. The hardened material of 2 is a hard rubber. [Industrial Applicability] The radically polymerizable compound having a dithiocarbonate structure and a thioallyl carbonate group according to the present invention is stable in the heat curing reaction and has little coloration and high refractive index. An optical material with excellent transparency. The cured product of the composition for an optical material of the present invention can be used as an optical lens such as a spectacle lens or a camera lens, an optical waveguide, an optical sealant, an optical adhesive, an optical film, a prism, a light guide plate for a liquid crystal panel, an optical fiber, or the like. It is used as an optical material such as a transparent panel, a transparent film, or a transparent plate. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] Fig. 1 is a 1H-NMR spectrum of S,S'-bis[2-(allyloxy orthothio)ethyl]dithiocarbonate obtained in Example 1. Fig. 2 is a 13C-NMR spectrum of S,S '-bis[2-(pyridyloxythio)ethyl]dithiocarbonate obtained in Example 1. Fig. 3 is an IR spectrum of S,S,-bis[2-(allyloxymethylthio)ethyl]dithiocarbonate obtained in Example 1. -49-

Claims (1)

200848396 X. Patent application scope 1 · A radical polymerizable compound represented by the general formula (1), [Chemical 1] (wherein R1 and R2 each independently represent a hydrogen atom or a methyl group, and X and γ each independently represent a group of branched alkyl groups, extended aryl groups and extended cycloalkyl groups having 1 to 10 carbon atoms; The selected two-valent base). 2. The radically polymerizable compound according to claim 1, wherein X and Y in the above general formula (1) are a methyl group, an ethyl group, a 1, 2, a propyl group or a 1,3 - stretching group. Propyl. 3. The radically polymerizable compound according to claim 1 or 2, wherein the reverse 1 and R2 in the above general formula (1) are a hydrogen atom. 4. The method for producing a radically polymerizable compound represented by the general formula (1) is characterized in that the dithiol represented by the general formula (2) is represented by the general formula (3) in the presence of a base. The (meth)allyl halide is reacted to obtain a thiol compound represented by the general formula (4), and then reacted with n,N,-carbonyldiimidazole, and the HS&quot; Wherein, L represents a divalent group selected from the group consisting of a branched alkyl group, an extended aryl group and a cycloalkyl group having a carbon number of 1 to 1 Å) -50 - 200848396 [Chemical 3] (wherein R4 represents a hydrogen atom or a methyl group, and Z represents a chlorine atom or a bromine atom) (4) (The mark in the formula is the same as above) [Chemical 5] (1) (wherein R1 and R2 each independently represent a hydrogen atom or a methyl group, and X and γ each independently represent a branchable alkyl group, an aryl group and a cycloalkyl group having a carbon number of 1 to 10; The selected two-valent group in the resulting group). 5. The method for producing a radically polymerizable compound according to claim 4, wherein X and γ in the above general formula (1) are a methyl group, an ethyl group, a 1,2-propyl group or a stretching group. Propyl. 6. The method for producing a radically polymerizable compound according to claim 4, wherein Ri and r2 in the above general formula (1) are hydrogen atoms. A polymer or a copolymer characterized by the radical polymerizable compound according to any one of claims 1 to 3 as a raw material monomer. The copolymer of the radically polymerizable compound and the other radically polymerizable compound according to any one of claims 1 to 3, wherein the copolymer is a copolymer of the radical polymerizable compound. 9. The copolymer of claim 8 which is a radical polymerizable compound as described in any one of claims 1 to 3, and allyl methacrylate and/or maleic acid diene Copolymer of ester. (1) A polymerizable composition for an optical material, which is characterized by containing the radical polymerizable compound according to any one of claims 1 to 3. 1 1 The polymerizable composition for an optical material according to the first aspect of the invention is further characterized in that it further contains another radical polymerizable compound. 1 2 The polymerizable composition for an optical material according to the first aspect of the invention, wherein the other radical polymerizable compound is at least a propyl methacrylate and/or a dipropyl propyl maleate. 1 3 - A cured product of a polymerizable composition for an optical material recorded in any one of claims 1 to 12. 1 4 A molded article for an optical material, characterized by comprising a cured product of claim 13 of the patent application. 1 5 The molded article for an optical material as set forth in claim 4 is selected from the group consisting of a lens, an optical waveguide, a film, a prism, a flat plate, or a fiber. The lens of the invention is characterized in that the optical material of any one of the first to fourth aspects of the invention is cured by a polymerizable composition. -52-