JP2008285644A - Radically polymerizable compound having dithiocarbonate structure and sulfur-containing allylcarbonate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical material which has a high refractive index and an excellent transparency and is stable and little colored at the time of thermal curing reaction. <P>SOLUTION: The following are provided: a radically polymerizable compound having a dithiocarbonate structure represented by general formula (1) (wherein R<SP>1</SP>and R<SP>2</SP>are each independently a hydrogen atom or a methyl group; and X and Y are each independently a 1-10C divalent group selected from the group consisting of optionally branched alkylene, arylene, and cycloalkylene groups) and a sulfur-containing allylcarbonate group; a production method thereof; a (co)polymer of the compound; a polymerizable composition for the optical material, containing the compound, and a cured material thereof; and a formed article for optical material, containing the cured material. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a radical polymerizable compound having a specific dithiocarbonate structure and a sulfur-containing allyl carbonate group, and an optical material having a high refractive index using the radical polymerizable compound.

  Organic glass is lighter than inorganic glass, has excellent impact resistance, and can be easily formed and colored with thermoplastics. As a substitute for inorganic glass, windows for buildings and vehicles, lighting equipment, signs, daily necessities, etc. Has been used. As such organic glass, a diethylene glycol bis (allyl carbonate) polymer represented by CR-39 (trade name: manufactured by PPG), a methyl methacrylate polymer, and the like are typical.

  When a spectacle lens is made of glass, the higher the refractive index of the glass, the thinner the lens can be. However, the refractive index of organic glass is 1.49 to 1.50, and inorganic glass (white crown In the case of glass, it is lower than 1.523). Therefore, when a lens is produced using organic glass, the edge (edge) becomes thicker than when a lens is produced using inorganic glass, and the merit of weight reduction is impaired. Furthermore, when a lens for correcting vision is made of organic glass, there is a drawback that the appearance becomes worse as the degree increases. Under such circumstances, there has been a demand for a resin for optical materials that gives a polymer having a high refractive index.

Various attempts have been made to increase the refractive index of organic glass.
For example, JP-A-63-46213 (Patent Document 1) describes a thiourethane resin obtained by reacting an isocyanate compound and a mercapto compound as an optical resin having a high refractive index. However, the thiourethane-based resin has a problem that the isocyanate compound as a raw material is toxic and a very unpleasant odor peculiar to the raw material thiol compound.

  Furthermore, JP-A-3-217712 (Patent Document 2) describes a (meth) acrylate compound containing a sulfur atom as an optical resin material having a high refractive index. However, since many of these materials have high viscosity and are too reactive, a lot of know-how is required for a storage method as a lens material, and it is not always easy to handle.

  JP-A-2-261808 (Patent Document 3), JP-A-10-175947 (Patent Document 4), and JP-A-11-49744 (Patent Document 5) disclose an optical material that provides a high refractive index. As the resin material, a radical polymerizable compound having a sulfur-containing allyl carbonate group is described. These compounds have a high refractive index and good curability by light. On the other hand, when peroxide is used as the polymerization initiator for the thermosetting reaction, oxidation is likely to occur in the sulfide structure portion in the molecule, and coloring and the like can occur. Problems can occur. In addition, it is difficult to control the polymerization.

JP-A-63-46213 Japanese Patent Laid-Open No. 3-217812 JP-A-2-261808 JP-A-10-175947 JP 11-49744 A

  It is an object of the present invention to provide a radically polymerizable compound that is capable of causing a stable thermosetting reaction and is less colored and an optical material that has high refractive index and excellent transparency using the compound. .

  As a result of intensive studies to solve the above problems, the present inventors have found that a radically polymerizable compound having a specific dithiocarbonate structure and a sulfur-containing allyl carbonate group is stable during thermosetting reaction, less colored, The inventors have found that an optical material having a refractive index and excellent transparency can be obtained, and the present invention has been completed.

That is, the present invention relates to the following [1] to [16].
[1] General formula (1)
(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and X and Y each independently represent an alkylene group, arylene group and cycloalkylene having 1 to 10 carbon atoms which may be branched. Represents a divalent group selected from the group consisting of groups).
[2] The radical polymerizable compound as described in 1 above, wherein X and Y in the general formula (1) are a methylene group, an ethylene group, a 1,2-propylene group or a 1,3-propylene group.
[3] The radically polymerizable compound as described in 1 or 2 above, wherein R ¹ and R ² in the general formula (1) are hydrogen atoms.
[4] General formula (2)
(Wherein L represents a divalent group selected from the group consisting of an alkylene group having 1 to 10 carbon atoms, an arylene group, and a cycloalkylene group, which may be branched), in the presence of a base, General formula (3)
(In the formula, R ⁴ represents a hydrogen atom or a methyl group, and Z represents a chlorine atom or a bromine atom.)
(The symbols in the formula represent the same meaning as described above.) After obtaining the thiol compound represented by the general formula (1), it is further reacted with N, N′-carbonyldiimidazole.
(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and X and Y each independently represent an alkylene group, arylene group and cycloalkylene having 1 to 10 carbon atoms which may be branched. Represents a divalent group selected from the group consisting of groups.).
[5] The method for producing a radical polymerizable compound as described in 4 above, wherein X and Y in the general formula (1) are a methylene group, an ethylene group, a 1,2-propylene group or a 1,3-propylene group.
[6] The method for producing a radically polymerizable compound as described in 4 or 5 above, wherein R ¹ and R ² in the general formula (1) are hydrogen atoms.
[7] A polymer or copolymer comprising the radical polymerizable compound according to any one of 1 to 3 as a kind of raw material monomer.
[8] The copolymer according to 7 above, which is a copolymer of the radical polymerizable compound according to any one of 1 to 3 and another radical polymerizable compound.
[9] The copolymer according to 8 above, which is a copolymer of the radical polymerizable compound according to any one of 1 to 3 above and allyl methacrylate and / or diallyl maleate.
[10] A polymerizable composition for an optical material containing the radical polymerizable compound as described in any one of 1 to 3 above.
[11] The polymerizable composition for an optical material as described in 10 above, which further contains another radical polymerizable compound.
[12] The polymerizable composition for an optical material as described in 11 above, wherein the other radical polymerizable compound is at least allyl methacrylate and / or diallyl maleate.
[13] A cured product of the polymerizable composition for an optical material according to any one of 10 to 12 above.
[14] A molded article for an optical material comprising the cured product as described in 13 above.
[15] The molded article for an optical material as described in 14 above, 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 lens formed by curing the polymerizable composition for an optical material as described in any one of 10 to 12 above.

  The composition for optical materials using the radical polymerizable compound of the present invention has a high refractive index of the cured product, excellent transparency, and little coloring during the thermosetting reaction. For this reason, it is particularly useful for optical materials such as optical lenses such as eyeglass lenses and camera lenses, optical waveguides, optical sealants, optical adhesives, optical films, prisms, light guide plates for liquid crystal panels, and optical fibers.

Hereinafter, the present invention will be described in more detail.
[Radically polymerizable compound having a dithiocarbonate structure and a sulfur-containing allyl carbonate group]
The radical polymerizable compound having a dithiocarbonate structure and a sulfur-containing allyl carbonate group of the present invention has the following general formula (1).
It is a compound shown by these. Hereinafter, it may be referred to as “radical polymerizable compound of the present invention”.
In the present specification, when the chemical formula and the compound name do not match, the chemical formula takes precedence.

In the general formula (1), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. Among these, a hydrogen atom is more preferable from the viewpoint of increasing the refractive index.

  In General Formula (1), X and Y each independently represent a divalent group selected from the group consisting of an alkylene group, an arylene group, and a cycloalkylene group, which may be branched, having 1 to 10 carbon atoms.

Specific examples of the alkylene group include methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, butylene group, amylene group, hexylene group and the like.
Examples of the arylene group include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a toluylene group, a naphthalenylene group, and a biphenylene group.
Examples of the cycloalkylene group include 1,3-cyclopentylene group, 1,2-cyclopentylene group, 1,1-cyclopentylene group, 1,4-cyclohexylene group, 1,3-cyclohexylene group, 1 , 2-cyclohexylene group, 1,1-cyclohexylene group and the like.

  Among these, as X and Y, an alkylene group having 1 to 4 carbon atoms and a cycloalkylene group having 6 to 10 carbon atoms are more preferable. From the viewpoint of achieving both a refractive index and an Abbe number, a methylene group, an ethylene group, A 2-propylene group and a 1,3-propylene group are particularly preferable.

  As the radically polymerizable compound represented by the general formula (1), S, S′-bis [2- (allyloxycarbonylthio) ethyl] dithiocarbonate is particularly preferable.

The radically polymerizable compound for optical materials described in the above-mentioned section of the prior art contains a sulfide skeleton (—CH ₂ —S—CH ₂ —) containing a sulfur atom in order to improve the refractive index. However, this structure has a problem in stability during curing, because sulfur atoms are easily oxidized, coloring occurs during polymerization and curing reaction, and curing is incomplete due to deactivation of the polymerization initiator. .
On the other hand, the radically polymerizable compound of the present invention, dithiocarbonate structure as sulfur-containing group (-S- (C = O) -S- ) and sulfur-containing allylcarbonate structure ^{_{(CH 2 = CR 3 -CH 2}} -O- ( C═O) —S— (R ³ represents R ¹ or R ² )). Since this structure makes it difficult for the sulfur atom to be oxidized by disposing a carbonyl having an electron-withdrawing property next to the sulfur atom, coloring does not occur during the polymerization or the curing reaction, and is stable.

[Production method]
Next, the manufacturing method of the radically polymerizable compound which has the dithiocarbonate structure shown by General formula (1) of this invention and a sulfur-containing allyl carbonate group is demonstrated.
The radical polymerizable compound having a dithiocarbonate structure and a sulfur-containing allyl carbonate group represented by the general formula (1) is 1. After reacting dithiol with a halogenated formate (meth) allyl in the presence of a base, 2. It can be produced by reacting with N, N′-carbonyldiimidazole.
In the present specification, “(meth) allyl” means “methallyl and / or allyl”, and “(meth) acrylate” means “methacrylate and / or acrylate”.

1. Reaction of dithiol with halogenated formate (meth) allyl in the presence of a base The dithiol used in the present invention is represented by the general formula (2)
(Wherein L represents a divalent group selected from the group consisting of an alkylene group having 1 to 10 carbon atoms, an arylene group, and a cycloalkylene group), and a halogenated compound. Formic acid (meth) allyl is represented by the general formula (3)
(Wherein R ⁴ represents a hydrogen atom or a methyl group, and Z represents a chlorine atom or a bromine atom).

These two compounds are reacted in the presence of a base to give a general formula (4)
(The symbols in the formula represent the same meaning as described above.) A thiol compound (hereinafter sometimes referred to as “thiol compound (4)”) is obtained.
Z in the general formula (3) is preferably a chlorine atom from the viewpoint of achieving both reactivity and economy, and L in the general formula (4) is a compound represented by the general formula (1). Select according to X and Y in the middle.

  The amount of the dithiol represented by the general formula (2) and the halogenated formate (meth) allyl represented by the general formula (3) is not particularly limited. It is preferable to use 0.1 to 1.5 moles of (meth) allyl, particularly preferably 0.5 to 1.1 moles. When the halogenated formic acid (meth) allyl is less than 0.1 mol, the reaction yield with respect to dithiol is low, and when it exceeds 1.5 mol, the amount of by-products increases.

This reaction can be carried out using either a method in which the by-product hydrogen halide is removed from the reaction system in the absence of a catalyst, or a method in which a hydrogen halide scavenger is added.
Examples of the hydrogen halide scavenger include pyridine, triethylamine, picoline, dimethylaniline, diethylaniline, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] undeca. Examples include organic bases such as -7-ene, and inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, and sodium bicarbonate.
Although there is no restriction | limiting in particular as the usage-amount of a hydrogen halide scavenger, 0.1-1.5 mol is preferable with respect to 1 mol of said dithiols, and 0.5-1.1 mol is especially preferable.

  In addition, the reaction may be performed without a solvent, or may be performed using a solvent that does not react with the substrate. It can also be carried out without problems even in the presence of water. Solvents include hydrocarbon solvents such as n-hexane, toluene, xylene and benzene, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and butyl acetate, diethyl ether, diethylene glycol dimethyl ether, Examples include ether solvents such as tetrahydrofuran and tetrahydropyran, halogen solvents such as dichloromethane, dichloroethane, chloroform and chlorobenzene, and polar solvents such as acetonitrile, N, N-dimethylformamide and dimethyl sulfoxide. These solvents may be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular in reaction temperature, Usually, the range of -30-100 degreeC is preferable, and 0-50 degreeC is especially preferable. If it is less than −30 ° C., the reaction becomes extremely slow, and if it exceeds 100 ° C., side reactions such as polymerization of the intermediate thiol compound by ene-thiol reaction tend to occur.

Regarding the reaction, a polymerization inhibitor may be added to suppress polymerization.
Polymerization inhibitors include p-benzosoquinone, naphthoquinone, quinones such as 2,5-diphenyl-p-benzoquinone, polyhydric phenols such as hydroquinone, pt-butylcatechol, 2,5-di-t-butylhydroquinone And phenols such as hydroquinone monomethyl ether, di-t-butylparacresol, and α-naphthol.
The thiol compound (4) thus obtained can be purified by treatment using distillation, liquid separation, recrystallization, chromatography, activated carbon, activated clay, synthetic adsorbent and the like.

2. 1 above. Reaction of the thiol compound (4) produced by the reaction of N with N, N′-carbonyldiimidazole. The method for producing the radically polymerizable compound represented by the general formula (1) of the present invention by reacting the thiol compound (4) produced in the above with N, N′-carbonyldiimidazole will be described in detail.

  Although the usage-amount of a thiol compound (4) and N, N'- carbonyldiimidazole is not specifically limited, Usually, 0.1 to 0 N, N'- carbonyldiimidazole is used with respect to 1 mol of thiol compounds. 0.7 mol is preferably used, and 0.3 to 0.5 mol is particularly preferable. When the amount of N, N′-carbonyldiimidazole is less than 0.1 mol, the reaction yield relative to the thiol compound (4) is low, and when the amount exceeds 0.7 mol, the amount of by-products increases.

This reaction can be carried out in the presence of a base and in the absence of a base.
When this reaction is carried out in the presence of a base, examples of the base used include methylamine, dimethylamine, triethylamine, pyridine, picoline, aniline, dimethylaniline, diethylaniline, toluidine, anisidine, 1,4-diazabicyclo [2.2. .2] Organic bases such as octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), or sodium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, hydroxide Examples include inorganic bases such as sodium, potassium hydroxide, calcium hydroxide, and magnesium oxide.

  Although there is no restriction | limiting in particular as the usage-amount of such a base, 0.1-5 mol is preferable with respect to 1 mol of thiol compounds (4), 0.5-3 mol is still more preferable, 0.8-1. Two moles are particularly preferred.

The reaction can be carried out without solvent or in an inert solvent.
Such a solvent is not particularly limited as long as it is inert to the reaction. Specific examples include hydrocarbon solvents such as n-hexane, benzene, toluene, xylene, methanol, ethanol, isopropanol. Alcohol solvents such as n-butanol, methoxyethanol, ethoxyethanol, butoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ketone solvents such as acetone, methyl ethyl ketone or methyl isobutyl ketone, ethyl acetate or butyl acetate Ester solvents such as diethyl ether, diethylene glycol dimethyl ether, ether solvents such as tetrahydrofuran or dioxane, dichloromethane, Halogen solvents such as form, carbon tetrachloride, 1,2-dichloroethane, tetrachloroethylene, chlorobenzene, o-dichlorobenzene, acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone And polar solvents such as dimethyl sulfoxide and sulfolane. These solvents may be used alone or in combination of two or more.

  There is no restriction | limiting in particular in reaction temperature, Usually, the range of -78-150 degreeC is preferable, the range of -20-120 degreeC is further more preferable, and the range of 0-100 degreeC is especially preferable.

  The reaction of the above-described thiol compound (4) with N, N′-carbonyldiimidazole produces the intermediate thiol compound (4) produced by the reaction between the first-stage dithiol and halogenated formate (meth) allyl. Once taken out, it may be carried out by a stepwise method in which the second stage carbonylation reaction is carried out, or the next carbonylation reaction may be carried out in one stage without taking out the thiol compound (4) in the middle. Good.

  When adopting a stepwise method, the thiol compound (4), which is an intermediate in the first step reaction, is further obtained by a known method (for example, distillation, recrystallization, chromatography, activated carbon treatment, etc.) as necessary. You may isolate | separate and refine | purify and you may isolate as a higher purity compound.

A polymerization inhibitor may be used in order to prevent the thiol compound (4) as an intermediate from causing an ene-thiol reaction and polymerizing during the production of the radical polymerizable compound of the present invention.
Examples of the polymerization inhibitor that can be used include various known compounds such as 4-methoxyphenol, 2,6-di-tert-butylcresol, hydroquinone, and phenothiazine.

  Although there is no restriction | limiting in particular in the usage-amount of these polymerization inhibitors, 0.001-5 mass parts is preferable normally with respect to 100 mass parts of raw material mixtures or reaction products in a reaction system, and 0.05-3 mass parts is More preferably, 0.01-1 mass part is especially preferable.

  After completion of the reaction, the radically polymerizable compound represented by the general formula (1) of the present invention, which is a product, is a known operation or treatment method (for example, neutralization, solvent extraction, water washing, liquid separation, solvent distillation, etc.) Isolated by post-treatment.

[Polymer of radically polymerizable compound of 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. Moreover, it can also be set as the copolymer with another radically polymerizable compound.
The radically polymerizable compound represented by the general formula (1) is bifunctional in the sense that there are two polymerizable double bonds, and forms a crosslinked structure even in homopolymerization (curing reaction), but the physical properties of the homopolymer For example, for the purpose of improving the balance between the refractive index and the Abbe number, it can also be copolymerized with other radical polymerizable compounds. When the radically polymerizable compound to be copolymerized has a polyfunctional radically polymerizable property, a cured product having a higher crosslinking density can be obtained.
Moreover, you may use a monofunctional radically polymerizable monomer in order to reduce the viscosity of a polymer and to improve a moldability.

  The radical polymerizable compound to be copolymerized with the radical polymerizable compound of the present invention is not particularly limited as long as it is a compound copolymerizable with the radical polymerizable compound of the general formula (1). Specific examples thereof include di (meth) allyl phthalate, di (meth) allyl isophthalate, di (meth) allyl terephthalate, (meth) allyl benzoate, α-naphthoic acid (meth) allyl, β-naphthoic acid (meth). Allyl, 2-phenylbenzoic acid (meth) allyl, 3-phenylbenzoic acid (meth) allyl, 4-phenylbenzoic acid (meth) allyl, o-chlorobenzoic acid (meth) allyl, m-chlorobenzoic acid (meth) Allyl, p-chlorobenzoic acid (meth) allyl, o-bromobenzoic acid (meth) allyl, m-bromobenzoic acid (meth) allyl, p-bromobenzoic acid (meth) allyl, 2,6-dichlorobenzoic acid ( (Meth) allyl, 2,4-dichlorobenzoic acid (meth) allyl, 2,4,6-tribromobenzoic acid (meth) allyl, 1,4-cyclohexanedicarbo Di (meth) allyl acid, di (meth) allyl 1,3-cyclohexanedicarboxylate, di (meth) allyl 1,2-cyclohexanedicarboxylate, di (meth) allyl 1-cyclohexene-1,2-dicarboxylate, 3-methyl-1,2-cyclohexanedicarboxylic acid di (meth) allyl, 4-methyl-1,2-cyclohexanedicarboxylic acid di (meth) allyl, endic acid di (meth) allyl, chlorendic acid di (meth) allyl , 3,6-methylene-1,2-cyclohexanedicarboxylic acid di (meth) allyl, trimellitic acid tri (meth) allyl, pyromellitic acid tetra (meth) allyl, diphenic acid di (meth) allyl, succinic acid di ( Allyl esters such as (meth) allyl and di (meth) allyl adipate; dibenzyl malate, dibenzyl fumarate, dipheny Maleic acid diesters / fumaric acid diesters such as malate, diphenyl fumarate, dibutyl malate, dibutyl fumarate, dimethoxyethyl maleate, dimethoxyethyl fumarate; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl ( (Meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, benzyl (meth) Acrylate, isobornyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexa Diol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclode (Meth) acrylic acid ester such as candimethanol di (meth) acrylate, ethoxylated cyclohexanedimethanol dimethacrylate, adamantyl (meth) acrylate, etc. Ter; aromatic vinyl compounds such as styrene, α-methylstyrene, methoxystyrene, divinylbenzene; vinyls of aliphatic carboxylic acids such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl stearate, vinyl caproate Esters; cycloaliphatic carboxylic acid vinyl esters and other alicyclic vinyl esters; benzoic acid vinyl esters and t-butyl benzoic acid vinyl esters and other aromatic vinyl esters; diallyl carbonate, diethylene glycol bisallyl carbonate, trade name CR-39 manufactured by PPG Allyl carbonate compounds such as polyethylene glycol bis (allyl) carbonate typified by: having a (meth) allyl ester group at the end and an ester structure derived from a polyvalent carboxylic acid and a polyhydric alcohol Ligomer; (meth) acrylic acid (meth) allyl, vinyl (meth) acrylate and di (meth) allyl maleate having polymerizable double bonds with different reactivity in the molecule; triallyl isocyanurate and cyanuric acid And nitrogen-containing polyfunctional allyl compounds such as triallyl.

  However, these radically polymerizable compounds are merely examples and are not limited to the above. These radically polymerizable compounds may be used in combination of two or more in order to obtain the desired physical properties.

  Among these radically polymerizable compounds, 1,4-cyclohexanedicarboxylic acid di (meth) allyl, trimethylolpropane tri (meth) acrylate, di (meth) allyl isophthalate from the viewpoint of achieving both a refractive index and an Abbe number. , Di (meth) allyl terephthalate, trimellitic acid tri (meth) allyl, pyromellitic acid tetra (meth) allyl, (meth) allyl ester group at the end, derived from polycarboxylic acid and polyhydric alcohol An oligomer having an ester structure is preferable.

  Moreover, the compound which has the radically polymerizable double bond in which reactivity differs, such as (meth) acrylic acid (meth) allyl, (meth) acrylic acid vinyl, and maleic acid di (meth) allyl, is also preferable. These compounds are useful in controlling the degree of curing during curing molding by radical polymerization from the difference in reactivity.

  When polymerizing the radically polymerizable compound of the present invention, thermal polymerization may be performed without using an initiator, but it is preferable to use a radical polymerization initiator. Any radical polymerization initiator that generates radicals by heat, ultraviolet rays, electron beams, radiation, or the like can be used. A thermal radical polymerization initiator and a polymerization initiator by radiation or the like may be used in combination.

  Examples of the thermal radical polymerization initiator include azo compounds such as 2,2′-azobisisobutyronitrile, 2,2′-azobisisovaleronitrile, dimethyl-2,2′-azobisisobutyrate; methyl ethyl ketone Ketone peroxides such as peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide; diacyl peroxides such as benzoyl peroxide, decanoyl peroxide, lauroyl peroxide; dicumyl peroxide, t-butylcumyl peroxide, Dialkyl peroxides such as di-t-butyl peroxide; 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-di-t-butylperoxycyclohexane Peroxyketals such as 2,2-di (t-butylperoxy) butane; t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, Di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate, t-butylperoxy-3,5,5-trimethylhexanoate, t-hexylperoxy-2-ethylhexanoate 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, di-t-butylperoxytrimethyladipate, t-hexylper Oxyisopropyl monocarbonate, t-butyl peroxylaurate, t-hexyl par Alkyl peroxyesters such as xylbenzoate; peroxycarbonates such as diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, t-butylperoxyisopropyl carbonate, and the like, but are not limited thereto. Do not mean. Two or more of these thermal radical polymerization initiators may be used in combination.

  Examples of radical polymerization initiators by ultraviolet rays, electron beams, and radiation include, for example, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, 1-hydroxy-cyclohexyl-phenylketone, 2-methyl-1- [4 -(Methylthio) phenyl] -2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-hydroxy-2-methyl-1-phenyl- Acetophenone derivatives such as propan-1-one; benzophenone derivatives such as benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4-trimethylsilylbenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide; benzoin, benzoin ethyl ether Ben Benzoin derivatives such as inpropyl ether, benzoin isobutyl ether, benzoin isopropyl ether; methylphenylglyoxylate, benzoin dimethyl ketal, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and the like, but are not limited thereto Absent. These ultraviolet rays, electron beams, and radiation radical polymerization initiators may be used in combination of two or more.

  The amount of these polymerization initiators to be added varies depending on the curing temperature, the composition ratio of the radically polymerizable composition, the type and amount of the additive, and cannot be generally limited. However, the radical of the general formula (1) of the present invention is not limited. 0.01-15 mass parts is preferable with respect to 100 mass parts of total amounts of a polymeric compound and the other radically polymerizable compound copolymerized as needed, and 0.1-10 mass parts is especially preferable. When the addition amount of the radical polymerization initiator is less than 0.01 parts by mass, polymerization and curing may be insufficient. Moreover, it is economically unpreferable to add exceeding 15 mass parts.

The polymerization temperature (curing temperature) may be appropriately selected according to the type of polymerization initiator. Polymerization with ultraviolet rays or the like is possible even at room temperature. In the case of thermal polymerization, it is desirable to appropriately determine the temperature corresponding to the decomposition temperature of the initiator, and it is generally 30 to 130 ° C. Alternatively, polymerization (curing) may be performed by changing the temperature stepwise. An inert solvent can also be used in the polymerization.
The resin obtained by polymerization of the radical polymerizable compound represented by the general formula (1) of the present invention has high transparency and is useful as a resin for optical materials having a high refractive index.

[Composition for optical materials]
The composition for optical materials of the present invention and the cured product thereof contain the radical polymerizable compound represented by the general formula (1) described above, and the compound of the general formula (1) is homopolymerized or other radical polymerization. The composition copolymerized with the functional compound is cured to obtain a cured product. Moreover, you may contain a radical polymerization initiator etc. as needed.
When the radically polymerizable compound to be copolymerized is polyfunctional, the crosslinking density can also be adjusted.
The radical polymerizable compound, radical polymerization initiator, and polymerization (curing) method to be copolymerized are as described above. However, since there is a problem of removal from the cured product, it is preferable not to use a solvent.

  The blending amount in the composition when the radical polymerizable compound of the present invention and other radical polymerizable compound are copolymerized is not particularly limited, but preferably contains 60% by mass or more of the radical polymerizable compound of the present invention, 75 The mass% or more is more preferable.

  In either case of homopolymerization or copolymerization, if the curing method is cast curing, a monofunctional radically polymerizable monomer is appropriately added as a reactive diluent to reduce the viscosity and facilitate injection into the mold. As a result, the viscosity can be adjusted. The viscosity is preferably 600 mPa · s or less, more preferably 300 mPa · s or less, and particularly preferably 200 mPa · s or less at the temperature when pouring into the mold. The viscosity is a value measured according to JIS Z8803. Examples of the monofunctional radical polymerizable monomer include monofunctional monomers among the compounds exemplified above as the radical polymerizable compound to be copolymerized with the radical polymerizable compound of the present invention.

  The composition for optical materials of the present invention uses various known additives such as ultraviolet absorbers, antioxidants, mold release agents, colorants (pigments, dyes), flow regulators, leveling agents, inorganic fillers and the like. It is also possible to do.

  Specific examples of the ultraviolet absorber include triazoles such as 2- (2′-hydroxy-tert-butylphenyl) benzotriazole, benzophenones such as 2,4-dihydroxybenzophenone, 4-tert-butylphenyl salicylate, etc. And hindered amines such as bis- (2,2,6,6-tetramethyl-4-piperidinyl) seba sheet, but are not limited thereto.

  The blending amount of the ultraviolet absorber varies depending on the type and amount of other blends, but is generally 0.01 to 2 with respect to 100 parts by weight of all radical polymerizable components in the composition for optical materials. Mass parts are preferred, 0.03 to 1.7 parts by mass are more preferred, and 0.05 to 1.4 parts by mass are most preferred. If the ultraviolet absorber is less than 0.01 parts by mass, a sufficient effect cannot be expected, and if it exceeds 2 parts by mass, it is economically undesirable.

  Antioxidants include 2,6-di-tert-butyl-4-methylphenol, tetrakis- [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane, etc. Examples thereof include sulfur-based antioxidants such as phenolic, dilauryl-3,3′-thiodipropionate, and phosphorus-based antioxidants such as trisnonylphenyl phosphite, but are not limited thereto.

  The compounding amount of the antioxidant varies depending on the type and amount of the other compound, but generally 0.01 to 5 parts per 100 parts by mass of all radical polymerizable components in the composition for optical materials. Mass parts are preferred, 0.05 to 4 parts by mass are more preferred, and 1 to 3 parts by mass are most preferred. If the antioxidant is less than 0.01 parts by mass, a sufficient effect cannot be expected, and if it exceeds 5 parts by mass, it is economically undesirable.

Examples of the release agent include, but are not limited to, stearic acid, butyl stearate, zinc stearate, stearic acid amide, fluorine compounds, silicon compounds, and the like.
The compounding amount of the release agent varies depending on the type and amount of the other compound, but is generally 0.01 to 2 with respect to 100 parts by mass of all radical polymerizable components in the composition for optical materials. Mass parts are preferred, 0.03 to 1.7 parts by mass are more preferred, and 0.05 to 1.4 parts by mass are most preferred. If the release agent is less than 0.01 parts by mass, a sufficient effect cannot be expected, and if it exceeds 2 parts by mass, it is economically undesirable, and problems such as stickiness on the surface of the cured product may occur.

  Colorants include anthraquinone, azo, carbonium, quinoline, quinoneimine, indigoid, phthalocyanine and other organic pigments, azoic dyes, sulfur dyes and other organic dyes, titanium yellow, yellow iron oxide, zinc yellow, Inorganic pigments such as chrome orange, molybdenum red, cobalt violet, cobalt blue, cobalt green, chromium oxide, titanium oxide, zinc sulfide, and carbon black can be exemplified, but are not limited thereto. Moreover, the compounding quantity is not specifically limited.

  Cast molding is suitable when the optical material composition of the present invention is molded into an optical material such as a plastic lens. Specific examples include a method in which a radical polymerization initiator is added to the composition, injected into a mold fixed with an elastomer gasket or a spacer through a tube or pipe, and cured by heat in an oven.

  The mold used is preferably made of metal or inorganic glass. In general, the mold after casting the plastic lens needs to be washed with a strong acid or a strong alkali solution. Therefore, an inorganic glass mold is particularly preferably used because it does not change in quality due to washing and is easily polished to obtain a flat surface.

The curing temperature at the time of molding the composition for optical materials of the present invention into a plastic lens or the like varies depending on the composition ratio of the composition, the type and amount of the additive, but is generally about 20 to 150 ° C., preferably 30. ~ 120 ° C.
Moreover, about the operation of hardening temperature, when the shrinkage | contraction and distortion at the time of hardening are considered, the method of hardening gradually while raising temperature is preferable. In general, the curing should be performed for 0.5 to 100 hours, preferably 3 to 50 hours, more preferably 10 to 30 hours.

  Moreover, the optical material molded body obtained by curing the composition for optical materials of the present invention can be subjected to various coating treatments as necessary. For example, a high-hardness film can be formed on a molded body using a coating liquid containing fine inorganic substances such as an organosilicon compound, tin oxide, silicon oxide, zirconium oxide, and titanium oxide in order to improve scratch resistance. In order to improve impact resistance, a primer layer mainly composed of polyurethane or polyester can be provided. In order to impart antireflection performance, an antireflection film can also be applied using silicon oxide, titanium oxide, zirconium oxide, tantalum oxide, or the like. In order to improve water repellency, a water repellent film can be formed on the antireflection film using an organosilicon compound having a fluorine atom.

[Optical materials]
Cured products of the composition for optical materials of the present invention are optical lenses such as spectacle lenses and camera lenses, optical waveguides, optical sealants, optical adhesives, optical films, prisms, light guide plates for liquid crystal panels, optical fibers, and transparent It can be used as an optical material for panels, transparent films, transparent plates and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention does not receive any limitation by these description.

Various physical properties of the materials synthesized in Examples and Comparative Examples were measured as follows.
1. Refractive index (n _D ) and Abbe number (ν _D )
Model used: Abbe refractometer 1T type (manufactured by Atago Co., Ltd.)
Measurement method: A test piece of 9 mm × 16 mm × 4 mm was prepared, and the refractive index (n _D ) and Abbe number (ν _D ) at 25 ° C. were measured using “Abbe refractometer 1T”. Diiodomethane was used as the contact liquid.

2. ¹ H-NMR, ¹³ C-NMR
Model used: JEOL EX-400 (400 MHz, manufactured by JEOL Ltd.)
Measurement method: Dissolved in deuterated chloroform and measured using tetramethylsilane as internal standard substance.

3. FT-IR
Model used: Spectrum GX (manufactured by PerkinElmer),
Measurement method: Measured by a liquid film method using a KBr plate.

4). Barcol hardness Measured according to JIS K6911 using a GYZJ934-1 type manufactured by Barber Coleman.

Example 1 Synthesis of S, S′-bis [2- (allyloxycarbonylthio) ethyl] dithiocarbonate (abbreviated as BADTC)

  Sodium hydroxide (8.07 g, 0.20 mol) was added to a three-necked flask equipped with a thermometer, a dropping funnel, and a stirring bar, and completely dissolved with 80.7 g of pure water, and further 24.0 ml of toluene was added. This flask was immersed in an ice bath, the temperature in the system was adjusted to 10 ° C. or lower, and ethanedithiol (chemical formula (6), manufactured by Tokyo Chemical Industry Co., Ltd., 19.00 g, 0.20 mol) was slowly added while stirring. After stirring for 20 minutes, a solution obtained by diluting allyl chloroformate (chemical formula (5), Tokyo Kasei Kogyo Co., Ltd., 24.36 g, 0.20 mol) with 24.0 ml of toluene was charged into a dropping funnel, and this was added to the ethanedithiol solution. Was added dropwise over 1 hour. After completion of dropping, the temperature in the system was kept at 10 ° C. or lower and stirred for 1 hour. The reaction solution was transferred to a separatory funnel, and a liquid separation operation was performed. Further, the toluene layer was repeatedly washed with water until the pH of the aqueous layer reached 7. The obtained toluene layer was dried over anhydrous sodium sulfate, sodium sulfate was removed by filtration operation, and a toluene solution of dehydrated O-allyl-S- (2-mercaptoethyl) thiocarbonate (compound of formula (7)) was obtained. Got.

  Separately, a three-necked flask equipped with a thermometer, a dropping funnel, a Dimroth condenser, and a stirrer was purged with nitrogen, and the previously obtained toluene solution was charged therein. Thereafter, the flask is immersed in an ice bath, the temperature of the contents is adjusted to 10 ° C. or lower, and N, N′-carbonyldiimidazole (chemical formula (8), manufactured by Hodogaya Chemical Co., Ltd., 16.4 g, 0.10 mol) is added to N. , N-dimethylformamide (DMF) in 115.0 ml was added dropwise from a dropping funnel over 1 hour.

  Thereafter, the temperature in the system was kept at 10 ° C. or lower and stirred for 3 hours, 50 ml of pure water was added to the reaction solution, transferred to a separatory funnel, and separated. The obtained organic layer was further treated in the order of 15 ml of 5% aqueous sodium hydroxide solution, 50 ml of pure water and 15 ml of 5% hydrochloric acid, and finally washed with pure water until the aqueous layer became neutral. The collected organic layer was dried over anhydrous sodium sulfate and filtered to remove sodium sulfate. Low boiling point substances were distilled off under reduced pressure to obtain 37.6 g of a crude product. Further, the crude product was purified by column chromatography using a mixed solvent of hexane and ethyl acetate as a developing solvent to obtain a colorless transparent liquid (yield: 21.4 g, yield: 56.0%).

¹ H-NMR, ¹³ C-NMR and IR of this liquid are measured, and the target compound is S, S′-bis [2- (allyloxycarbonylthio) ethyl] dithiocarbonate (chemical formula (9)). It was confirmed. The results of ¹ H-NMR, ¹³ C-NMR and IR are shown in FIGS.

Example 2: Curing reaction of BADTC BADTC (2.500 g) obtained in Example 1 was added to 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane as a radical polymerization initiator. (Nippon Yushi Co., Ltd., trade name: Perhexa TMH, 0.010 g) was added and poured into a 4 mm thick mold consisting of two glass plates and a silicon tube as a spacer. Curing temperature program in which this is put in an oven, heated at 70 ° C. for 7 hours, then heated to 90 ° C. over 10 hours, further heated to 120 ° C. over 3 hours, and then heated at 120 ° C. for 2 hours. And heat cured.
The physical properties (refractive index, Abbe number and Barcol hardness) of the colorless and transparent cured product obtained as a result were measured. Table 1 shows the resin composition, and Table 2 shows the measurement results of the physical properties.

Example 3: Curing of copolymer composition of BADTC and trimethylolpropane trimethacrylate BADTC (2.375 g) obtained in Example 1 and trimethylolpropane trimethacrylate (Tokyo Chemical Industry Co., Ltd., 0.125 g) T-hexyl peroxy-2-ethylhexanoate (manufactured by NOF Corporation, trade name: Perhexyl O, 0.075 g) and perhexa TMH (0.025 g) were added to the mixture of Thermal curing was performed with the same mold and curing temperature program as in Example 1.
The physical properties of the colorless and transparent cured product obtained as a result were measured. Table 1 shows the resin composition, and Table 2 shows the measurement results of the physical properties.

Example 4: Curing of BADTC and diallyl isophthalate copolymer composition A mixture of BADTC (1.803 g) and diallyl isophthalate (0.203 g) obtained in Example 1 is a radical polymerization initiator. 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (Nippon Yushi Co., Ltd., trade name: Perocta O, 0.061 g) and Perhexa TMH (0.020 g) were added, Poured into a 4 mm thick mold consisting of a glass plate and a silicon tube as a spacer. This was put in an oven, heated from 60 ° C. to 120 ° C. over 16 hours, and heat-cured with a curing temperature program of heating for 2 hours.
The physical properties of the colorless and transparent cured product obtained as a result were measured. Table 1 shows the resin composition, and Table 2 shows the measurement results of the physical properties.

Example 5: Curing of copolymer composition of BADTC and diallyl 1,4-cyclohexanedicarboxylate BADTC (1.807 g) obtained in Example 1 and diallyl 1,4-cyclohexanedicarboxylate (0.202 g) Perocta O (0.066 g) and Perhexa TMH (0.020 g) were added to this mixture and heat cured using the same mold and curing temperature program as in Example 4.
The physical properties of the colorless and transparent cured product obtained as a result were measured. Table 1 shows the resin composition, and Table 2 shows the measurement results of the physical properties.

Example 6: Curing of copolymer composition of BADTC and isobornyl methacrylate BADTC (1.907 g) obtained in Example 1 and isobornyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: LIGHT ESTER IB-X, Perocta O (0.065 g) and Perhexa TMH (0.023 g) were added to the mixture with 0.105 g) and heat cured using the same mold and curing temperature program as in Example 4.
The physical properties of the colorless and transparent cured product obtained as a result were measured. Table 1 shows the resin composition, and Table 2 shows the measurement results of the physical properties.

Example 7: Curing of copolymer composition of BADTC and dicyclopentanyl methacrylate BADTC (1.900 g) obtained in Example 1 and dicyclopentanyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., trade name: FA-513M) , 0.101 g), Perocta O (0.064 g) and Perhexa TMH (0.023 g) were added and heat cured using the same mold and curing temperature program as in Example 4.
The physical properties of the colorless and transparent cured product obtained as a result were measured. Table 1 shows the resin composition, and Table 2 shows the measurement results of the physical properties.

Example 8: Curing of copolymer composition of BADTC and allyl ester oligomer-1 BADTC (1.801 g) obtained in Example 1 and allyl ester oligomer-1 {mixture of the following chemical formula (10), n = 0 Perocta O (0.064 g) and perhexa TMH (0.029 g) were added to a mixture of (monomer) 40 mass%, n = 1 or more 60 mass%} (0.206 g), and the same as in Example 4 Thermal curing was performed using a mold and curing temperature program.
The physical properties of the colorless and transparent cured product obtained as a result were measured. Table 1 shows the resin composition, and Table 2 shows the measurement results of the physical properties.

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 isophthalate, 154.5 g (2.03 mol) of propylene glycol, and 1.50 g of dibutyltin oxide and heated at 180 ° C. in a nitrogen stream. The allyl alcohol produced was distilled off. When about 140 g of allyl alcohol was distilled, the pressure in the reaction system was reduced to 1.33 kPa to increase the allyl alcohol distillation rate. After the theoretical amount (235.9 g) of allyl alcohol was distilled off, and further maintained at 180 ° C./0.13 kPa for 1 hour, the reactor was cooled to obtain 1420.1 g of allyl ester oligomer-1.

Example 9: Curing of copolymer composition of BADTC and allyl ester oligomer-2 BADTC (1.802 g) obtained in Example 1 and allyl ester oligomer-2 {mixture of the following chemical formula (11), n = 0 Perocta O (0.064 g) and Perhexa TMH (0.021 g) were added to a mixture of (monomer) 45 mass%, n = 1 or more 55 mass%} (0.203 g), and the same as in Example 4 Thermal curing was performed using a mold and curing temperature program.
The physical properties of the colorless and transparent cured product obtained as a result were measured. Table 1 shows the resin composition, and Table 2 shows the measurement results of the physical properties.

Allyl ester oligomer-2 was produced as follows.
A 3-liter three-necked flask equipped with a distillation apparatus was charged with 1500.0 g (5.95 mol) diallyl 1,4-cyclohexanedicarboxylate, 177.3 g (1.32 mol) trimethylolpropane, and 1.50 g dibutyltin oxide, and a nitrogen stream. The allyl alcohol produced by heating at 180 ° C. was distilled off. When about 138 g of allyl alcohol was distilled, the pressure inside the reaction system was reduced to 1.33 kPa to increase the allyl alcohol distillation rate. After the theoretical amount (230.2 g) of allyl alcohol was distilled off, the mixture was further maintained at 180 ° C./0.13 kPa for 1 hour, and then the reactor was cooled to obtain 1448.5 g of allyl ester oligomer-2.

Example 10: Curing of copolymer composition of BADTC and allyl ester oligomer-3 BADTC (1.808 g) obtained in Example 1 and allyl ester oligomer-3 {mixture represented by the following chemical formula (12) n = Perocta O (0.061 g) and Perhexa TMH (0.022 g) were added to a mixture of 0 (monomer) 40 mass%, n = 1 or more 60 mass%} (0.212 g), and Example 4 Heat cured using the same mold and cure temperature program.
The physical properties of the colorless and transparent cured product obtained as a result were measured. Table 1 shows the resin composition, and Table 2 shows the measurement results of the physical properties.

Allyl ester oligomer-3 was produced as follows.
In a 3-liter three-necked flask equipped with a distillation apparatus, diallyl isophthalate 1500 g (6.09 mol), 2,2-bis [4- (2-hydroxyethoxy) -3,5-dibromophenyl] propane 554.7 g (0.88 mol) ), 1.50 g of dibutyltin oxide was charged, and allyl alcohol formed by heating at 180 ° C. under a nitrogen stream was distilled off. When about 61 g of allyl alcohol was distilled off, the pressure in the reaction system was reduced to 1.33 kPa to increase the distillation rate of allyl alcohol. After the theoretical amount (102.0 g) of allyl alcohol was distilled off, the mixture was further maintained at 180 ° C./0.13 kPa for 1 hour, and then the reactor was cooled to obtain 1954.2 g of allyl ester oligomer-3.

Example 11: Curing of copolymer composition of BADTC and triallyl trimellitic acid BADTC (1.907 g) obtained in Example 1 and triallyl trimellitic acid (manufactured by Wako Pure Chemical Industries, Ltd., 0.103 g) Perocta O (0.061 g) and Perhexa TMH (0.022 g) were added to the mixture and heat cured using the same mold and cure temperature program as in Example 4.
The physical properties of the colorless and transparent cured product obtained as a result were measured. Table 1 shows the resin composition, and Table 2 shows the measurement results of the physical properties.

Example 12: Curing of copolymer composition of BADTC and triallyl isocyanurate To a mixture of BADTC (1.803 g) obtained in Example 1 and triallyl isocyanurate (Wako Pure Chemical Industries, 0.201 g) Perocta O (0.061 g) and Perhexa TMH (0.025 g) were added and heat cured using the same mold and curing temperature program as in Example 4.
The physical properties of the colorless and transparent cured product obtained as a result were measured. Table 1 shows the resin composition, and Table 2 shows the measurement results of the physical properties.

Example 13: Curing of BADTC and diallyl maleate copolymer composition To a mixture of BADTC (1.806 g) and diallyl maleate (0.202 g) obtained in Example 1, perocta O (0.062 g) was added. And Perhexa TMH (0.023 g) were added and heat cured using the same mold and curing temperature program as in Example 4.
The physical properties of the colorless and transparent cured product obtained as a result were measured. Table 1 shows the resin composition, and Table 2 shows the measurement results of the physical properties.

Example 14: Curing of copolymer composition of BADTC and allyl methacrylate To a mixture of BADTC (4.759 g) obtained in Example 1 and allyl methacrylate (Wako Pure Chemical Industries, Ltd., 0.256 g) Perocta O (0.150 g) and Perhexa TMH (0.053 g) were added and heat cured using the same mold and curing temperature program as in Example 4.
The physical properties of the colorless and transparent cured product obtained as a result were measured. Table 1 shows the resin composition, and Table 2 shows the measurement results of the physical properties.

Example 15: Curing of copolymer composition of BADTC, allyl ester oligomer-2 and allyl methacrylate BADTC (4.251 g) obtained in Example 1, allyl ester oligomer-2 (0.509 g), allyl methacrylate Perocta O (0.151 g) and Perhexa TMH (0.060 g) were added to the mixture with (0.251 g) and heat cured using the same mold and curing temperature program as in Example 4.
The physical properties of the colorless and transparent cured product obtained as a result were measured. Table 1 shows the resin composition, and Table 2 shows the measurement results of the physical properties.

Example 16: Curing of copolymer composition of BADTC, allyl ester oligomer-1, allyl methacrylate BADTC (4.251 g) obtained in Example 1, allyl ester oligomer-1 (0.501 g), allyl methacrylate Perocta O (0.154 g) and Perhexa TMH (0.053 g) were added to the mixture with (0.257 g) and heat cured using the same mold and curing temperature program as in Example 4.
The physical properties of the colorless and transparent cured product obtained as a result were measured. Table 1 shows the resin composition, and Table 2 shows the measurement results of the physical properties.

Example 17: Curing of copolymer composition of BADTC, diallyl 1,4-cyclohexanedicarboxylate and allyl methacrylate BADTC (4.259 g) obtained in Example 1 and diallyl 1,4-cyclohexanedicarboxylate (0. 252 g) and allyl methacrylate (0.264 g), Perocta O (0.155 g) and Perhexa TMH (0.057 g) are added and heat cured using the same mold and curing temperature program as in Example 4. It was.
The physical properties of the colorless and transparent cured product obtained as a result were measured. Table 1 shows the resin composition, and Table 2 shows the measurement results of the physical properties.

Example 18: Curing of BADTC, allyl ester oligomer-2, diallyl maleate copolymer composition BADTC (4.504 g) obtained in Example 1, allyl ester oligomer-2 (0.256 g), diallyl maleate Perocta O (0.151 g) and Perhexa TMH (0.053 g) were added to the mixture with (0.251 g) and heat cured using the same mold and curing temperature program as in Example 4.
The physical properties of the colorless and transparent cured product obtained as a result were measured. Table 1 shows the resin composition, and Table 2 shows the measurement results of the physical properties.

Example 19: Curing of BADTC, CR-39 Copolymer Composition A mixture of BADTC (1.810 g) obtained in Example 1 and CR-39 (PPG, 0.201 g) was mixed with perocta O ( 0.065 g) and Perhexa TMH (0.022 g) were added and heat cured using the same mold and curing temperature program as in Example 4.
The physical properties of the colorless and transparent cured product obtained as a result were measured. Table 1 shows the resin composition, and Table 2 shows the measurement results of the physical properties.

Example 20: Curing of a copolymer composition of BADTC, diallyl isophthalate, and benzyl methacrylate BADTC (1.802 g) obtained in Example 1, diallyl isophthalate (0.104 g), benzyl methacrylate (Wako Pure Chemical Industries, Ltd.) Perocta O (0.062 g) and Perhexa TMH (0.020 g) were added to a mixture with Kogyo Kogyo Co., Ltd. (0.102 g), and heat cured using the same mold and curing temperature program as in Example 4.
The physical properties of the colorless and transparent cured product obtained as a result were measured. Table 1 shows the resin composition, and Table 2 shows the measurement results of the physical properties.

Example 21: Curing of copolymer composition of BADTC, allyl ester oligomer-2, benzyl methacrylate BADTC (1.906 g) obtained in Example 1, allyl ester oligomer-2 (0.093 g), benzyl methacrylate Perocta O (0.062 g) and Perhexa TMH (0.026 g) were added to the mixture with (0.018 g) and heat cured using the same mold and curing temperature program as in Example 4.
The physical properties of the colorless and transparent cured product obtained as a result were measured. Table 1 shows the resin composition, and Table 2 shows the measurement results of the physical properties.

Example 22: Curing of copolymer composition of BADTC, allyl ester oligomer-4 and allyl methacrylate BADTC (2.250 g) obtained in Example 1 and allyl ester oligomer-4 {shown by the following chemical formula (13) Compound, provided that n = 0 (monomer) is 40% by mass, n = 1 or more is 60% by mass} (0.600 g), and allyl methacrylate (0.150 g) is mixed with perocta O (0.090 g). And Perhexa TMH (0.030 g) were added, put into the same mold as in Example 4, heated from 45 ° C. to 120 ° C. over 16 hours, and heat cured with a curing temperature program of heating for 2 hours.
The physical properties of the colorless and transparent cured product obtained as a result were measured. Table 1 shows the resin composition, and Table 2 shows the measurement results of the physical properties.

Allyl ester oligomer-4 was produced as follows.
In a 1-liter three-necked flask equipped with a distillation apparatus, diallyl terephthalate (400.04 g, 1.624 mol) and 2,2-bis [4- (2-hydroxyethoxy) -3,5-dibromophenyl] propane (146.68 g, 0) .23 mol) and 0.127 g of dibutyltin oxide were charged and heated at 180 ° C. in a nitrogen stream to distill off allyl alcohol produced. When about 13.7 g of allyl alcohol was distilled off, the pressure inside the reaction system was reduced to 1.33 kPa to increase the distillation rate of allyl alcohol. After the theoretical amount (27.0 g) of allyl alcohol was distilled off, and further maintained at 180 ° C./0.13 kPa for 1 hour, the reactor was cooled to obtain 519.0 g of allyl ester oligomer-4.

Example 23: Curing of copolymer composition of BADTC and triallyl cyanurate A mixture of BADTC (2.550 g) obtained in Example 1 and triallyl cyanurate (Wako Pure Chemical Industries, Ltd., 0.450 g) was mixed with perocta. O (0.090 g) and perhexa TMH (0.030 g) were added and heat-cured in the same manner as in Example 22.
The physical properties of the colorless and transparent cured product obtained as a result were measured. Table 1 shows the resin composition, and Table 2 shows the measurement results of the physical properties.

Example 24: Curing of copolymer composition of BADTC, triallyl cyanurate and allyl methacrylate BADTC (2.550 g), triallyl cyanurate (0.300 g) and allyl methacrylate (0.150 g) obtained in Example 1 Perocta O (0.091 g) and Perhexa TMH (0.030 g) were added to the mixture and heat cured in the same manner as in Example 22.
The physical properties of the colorless and transparent cured product obtained as a result were measured. Table 1 shows the resin composition, and Table 2 shows the measurement results of the physical properties.

Example 25: Curing of copolymer composition of BADTC, divinylbenzene and diallyl maleate BADTC (1.500 g) obtained in Example 1, divinylbenzene (manufactured by Wako Pure Chemical Industries, Ltd., 0.100 g) and maleic acid Perocta O (0.060 g) and Perhexa TMH (0.020 g) were added to a mixture of diallyl (0.399 g), and heat cured as in Example 22.
The physical properties of the colorless and transparent cured product obtained as a result were measured. Table 1 shows the resin composition, and Table 2 shows the measurement results of the physical properties.

Example 26: Curing of copolymer composition of BADTC, divinylbenzene, and allyl methacrylate BADTC (1.700 g) obtained in Example 1, divinylbenzene (0.100 g) and allyl methacrylate (0.201 g) Perocta O (0.060 g) and Perhexa TMH (0.019 g) were added to the mixture, and heat-cured in the same manner as in Example 22.
The physical properties of the colorless and transparent cured product obtained as a result were measured. Table 1 shows the resin composition, and Table 2 shows the measurement results of the physical properties.

Example 27: Curing of copolymer composition of BADTC, allyl methacrylate, diallyl maleate BADTC (2.549 g) obtained in Example 1, allyl methacrylate (0.015 g), diallyl maleate (0.301 g) Perocta O (0.090 g) and Perhexa TMH (0.030 g) were added to the mixture and heat cured in the same manner as in Example 22.
The physical properties of the colorless and transparent cured product obtained as a result were measured. Table 1 shows the resin composition, and Table 2 shows the measurement results of the physical properties.

Example 28: Curing of BADTC Perocta O (0.060 g) perhexa TMH (0.020 g) was added to the BADTC (2.000 g) obtained in Example 1, and the same mold and curing temperature program as in Example 4 were used. Used and cured.
The physical properties of the colorless and transparent cured product obtained as a result were measured. Table 1 shows the resin composition, and Table 2 shows the measurement results of the physical properties.

Example 29: Lens molding of copolymer composition of BADTC, allyl ester oligomer-2 and allyl methacrylate BADTC (21.20 g) obtained in Example 1, allyl ester oligomer-2 (2.550 g), methacrylic acid Perocta O (0.750 g) and Perhexa TMH (0.250 g) were added to a mixture with allyl (1.250 g) and stirred until uniform. The obtained composition was poured into a lens mold having a power of -2.00 consisting of a glass mold and a resin gasket, and was thermally cured using the same curing temperature program as in Example 15. After curing, the lens mold was removed to obtain a lens-shaped molded body.

Comparative Example 1: Curing of bis (allyloxycarbonylthioethyl) sulfide Based on Example 1 in paragraph [0025] of JP-A-10-175947 (Patent Document 4), a compound represented by the chemical formula (14): bis ( Allyloxycarbonylthioethyl) sulfide was synthesized.

Perhexa TMH (0.100 g) is added to this bis (allyloxycarbonylthioethyl) sulfide (2.500 g) and heated to form a 4 mm thick mold consisting of two glass plates and a silicon tube as a spacer. Poured. Curing temperature program in which this is put in an oven, heated at 70 ° C. for 7 hours, then heated to 90 ° C. over 10 hours, further heated to 120 ° C. over 3 hours, and then heated at 120 ° C. for 2 hours. And heat cured.
The physical properties of the resulting yellow transparent cured product were measured. Table 1 shows the resin composition, and Table 2 shows the measurement results of the physical properties.

Comparative Example 2: Curing of bis (allyloxycarbonylthioethyl) sulfide To bis (allyloxycarbonylthioethyl) sulfide (2.000 g) of Comparative Example 1, perocta O (0.060 g) perhexa TMH (0.020 g) was added. In addition, it was heat cured using the same mold and curing temperature program as in Example 4. The obtained cured product was rubbery.
The physical properties of the colorless and transparent cured product obtained as a result were measured. Table 1 shows the resin composition, and Table 2 shows the measurement results of the physical properties.

Abbreviations used in Table 1 and Table 2 are as follows.
BADTC: S, S′-bis [2- (allyloxycarbonylthio) ethyl] dithiocarbonate TMPTMA: trimethylolpropane trimethacrylate DAIP: diallyl isophthalate H-DATP: diallyl 1,4-cyclohexanedicarboxylate IBMA: isobornyl Methacrylate DCPMA: Dicyclopentanyl methacrylate AEO-1-4: Allyl ester oligomer-1-4
TAT: triallyl trimelliate TAIC: triallyl isocyanurate DAM: diallyl maleate AMA: allyl methacrylate CR-39: diethylene glycol bisallyl carbonate BzMA: benzyl methacrylate TAC: triallyl cyanurate DVB: divinylbenzene ACS: bis (allyloxycarbonyl) Thioethyl) sulfide HO: perhexyl O
OO: Perocta O
TMH: Perhexa TMH

  As a result, the cured products obtained from the radical polymerizable compound of the present invention and the optical material composition are all colorless and transparent, have a high refractive index, and are useful as optical materials. On the other hand, the cured product of Comparative Example 1 had a poor balance between the refractive index and the Abbe number, and coloration was also observed. The cured product of Comparative Example 2 was hard rubber.

The radically polymerizable compound having a dithiocarbonate structure and a sulfur-containing allyl carbonate group according to the present invention provides an optical material that is stable during thermosetting reaction and less colored, has a high refractive index, and is excellent in transparency.
Cured products of the composition for optical materials of the present invention are optical lenses such as spectacle lenses and camera lenses, optical waveguides, optical sealants, optical adhesives, optical films, prisms, light guide plates for liquid crystal panels, optical fibers, and transparent It can be used as an optical material for panels, transparent films, transparent plates and the like.

2 is a ¹ H-NMR spectrum of S, S′-bis [2- (allyloxycarbonylthio) ethyl] dithiocarbonate obtained in Example 1. FIG. 2 is a ¹³ C-NMR spectrum of S, S′-bis [2- (allyloxycarbonylthio) ethyl] dithiocarbonate obtained in Example 1. FIG. 2 is an IR spectrum of S, S′-bis [2- (allyloxycarbonylthio) ethyl] dithiocarbonate obtained in Example 1. FIG.

Claims (16)

General formula (1)
(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and X and Y each independently represent an alkylene group, arylene group and cycloalkylene having 1 to 10 carbon atoms which may be branched. Represents a divalent group selected from the group consisting of groups).   The radically polymerizable compound according to claim 1, wherein X and Y in the general formula (1) are a methylene group, an ethylene group, a 1,2-propylene group, or a 1,3-propylene group. The radically polymerizable compound according to claim 1 or 2, wherein R ¹ and R ² in the general formula (1) are hydrogen atoms. General formula (2)
(Wherein L represents a divalent group selected from the group consisting of an alkylene group having 1 to 10 carbon atoms, an arylene group, and a cycloalkylene group, which may be branched), in the presence of a base, General formula (3)
(In the formula, R ⁴ represents a hydrogen atom or a methyl group, and Z represents a chlorine atom or a bromine atom.)
(The symbols in the formula represent the same meaning as described above.) After obtaining the thiol compound represented by the general formula (1), it is further reacted with N, N′-carbonyldiimidazole.
(In the formula, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and X and Y each independently represent an alkylene group, arylene group and cycloalkylene having 1 to 10 carbon atoms which may be branched. Represents a divalent group selected from the group consisting of groups.).   The method for producing a radical polymerizable compound according to claim 4, wherein X and Y in the general formula (1) are a methylene group, an ethylene group, a 1,2-propylene group, or a 1,3-propylene group. The method for producing a radical polymerizable compound according to claim 4 or 5, wherein R ¹ and R ² in the general formula (1) are hydrogen atoms.   The polymer or copolymer which makes the radically polymerizable compound in any one of Claims 1-3 a kind of raw material monomer.   The copolymer according to claim 7, which is a copolymer of the radical polymerizable compound according to any one of claims 1 to 3 and another radical polymerizable compound.   The copolymer according to claim 8, which is a copolymer of the radical polymerizable compound according to any one of claims 1 to 3 and allyl methacrylate and / or diallyl maleate.   The polymeric composition for optical materials containing the radically polymerizable compound in any one of Claims 1-3.   The polymerizable composition for an optical material according to claim 10, further comprising another radical polymerizable compound.   The polymerizable composition for an optical material according to claim 11, wherein the other radical polymerizable compound is at least allyl methacrylate and / or diallyl maleate.   Hardened | cured material of the polymeric composition for optical materials in any one of Claims 10-12.   The molded object for optical materials containing the hardened | cured material of Claim 13.   The molded article for an optical material according to claim 14, selected from the group consisting of a lens, an optical waveguide, a film, a prism, a flat plate, or a fiber.   A lens formed by curing the polymerizable composition for an optical material according to claim 10.