JPH1143514A - Styrenic monomer, styrenic monomer composition, styrenic polymers and plastic optical material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compounds useful for plastic lens for eyeglasses, camera lens, optical elements, etc., having high refractive index and Abbe's number, exhibiting excellent impact resistance while retaining excellent physical properties such as heat resistance, stainability and specific gravity, etc. SOLUTION: The styrenic monomer is expressed by formula I (R is a 2 to 11C alkylene containing sulfur atom; X is H, methyl), for example, compound expressed by formula II. The styrenic monomer of formula I is obtained by carrying out the reaction of a sulfur atom containing dihydroxy compound (for example; the compound of formula III) having hydroxy groups blocked with 2-tetrahydro-pyranyl group, etc., with a vinyl(or isopropenyl)benzyl halogen compounds such as 4-vinylbenzylchloride, etc., in the presence of a catalyst such as sodium hydroxide, etc., followed by deprotection.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a styrene-based monomer, a styrene-based monomer composition, a styrene-based polymer and a styrene-based monomer which are suitably used as raw materials for plastic lenses for eyeglasses, camera lenses, optical elements and the like. The present invention relates to a plastic optical material having excellent impact properties and a high refractive index.

[0002]

2. Description of the Related Art In recent years, in the field of spectacle lenses, organic glass has been widely used in place of inorganic glass.
Organic glass is used because organic glass is excellent in impact resistance, light weight, moldability, and dyeability.

Examples of the resin forming such an organic glass include polymethyl methacrylate, polydiethylene glycol bisallyl carbonate, and polystyrene.

[0004]

However, polymethyl methacrylate has an Abbe number indicating the degree of chromatic aberration of 58.
However, the refractive index is as low as about 1.49. For this reason, when producing a lens for strong myopia, there is a problem that the edge of the lens must be thickened.

[0005] Polydiethylene glycol bisallyl carbonate is excellent in impact resistance and has a large Abbe number of 58. However, the specific gravity is relatively large at about 1.33, and the refractive index is as low as about 1.49 similarly to polymethyl methacrylate. For this reason, when producing a lens for strong myopia, there is a problem that the edge of the lens must be thickened.

Furthermore, polystyrene has a refractive index of 1.59.
And high, but inferior in impact resistance. Moreover,
There is a problem that heat resistance, dyeability and adhesion of a hard coat film are also poor. Japanese Patent Application Laid-Open No. 6-184241 discloses a styrene polymer having an ether bond represented by the following general formula (5). Inferior.

[0007]

Embedded image The present invention has been made by paying attention to the above-mentioned problems of the prior art. The objective is to maintain styrene-based monomers and styrene-based monomers that have high refractive index and Abbe number and can exhibit excellent impact resistance while maintaining good physical properties such as heat resistance, dyeability and specific gravity. To provide a monomer composition, a styrenic polymer and a plastic optical material.

[0008]

Means for Solving the Problems In order to achieve the above object, the styrene monomer of the first invention is represented by the following general formula (1).

[0009]

Embedded image (Wherein, R is an alkylene group having a total of 2 to 11 carbon atoms including a sulfur atom, and X is a hydrogen atom or a methyl group.) The styrene monomer of the second invention is a styrene monomer of the first invention. In the general formula (1) is an alkylene group represented by the following general formula (2).

-(CH ₂ CH ₂ S) _m- (CH ₂ ) _n- (2) (where m and n are each an integer of 1 to 5) The styrene of the third invention The system polymer is obtained by polymerizing a monomer containing the styrene monomer of the first invention.

The styrenic polymer for a plastic optical material of the fourth invention is obtained by polymerizing the monomer containing the styrenic monomer of the first or second invention by a heat curing method or an active energy ray curing method. It is made.

A plastic optical material according to a fifth aspect of the present invention is obtained by molding the styrene-based polymer according to the third or fourth aspect into a predetermined shape. The styrene monomer composition of the sixth invention comprises the styrene monomer of the first or second invention and at least one monomer having a vinyl group.

[0013] The styrene monomer composition of the seventh invention comprises:
In the sixth invention, the monomer having a vinyl group is
It is a monomer having a (meth) acryloyl group. In a styrene-based monomer composition according to an eighth aspect, in the seventh aspect, the monomer having a (meth) acryloyl group is a monomer represented by the following general formula (3).

[0014]

Embedded image (Where Y is a hydrogen atom or a methyl group, and A is C 2
An alkylene group of 6 to 6, p represents an integer of 1 to 25; In a styrene-based monomer composition according to a ninth aspect, in the sixth aspect, the monomer having a vinyl group is a monomer represented by the following general formula (4).

[0015]

Embedded image (Where α represents a hydrogen atom or a methyl group, β represents a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 6 carbon atoms or a vinyl group.) The styrene polymer of the tenth invention is It is obtained by polymerizing the styrene monomer composition according to any one of the sixth to ninth inventions.

According to an eleventh aspect of the present invention, there is provided a styrenic polymer for a plastic optical material, wherein the styrenic monomer composition according to any one of the sixth to ninth aspects is cured by heating or active energy ray curing. By polymerization.

A plastic optical material according to a twelfth aspect is:
The styrene polymer of the tenth or eleventh invention is formed into a predetermined shape.

[0018]

Embodiments of the present invention will be described below in detail. The novel styrene monomer is represented by the following general formula (1). R in the general formula (1)
Is an alkylene group having 2 to 11 carbon atoms including a sulfur atom. The total number of carbon atoms in R is preferably from 3 to 7, more preferably from 3 to 5. When the total number of carbon atoms exceeds 11, physical properties such as heat resistance of the obtained styrene-based polymer are reduced.

If the ratio of the number of carbon atoms to the number of sulfur atoms in R is too large, the refractive index becomes small. Therefore, the ratio is preferably 2 to 5, more preferably 2 to 4, and more preferably 2 to 4. 3 is particularly preferred.

[0020]

Embedded image (Where R is an alkylene group having 2 to 11 carbon atoms including a sulfur atom, and X is a hydrogen atom or a methyl group.) The styrene monomer represented by the general formula (1) is Since the molecular styrene has a specific structure linked via an alkylene group containing a sulfur atom, the refractive index and Abbe number of a plastic optical material made of a polymer obtained by polymerizing a styrene monomer are determined. It has functions that can be improved. Further, the polymer obtained from the styrene-based monomer has a bonding structure via a hydrogen bond and has a cross-linked structure with two molecules of styrene, so that the obtained polymer has impact resistance, heat resistance and resistance to heat. It has a function to enhance solvent properties.

Further, since the styrenic monomer has a hydroxyl group which is a polar group, it has a function of improving the dyeability of the obtained polymer. In addition, since the styrene monomer has two benzene rings, it has a function of reducing the specific gravity of the obtained polymer.

In the general formula (1), R is the following general formula (2)
Is preferably represented by -(CH ₂ CH ₂ S) _m- (CH ₂ ) _n- (2) (where m and n are each an integer of 1 to 5) represented by the general formula (2). The ones in which the ratio of the number of carbon atoms to the number of sulfur atoms is small, that is, the sulfur density is high, and the resulting polymer has a high refractive index,
HSCH ₂ CH ₂ OH or HSCH ₂ CH
_This is because it is easy and economical to obtain things such as 2SH.

The above m and n are each an integer of 1 to 5, and when m exceeds 5, the heat resistance of the obtained styrene-based polymer decreases, and when n exceeds 5, the obtained styrene-based polymer becomes Has a low refractive index. These m and n are each preferably 1 to 3, and more preferably 1 to 2.

In the general formula (1), CH ₂ ＣCX-
The group may be bonded to any of the ortho, meta and para positions with respect to the benzene ring, but is usually preferably in the meta or para position for ease of formation. The ortho position has a large steric hindrance and is difficult to generate, but may be in the ortho position.

The typical compounds of the styrene monomer represented by the general formula (1) are exemplified by the following chemical formulas (6) to (6).
Examples include the compound shown in (29), but are not limited thereto.

[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

Embedded image The styrene-based monomer represented by the general formula (1) is a novel compound as described above, and is synthesized by a dihydroxy compound having a protected hydroxyl group and containing a sulfur atom, and vinyl (or isopropenyl). A benzyl halide is reacted in the presence of a catalyst and then deprotected. As the catalyst, triethylamine, imidazole, 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), sodium hydroxide, potassium hydroxide, potassium carbonate, sodium hydride and the like are used. You. Examples of the hydroxyl-protecting group include a 2-tetrahydropyranyl group, a 2-tetrahydrofuranyl group, a 1-ethoxyethyl group, a 1-isopropoxyethyl group, a 1-butoxyethyl group, a 1- (2-ethylhexyloxy) ethyl group, −
(T-butoxy) ethyl group, 1- (t-amyloxy)
Ethyl group, 1- (cyclohexyloxy) ethyl group, t
-Butyldimethylsilyl group and the like.

Further, as another method, a mercapto compound having a vinyl (or isopropenyl) benzyloxyl group is reacted with a halide of 2,3-epoxypropane or a dihalogen compound having a hydroxyl group in the presence of a base. can get.

The styrenic monomer composition contains the styrenic monomer and another monomer having a vinyl group. Examples of such a monomer having a vinyl group include:
For example, a monomer having a (meth) acryloyl group is used for increasing the Abbe number or improving the impact resistance.

Next, a novel styrene-based polymer is obtained by polymerizing the styrene-based monomer represented by the general formula (1) or the styrene-based monomer composition. That is, the styrene-based polymer is a homopolymer of a styrene-based monomer, or a copolymer obtained by copolymerizing a styrene-based monomer as an essential component with another copolymerizable monomer. . In the case of a copolymer, a copolymer obtained by copolymerizing a monomer mixture containing a styrene-based monomer represented by the general formula (1) as a main component effectively exhibits the function of the styrene-based monomer. Preferred for

Other copolymerizable monomers include, for example, styrene, α-methylstyrene, vinyltoluene,
Ethylstyrene, p-chlorostyrene, o-chlorostyrene, chloromethylstyrene, p-bromostyrene, m
-Bromostyrene, divinylbenzene, divinylbiphenyl, vinylphenol, vinylnaphthalene, 2,4-
Examples include vinyl aromatic monomers such as diphenyl-4-methyl-1-pentene, vinyl carbazole, vinyl pyridine, vinyl thiophene, and vinyl furan.

Further, other copolymerizable monomers include vinyl acetate, vinyl propionate, vinyl benzoate, (meth) acrylic acid and methyl (meth) acrylic acid.
, Ethyl (meth) acrylate, isopropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, methyl triglycol (Meth) acrylate, n-butoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate Phenoxypropyl (meth) acrylate, 2-
Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, allyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, p-chlorophenyl (meth) ) Acrylate, p-chlorobenzyl (meth) acrylate
P-bromophenyl (meth) acrylate, p-bromobenzyl (meth) acrylate, naphthyl (meth)
Acrylate, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, (meth) acrylonitrile, 2-hydroxy-3-phenoxypropyl (meth)
Acrylate, ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate
G, 1,3-butyleneglycol di (meth) acrylate
Diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol Rudi (meth) acrylate, glycerin di (meth) acrylate, 3-acryloylglycerin monomethacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 2 , 2-bis [4-[(meth) acryloyloxy] phenyl] propane, 2,2-bis [4-
[(Meth) acryloyloxyethoxy] phenyl] propane, 2,2-bis [4-[(meth) acryloyloxydiethoxy] phenyl] propane, 2,2-bis [4-[(meth) acryloyloxytriethoxy] Phenyl] propane, 2,2-bis [4-[(meth) acryloyloxytetraethoxy] phenyl] propane,
2,2-bis [4-[(meth) acryloyloxyhexaethoxy] phenyl] propane, 2,2-bis [4-
[(Meth) acryloyloxypropyloxy] phenyl] propane, 2,2-bis [4-[(meth) acryloyloxypolyethoxy] phenyl] propane, 2,2
-Bis [4- [2- (methacryloyloxy) ethoxycarbonyloxy] phenyl] propane, 2,2-bis [4- [3-[(meth) acryloyloxy] -2-
[Hydroxypropyloxy]] phenyl] propane,
2,2-bis [4- [2- [3-[(meth) acryloyloxy] -2-hydroxypropoxy] propoxy]
Phenyl] propane, bisphenol S-di (meth) acrylate, bisphenolketone di (meth) acrylate, bisphenolsulfidedi (meth) acrylate
G, 2,2-bis [4- [3-[(meth) acryloyloxy] -2-hydroxypropoxy] phenyl] propane, trimethylolpropane tri (meth) acryle
Diethylene glycol bisallyl carbonate, diisopropyl fumarate, diisopropyl maleate, diallyl fumarate, diallyl maleate, dibenzyl fumarate, dibenzyl maleate, dibenzyl mesa cone
G, maleic anhydride, itaconic anhydride, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, allyl cyanurate, allyl isocyanurate, diallyl naphthalenedicarboxylate, allyl methacrylate and the like. These monomers are used alone or as a mixture.

Further, as the other monomer having a copolymerizable vinyl group in the sixth invention, a monomer represented by the following general formula (3), which is effective for increasing the Abbe number, is preferable. .

[0056]

Embedded image (In the formula, Y represents a hydrogen atom or a methyl group. A represents an alkylene group having 2 to 6 carbon atoms. P is an integer of 1 to 25.) As such a monomer, for example, Ethylene glyco-
Rudimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, pentaethylene glycol dimethacrylate, hexaethylene glycol dimethacrylate, heptaethylene glycol dimethacrylate, Octaethylene glycol dimethacrylate, nonaethylene glycol dimethacrylate, decaethylene glycol dimethacrylate, tetradecaethylene glycol dimethacrylate, tricosaethylene glycol dimethacrylate, 1,2-propylene glycol dimethacrylate -G, 1,3-propylene glyco-
Rudimethacrylate, 1,3-butyleneglycoldimethacrylate, 1,4-butyleneglycoldimethacrylate, 1,6-hexanediol-dimethacrylate,
Neopentyl glycol dimethacrylate, heptapropylene glycol dimethacrylate, ethylene glycol
Rudiacrylate, hexaethylene glycol diacrylate, nonaethylene glycol diacrylate, tetradecaethylene glycol diacrylate, tripropylene glycol diacrylate, heptapropylene glycol diacrylate, dodecapropylene glycol diacrylate -And the like.

Further, as the monomer having a vinyl group,
The following general formula (3) effective for increasing the refractive index and Abbe number
The monomer represented by 0) is preferred.

[0058]

Embedded image (Wherein, Y represents a hydrogen atom or a methyl group; B represents an alkylene group having 2 to 6 carbon atoms; a represents a hydrogen atom, a chlorine atom or a bromine atom; and q represents an integer of 1 to 20). Z is an alkylene group having 1 to 10 carbon atoms, an oxygen atom, a sulfoxide group or a sulfone group.) Examples of such a monomer include 2,2-bis [4
-(Methacryloyloxy) phenyl] propane, 2,
2-bis [4- (methacryloyloxyethoxy) phenyl] propane, 2,2-bis [4- (methacryloyloxydiethoxy) phenyl] propane, 2,2-bis [4- (methacryloyloxytriethoxy) phenyl] propane 2,2-bis [4- (methacryloyloxytetraethoxy) phenyl] propane, 2,2-bis [4- (methacryloyloxypentaethoxy) phenyl] propane, 2,2-bis [4- (methacryloyloxyhexaethoxy) ) Phenyl] propane, 2,2-
Bis [4- (methacryloyloxydecaethoxy) phenyl] propane, 2,2-bis [4- (methacryloyloxypentadecaethoxy) phenyl] propane, 2,
2-bis [4- (acryloyloxydiethoxy) phenyl] propane, 2,2-bis [4- (acryloyloxyethoxy) phenyl] propane, 1,1-bis [4
-(Methacryloyloxydiethoxy) phenyl] cyclohexane, bis [4- (methacryloyloxy) phenyl] ether, bis [4- (methacryloyloxy)
Phenyl] sulfone, 2,2-bis [4-[(meth)
Acryloyloxypropyloxy] phenyl] propane, 2,2-bis [4-[(meth) acryloyloxyhexyloxy] phenyl] propane, 2,2-bis [4- (methacryloyloxyethoxy) 3,5-dibromophenyl] And propane.

Further, as the monomer having a vinyl group,
The following general formula (3) effective for increasing the refractive index and Abbe number
The monomer represented by 1) is preferred.

[0060]

Embedded image (Where Y represents a hydrogen atom or a methyl group; D represents an alkylene group having 2 to 6 carbon atoms; b is a hydrogen atom, a chlorine atom or a bromine atom; and r is an integer of 1 to 20). Z is an alkylene group having 1 to 10 carbon atoms, an oxygen atom, a sulfoxide group or a sulfone group.) Examples of such a monomer include 2,2-bis [4
-(Methacryloyloxyethoxycarbonyloxy)
Phenyl] propane, 2,2-bis [4- (methacryloyloxydiethoxycarbonyloxy) phenyl] propane, 2,2-bis [4- (methacryloyloxytriethoxycarbonyloxy) phenyl] propane,
2,2-bis [4- (methacryloyloxytetraethoxycarbonyloxy) phenyl] propane, 2,2-
Bis [4- (methacryloyloxypentaethoxycarbonyloxy) phenyl] propane, 2,2-bis [4
-(Methacryloyloxyhexaethoxycarbonyloxy) phenyl] propane, 2,2-bis [4- (methacryloyloxydecaethoxycarbonyloxy) phenyl] propane, 2,2-bis [4- (methacryloyloxypentadecaethoxycarbonyloxy) Phenyl] propane, 2,2-bis [4- (methacryloyloxybutoxycarbonyloxy) phenyl] propane,
2,2-bis [4- (acryloyloxyethoxycarbonyloxy) phenyl] propane, bis [4- (acryloyloxytrihexyloxycarbonyloxy)
Phenyl] ether, 2,2-bis [4- (methacryloyloxyethoxycarbonyloxy) -3,5-dibromophenyl] propane and the like.

Further, as the monomer having a vinyl group,
A monomer represented by the following general formula (32), which is effective for increasing the Abbe number, is preferred.

[0062]

Embedded image (Wherein, Y represents a hydrogen atom or a methyl group.
Represents an alkylene group having 2 to 6 carbon atoms. t is an integer of 0 to 25. G represents a phenyl group, a benzyl group, or an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom. Examples of such a monomer include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, hexyl methacrylate, (methoxydiethylene glycol) monomethacrylate, and (methoxytetraethylene). (Glycol) monomethacrylate, (methoxynonaethyleneglycol) monomethacrylate, (methoxypentadecaethyleneglycol) monomethacrylate
, (Methoxytricosaethylene glycol) monomethacrylate, (methoxyethylene glycol) monoacrylate, (methoxydiethylene glycol) monoacrylate, (methoxytetraethylene glycol) monoacrylate, (methoxy (Decaethylene glycol) monoacrylate, (Methoxydodecaethylene glycol)
G) monoacrylate, (methoxyhexadecaethylene glycol) monoacrylate, phenyl methacrylate
Benzyl methacrylate, phenyl acrylate,
Benzyl acrylate, phenoxyethyl methacrylate
Phenoxydiethylene glycol methacrylate,
Phenoxyethyl acrylate, (phenoxydiethylene glycol) monoacrylate, (phenoxynonaethylene glycol) monoacrylate, (phenoxypentadecaethylene glycol) monomethacrylate, phenoxypropyl methacrylate, phenoxy Hexyl methacrylate, 2- (2,4,6-tribromophenyloxy) ethyl acrylate, 2,4,6-tribromophenyl methacrylate and the like can be mentioned.

Further, as the monomer having a vinyl group,
A monomer represented by the following general formula (33), which is effective for increasing the Abbe number, is preferable.

[0064]

Embedded image (Wherein, Y represents a hydrogen atom or a methyl group; J represents an alkylene group having 2 to 6 carbon atoms; u is an integer of 0 to 10; K represents an alkylene group having 1 to 6 carbon atoms). And v is 3 or 4. When v is 3, L is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
There is no L. Examples of such monomers include, for example, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetramethacrylate, tetramethylolmethanetetraacrylate.
, Trimethylolpropane tri (methacryloyl ethoxyl), trimethylol propane tri (acryloyl ethoxy), trimethylol propane tri (methacryloyl diethoxy), trimethylol propane tri (acryloyl diethoxyl), trimethylol tripropytritriol Triethoxyl), trimethylolpropane tri (methacryloyl hexaethoxy), and trimethylol propane tri (acryloyl hexaethoxy).

Further, as the monomer having a vinyl group,
Preferred is a monomer represented by the following general formula (4), which is effective for increasing the refractive index.

[0066]

Embedded image (In the formula, α represents a hydrogen atom or a methyl group; β represents a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 6 carbon atoms, or a vinyl group.) As such a monomer, For example, styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, p-ethylstyrene, m-ethylstyrene, p-isopropylstyrene, m-isopropylstyrene, p-methylstyrene
(T-butyl) styrene, m- (t-butyl) styrene, p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene, p-vinylstyrene, m-vinylstyrene , Α-methyl-p-chlorostyrene, α-methyl-m-chlorostyrene, α-methyl-p-bromostyrene, α-methyl-m-bromostyrene and the like.

Further, other copolymerizable monomers include vinyl acetate, vinyl propionate, vinyl benzoate, (meth) acrylic acid, 2-ethylhexyl (meth)
Acrylate, glycidyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, allyl (meth) acrylate ,
p-Chlorophenyl (meth) acrylate, p-chlorobenzyl (meth) acrylate, p-bromophenyl (meth) acrylate, p-bromobenzyl (meth) acrylate, naphthyl (meth) acrylate G, (meta)
Acrylamide, N, N-dimethyl (meth) acrylamide, (meth) acrylonitrile, 2-hydroxy-3
-Phenoxypropyl (meth) acrylate, glycerin di (meth) acrylate, (3-acryloylglycerin) monomethacrylate, 2,2-bis [4- [3-
[(Meth) acryloyloxy] -2- [hydroxypropyloxy]] phenyl] propane, 2,2-bis [4- [2- [3-[(meth) acryloyloxy]-
2-hydroxypropoxy] propoxy] phenyl] propane, bisphenol ketone di (meth) acryle
2,2-bis [4- [3-[(meth) acryloyloxy] -2-hydroxypropoxy] phenyl] propane, diethylene glycol bisallyl carbonate,
Diisopropyl fumarate, diisopropyl maleate,
Diallyl fumarate, diallyl maleate, dibenzyl fumarate, dibenzyl maleate, dibenzyl mesa cone
G, maleic anhydride, itaconic anhydride, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, allyl cyanurate, allyl isocyanurate, diallyl naphthalenedicarboxylate, allyl methacrylate, 2,9-
Dihydroxy-1,10-bis (methacryloyloxy) -4,7-dioxadecane, p-phenylstyrene, divinylbiphenyl, vinylphenol, vinylnaphthalene, 2,4-diphenyl-4-methyl-1-pentene, vinylcarbazole , Vinylpyridine, vinylthiophene, vinylfuran, p- (chloromethyl) styrene, m- (chloromethyl) styrene, p- (hydroxymethyl) styrene, m- (hydroxymethyl) styrene and the like. These monomers are used alone or as a mixture.

The monomer having a vinyl group in the sixth invention is, for example, a combination of a monomer having a (meth) acryloyl group and a monomer represented by the general formula (4). Things are used.

In this case, examples of the monomer having a (meth) acryloyl group include the following monomers (A) to (D). (A) a monomer represented by the general formula (3) (B) a monomer represented by the general formula (30) (C) a monomer represented by the general formula (31) (D The monomer represented by the general formula (32) (E) The monomer represented by the general formula (33) The monomer having a vinyl group has a (meth) acryloyl group And specifically, the general formula (3)
And a combination of the monomer represented by the general formula (30).

Further, the monomer having a vinyl group is a monomer having a (meth) acryloyl group represented by the following general formula (3):
A monomer represented by the general formula (30), which is also a monomer having a (meth) acryloyl group, and a monomer represented by the general formula (4) It may be a combination.

Further, the monomer having a vinyl group is a monomer having a (meth) acryloyl group, and specifically, a monomer represented by the general formula (3) and a monomer represented by the general formula (31) It may be composed of a combination with the represented monomer.

Further, the monomer having a vinyl group is (meth)
A monomer represented by the general formula (3), which is a monomer having an acryloyl group, and a monomer represented by the general formula (31), which is also a monomer having a (meth) acryloyl group, It may be a combination of a monomer having a vinyl group and a monomer represented by the general formula (4).

In addition, the monomer having a vinyl group is a monomer having a (meth) acryloyl group, and specifically, a monomer represented by the general formula (3) and a monomer represented by the general formula (32) May be used in combination with the monomer represented by

The monomer having a vinyl group is (meth)
A monomer represented by the general formula (3), which is a monomer having an acryloyl group, and a monomer represented by the general formula (32), which is also a monomer having a (meth) acryloyl group, It may be a combination of a monomer having a vinyl group and a monomer represented by the general formula (4).

In addition, the monomer having a vinyl group is a monomer having a (meth) acryloyl group, specifically, a monomer represented by the general formula (3) and a monomer represented by the general formula (33) May be used in combination with the monomer represented by

The monomer having a vinyl group is (meth)
A monomer represented by the general formula (3), which is a monomer having an acryloyl group, and a monomer represented by the general formula (33), which is also a monomer having a (meth) acryloyl group, It may be a combination of a monomer having a vinyl group and a monomer represented by the general formula (4).

In the copolymer, the composition ratio between the styrene monomer represented by the general formula (1) and the other copolymerizable monomer depends on the optical characteristics required for the desired optical material. ,
It depends on the mechanical properties and the polymerization conditions required for production. For this reason, although it cannot be uniformly defined, the styrene monomer represented by the general formula (1) is not less than 10% by weight,
Preferably, it is set to be 20% by weight or more. When the amount of the styrene-based monomer is less than 10% by weight, the obtained copolymer does not have the effect of improving the refractive index and impact resistance.

Next, the plastic optical material is usually obtained by polymerizing a styrene-based monomer or a styrene-based monomer composition and simultaneously molding it into a predetermined shape, or a styrene-based monomer or a styrene-based monomer. It can also be obtained by processing after the polymerization of the body composition. Examples of the molding method include a heat curing method and an active energy ray curing method. The heat-curing method is a method in which a monomer mixture is prepared by mixing the above-mentioned monomer and a polymerization initiator, and the mixture is poured into a mold having a molding concave portion having a desired shape, followed by heat-curing.

Examples of the polymerization initiator used in the polymerization include an azo polymerization initiator or an organic peroxide having a 10-hour half-life temperature of 120 ° C. or less. One or more of these polymerization initiators are used. Among these polymerization initiators, azo-based polymerization initiators include, for example, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-
Azobisisobutyronitrile, 2,2′-azobis (2
-Methylobtyronitrile), 1,1-azobis (cyclohexane-1-carbonitrile), dimethyl 2,2′-
Azobisisobutyrate is preferred.

Examples of the organic peroxide include benzoyl peroxide, diisopropyl peroxydica carbonate, di-n-propyl peroxydica carbonate, and bis (4-
(t-butylcyclohexyl) peroxydica-bone-
G, t-butyl peroxyisopropyl carbonate,
t-butyl peroxybenzoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy neodecanoate, di-t-butyl peroxide,
1,1-bis (t-butyl) peroxy-3,3,5-
Trimethylcyclohexane and the like are preferred.

The amount of the polymerization initiator used is preferably 0.05 to 5% by weight in the monomer or the monomer composition, and 0.1 to 4% by weight.
% By weight is more preferred. When the amount is less than 0.05% by weight, the curing of the monomer is insufficient, and the physical properties of the obtained molded article are deteriorated. When the amount exceeds 5% by weight, control of the curing reaction becomes difficult, and It is not preferable because cracks easily occur on the surface.

During the curing reaction, it is desirable to carry out the reaction with an inert gas such as nitrogen, helium, carbon dioxide or the like or in an atmosphere thereof in order to prevent the curing rate from being lowered by oxygen and to prevent the molded product from being colored. Curing temperature and curing time,
Although it depends on the curing agent to be used, it is preferably in the range of 20 to 130 ° C. for 5 to 48 hours. Shortening of curing time,
The temperature can be raised as appropriate for the purpose of completing the curing reaction and decomposing the unreacted curing agent. For example, the temperature is gradually increased from a temperature about 30 ° C. lower than the 10-hour half-life temperature of the curing agent to be used, and finally, the temperature is increased by about 30 ° C. from the 10-hour half-life temperature.
Complete curing at elevated temperatures.

Since the molded product obtained by such heat curing has internal strain, it is preferably 60 to 140.
C., more preferably 100 to 130.degree. C., for 30 minutes to less than 6 hours, preferably 1 to 4 hours to perform the annealing treatment. When the viscosity of the monomer or the monomer composition is low or the curing shrinkage is large, it can be preliminarily polymerized and then charged into a desired mold and cured.

On the other hand, the active energy ray curing method is a method in which a monomer and a sensitizer are charged in a mold and irradiated with an active energy ray such as an ultraviolet ray or an electron beam to be cured. Examples of the sensitizer include benzophenone, 4-phenylbenzophenone, 4-phenoxybenzophenone, 2,2-diethoxyacetophenone, and 2-hydroxy-2-methyl-
1-phenylpropan-1-one, benzyldimethylketal and the like are used. These are used alone or as a mixture.

The amount of the sensitizer used is 0.0% in the monomer composition.
The content is preferably 1 to 1% by weight, more preferably 0.02 to 0.5% by weight. If the amount used is less than 0.01% by weight, the polymerization of the monomer becomes insufficient, and the physical properties of the obtained molded product decrease. If the content exceeds 1% by weight, it is difficult to control the polymerization reaction, and the molded product is liable to be colored and surface cracks, which is not preferable.

At the time of the curing reaction, an inert gas such as nitrogen,
It is desirable to perform the replacement with helium, carbon dioxide, or the like or in the atmosphere. The active energy ray preferably has a wavelength in the range of about 100 to 600 nm. Examples of the radiation source include a chemical lamp, a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, and a metal halogen lamp. For example, ultraviolet rays of 10 to 400 nm
Irradiation and curing may be performed to 50 J / cm ² . Furthermore, in order to remove the internal distortion of the cured molding,
It is preferable to perform an annealing treatment similar to the heat curing method.

Further, the heat curing method and the active energy ray curing method can be used in combination. That is, after a polymerization initiator and a sensitizer are mixed with a monomer, and preliminarily heated by a polymerization initiator, the mixture is charged into a desired mold and polymerization is performed by irradiation with active energy rays. Conversely, after performing polymerization by irradiation with active energy rays, the polymerization can be completed by heating polymerization.

Further, when the styrene portion of the styrenic monomer represented by the general formula (1) is polymerized by a heat curing method, it simultaneously reacts with the hydroxyl group of the monomer represented by the general formula (1). A compound having a functional group described below may coexist. As such a compound, for example, an isocyanate compound which forms a urethane bond with a hydroxyl group is used. As an example of the isocyanate compound, 3-isocyanate compound is used.
Isopropenyl-α, α-dimethylbenzyl isocyanate, 4-isopropenyl-α, α-dimethylbenzyl isocyanate, 3-vinylbenzyl isocyanate,
m-xylylene diisocyanate, p-xylylene diisocyanate, α, α, α ′, α′-tetramethyl-m
-Xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetrachloro-m-xylylene diisocyanate, tetrachloro-
p-xylylene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, benzyl isocyanate G, phenyl isocyanate, norbornane diisocyanate, hydrogenated meta-xylylene diisocyanate, hydrogenated paraphenylene diisocyanate and the like. The urethane formation conditions may be set conditions when a polymerization initiator is used. In this case, the amounts of the styrene monomer represented by the general formula (1) and the isocyanate compound are determined based on the isocyanate group (NC)
O) / hydroxyl group (OH) molar ratio of 0.001
From 2.0 to 2.0, preferably from 0.01 to 1.0 from the viewpoint of reactivity.

In the monomer composition, if necessary, a dye,
Colorants such as pigments, ultraviolet absorbers, antioxidants, various stabilizers, antistatic agents, photochromic compounds, fluorescent brighteners, reaction accelerators, internal mold release agents, polymerization degree adjusting agents (2,4-
Diphenyl-4-methyl-1-pentene, a mercapto compound, etc.).

As described above, a plastic optical material having a predetermined shape can be obtained by polymerizing the monomer in a mold by a heat curing method or an active energy ray curing method and simultaneously molding the monomer into a predetermined shape. Alternatively, the plastic optical material is obtained by pre-polymerizing a monomer by a heat curing method or an active energy ray curing method, and then further polymerizing in a mold to form a predetermined shape. Further, the plastic optical material is obtained by polymerizing the monomer by a heat curing method or an active energy ray curing method to obtain a molded product having a predetermined shape,
This molded product is obtained by cutting and polishing into a lens shape.

The plastic optical material is prepared by previously polymerizing a styrene monomer or a styrene monomer composition to produce a styrene polymer, and molding the polymer by injection molding, extrusion molding, or the like. It can also be obtained by molding into a predetermined shape by a method.

Further, a hard coat film is provided on the surface of the molded product, so that the abrasion resistance of the surface can be further improved. The application of the hard coat agent is also performed on the surface of the molded product to which the primer liquid has been applied in order to improve the adhesion of the molded product after hardening or the hard coat film. A solution such as polyurethane or melamine is used as the primer solution. As a coating method, a dipping method, a spin coating method, a flow coating method, a spraying method or the like is employed.

Further, an antireflection film is provided on the surface of the molded product,
Visible light transmittance can be increased by suppressing surface reflection. As described above, according to this embodiment, the following effects are exhibited. R in the styrene monomer represented by the general formula (1)
Is composed of an alkylene group having a total carbon number of 2 to 11, including a sulfur atom. Therefore, the refractive index of a plastic optical material made of a polymer obtained by polymerizing a styrene-based monomer can be increased to 1.60 or more. Moreover, the Abbe number can be kept high, the dispersion of the refractive index can be reduced, and the chromatic aberration can be suppressed. -Since the hydroxyl group is contained in the general formula (1), the polymer obtained from the styrene monomer has a bonding structure via a hydrogen bond, thereby improving the impact resistance of the plastic optical material. be able to. Furthermore, unlike styrene, the styrene monomer of the general formula (1) is a bifunctional monomer to which two molecules of styrene are bonded via an organic group, and has a crosslinked structure (network structure) by polymerization. Therefore, the effect can be further enhanced. Further, the physical properties such as heat resistance and solvent resistance of the styrene-based polymer can be improved based on the intermolecular hydrogen bond and crosslinked structure of the styrene-based monomer of the general formula (1). -A urethane bond is formed by reacting a hydroxyl group in the styrene-based monomer of the general formula (1) with the isocyanate compound, and the impact resistance can be further improved by the hydrogen bonding effect. -Since the polymer obtained by polymerizing the styrene monomer of the general formula (1) has a hydroxyl group, it has excellent surface adhesion and is advantageous for forming a hard coat film. -The polymer obtained by polymerizing the styrene monomer of the general formula (1) is excellent in light resistance and weather resistance because sulfur is not directly bonded to the benzyl position or the benzene ring. The polymer obtained by polymerizing the styrene-based monomer of the general formula (1) has a hydroxyl group, and therefore has excellent dyeability and is advantageous for dyeing plastic optical materials such as lenses with dyes. . By blending monomers having a vinyl group such as a monomer having a (meth) acryloyl group with the styrene monomer of the general formula (1), the Abbe number is determined based on the properties of those monomers. Can be increased. Also, by using a monomer having a bifunctional (meth) acryloyl group, the obtained polymer has a cross-linked structure and can further improve physical properties such as impact resistance and solvent resistance. it can. -By using the monomer represented by the general formula (4), the refractive index can be kept high based on the properties of the monomer having a benzene ring.

[0094]

EXAMPLES Hereinafter, the embodiment will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. The abbreviations of the monomers used in the following description are shown below.

The abbreviation MONO-1 of the monomer represents the compound of the above formula (6). MO
NO-2 represents a mixture of the chemical formulas (6), (7) and (8).

MONO-3 is a compound of the above formula (9). MONO-4 represents a mixture of the chemical formulas (9), (10) and (11). MONO-5 represents a compound of the above formula (12).

MONO-6 is represented by the above formulas (14) and (1)
5 shows a mixture of 5) and (16). MONO-7 represents a mixture of the chemical formulas (19), (20) and (21). R
EFE-1 represents the aforementioned chemical formula (5).

ST: styrene BZ: benzyl methacrylate PA: (phenoxydiethylene glycol) acrylate MP: 2,2-bis [4- (methacryloyloxyethoxy) phenyl] propane TP: 2,2-bis [ 4- (methacryloyloxytriethoxy) phenyl] propane PP: 2,2-bis [4- (methacryloyloxypentaethoxy) phenyl] propane CP: 2,2-bis [4- [2- (methacryloyloxy) ethoxycarbonyloxy ] Phenyl] propane 2G: (diethylene glycol) dimethacrylate 4G: (tetraethylene glycol) dimethacrylate
G 4A: (tetraethylene glycol) diacrylate 9G: (nonaethylene glycol) dimethacrylate 9A: (nonaethylene glycol) diacrylate 14G: (tetradecaethylene glycol) dimethacrylate 14A: (tetradecaethylene glycol) diacrylate TM: trimethylolpropane trimethacrylate MM: (methoxydiethylene glycol) monomethacrylate MS: α-methylstyrene 3M: 3-methylstyrene CS: 4 -Chlorostyrene BR: 2,2-bis [4- (methacryloyloxyethoxycarbonyloxy) 3,5-dibromophenyl]
Propane DV: divinylbenzene DP: 2,4-diphenyl-4-methyl-1-pentene XC: xylylene diisocyanate SC: hydrogenated xylylene diisocyanate Will be described. Example 1 Synthesis of MONO-1 In a nitrogen atmosphere, 1,
36.0 g of 3-dichloro-2-propanol (279 m
mol) and 2,3.5 g of 3,4-dihydro-2H-pyran
(279 mmol) in a 30 ml solution of dichloromethane in 0.070 g of pyridinium-p-toluenesulfonate
(0.28 mmol) and reacted at room temperature for 24 hours.

The reaction solution was concentrated under reduced pressure, and 2-D was added to the residue.
44.7 g (572 mmol) of mercaptoethanol,
250 ml of ethanol, 44.7 g of sodium hydroxide
(1.12 mol) and reacted at 80 ° C. for 16 hours under a nitrogen atmosphere. The reaction solution was extracted with ethyl acetate-10% saline, and the organic layer was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (dichloromethane-methanol 20: 1) to give 76.1 g of a diol derivative represented by the following chemical formula (34).
(256 mmol) were obtained.

[0100]

Embedded image To 172 ml of a toluene solution containing 76.1 g (256 mmol) of this diol form, 4-vinylbenzyl chloride was added.
1 g (525 mmol), 85.8 g sodium hydroxide
(2.15 mol), 172 ml of water and 8.28 g (25.7 mmol) of tetrabutylammonium bromide were added and reacted at room temperature for 48 hours. The reaction solution was extracted with ethyl acetate-water, the organic layer was dehydrated with sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (dichloromethane) to obtain 129 g (244 mmol) of a protected alcohol represented by the following chemical formula (35).

[0101]

Embedded image To 492 ml of a methanol solution containing 129 g (244 mmol) of the protected alcohol was added 3.07 g (12.2 mmol) of pyridinium-p-toluenesulfonate.
The reaction was performed at room temperature for 24 hours. The reaction solution was concentrated under reduced pressure, and the obtained residue was extracted with ethyl acetate-water.
After the organic layer was dehydrated with sodium sulfate, the residue obtained by concentration under reduced pressure was subjected to silica gel column chromatography.
(Dichloromethane-methanol 100: 1) to give 106 g (238 mm) of MONO-1.
ol) obtained.

Purity (liquid chromatography): 9
9.8% mass spectrum [FAB method, ie Matric
After mixing the sample with the nitrobenzyl alcohol
To the molecular weight M and H⁺Added ion M ⁺+1
It is a method of detecting. ] M⁺+1: 445 elemental analysis (C_{twenty five}H₃₂O_ThreeS_Two): CHS measured value (%) 67.56 7.20 14.38 Calculated value (%) 67.53 7.25 14.42 Infrared absorption spectrum (cm)^-1, CHCl_Three): 3448
(-OH), 1629, 1604 (CH_Two= CH-Ph-)¹ H-nuclear magnetic resonance spectrum (ppm, CDCl_Three): 7.
38-7.25 (8H), 6.75-6.65 (2
H) 5.76-5.70 (2H), 5.25-5.2
1 (2H), 4.52 (4H), 3.82 (1H),
3.65 to 3.60 (4H), 3.31 (1H), 2.
82 to 2.61 (8H) (Example 2, synthesis of MONO-2)
33.4 g of 3-dichloro-2-propanol (259 m
mol) and 2,1.8 g of 3,4-dihydro-2H-pyran
(259 mmol) in 28 ml of dichloromethane
0.065 g of lydinium-p-toluenesulfonate
(0.26 mmol) and react at room temperature for 24 hours.
I let you.

The reaction solution was concentrated under reduced pressure, and 2-D was added to the residue.
41.5 g (531 mmol) of mercaptoethanol,
232 ml of ethanol, 41.5 g of sodium hydroxide
(1.04 mol), and reacted at 80 ° C. for 16 hours under a nitrogen atmosphere. The reaction solution was extracted with ethyl acetate-10% saline, and the organic layer was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (dichloromethane-methanol 20: 1) to give 69.5 g of a diol derivative represented by the following chemical formula (36).
(234 mmol) obtained.

[0104]

Embedded image To 157 ml of a toluene solution containing 69.5 g (234 mmol) of the diol form, vinylbenzyl chloride [m-p
Body mixture (6: 4)] 73.2 g (480 mmo
l), 78.6 g of sodium hydroxide (1.97 mo)
l), water (157 ml) and tetrabutylammonium bromide (7.54 g, 23.4 mmol) were added, and the mixture was reacted at room temperature for 48 hours. The reaction solution was extracted with ethyl acetate-water, the organic layer was dehydrated with sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (dichloromethane) to obtain 115 g (217 mmol) of a protected alcohol represented by the following chemical formula (37).

[0105]

Embedded image To 439 ml of a methanol solution containing 115 g (217 mmol) of the protected alcohol, 2.74 g (10.9 mmol) of pyridinium-p-toluenesulfonate was added.
The reaction was performed at room temperature for 24 hours. The reaction solution was concentrated under reduced pressure, and the obtained residue was extracted with ethyl acetate-water.
After dehydrating the organic layer with sodium sulfate, the residue obtained by concentration under reduced pressure is subjected to silica gel column chromatography.
(Dichloromethane-methanol 100: 1) to give 92.8 g (209 m) of MONO-2.
mol).

Purity (liquid chromatography): 9
9.7% Mass spectrum (FAB method, matrix-nitrobenzyl alcohol - le) M ⁺ +1: (as _{C 25 H 32 O 3 S 2} ) 445 Elemental analysis: C H S measured value (%) 67.48 7. 29 14.46 Calculated value (%) 67.53 7.25 14.42 Infrared absorption spectrum (cm ^-1 , CHCl ₃ ): 3446
_{(-OH), 1630,1605 (CH 2} = CH-Ph-) 1 H- nuclear magnetic resonance spectrum _{(ppm, CDCl 3): 7} .
38 to 7.23 (8H), 6.76 to 6.65 (2
H) 5.79-5.70 (2H), 5.27-5.2
1 (2H), 4.53 to 4.52 (4H), 3.82
(1H), 3.66 to 3.60 (4H), 3.30 (1
H) 2.82 to 2.61 (8H) (Example 3, Synthesis of MONO-3)
29.3 g of 3-dichloro-2-propanol (227 m
mol) and 19.1 g of 3,4-dihydro-2H-pyran
(227 mmol) in 25 ml of dichloromethane in 0.057 g of pyridinium-p-toluenesulfonate
(0.23 mmol) was added and reacted at room temperature for 24 hours.

The reaction solution was concentrated under reduced pressure, and 5-
64.3 g of mercapto-3-thia-1-pentanol
(465 mmol), 203 ml of ethanol and 36.3 g (908 mmol) of sodium hydroxide were added, and reacted at 80 ° C. for 16 hours under a nitrogen atmosphere. The reaction solution was extracted with ethyl acetate-10% saline, and the organic layer was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (dichloromethane-methanol 20: 1) to obtain 78.5 g (188 mmol) of a diol derivative represented by the following chemical formula (38).

[0108]

Embedded image To 150 ml of a toluene solution containing 78.5 g (188 mmol) of the diol was added 4-vinylbenzyl chloride.
8 g (385 mmol), 75.2 g of sodium hydroxide
(1.88 mol), 150 ml of water and 6.06 g (18.8 mmol) of tetrabutylammonium bromide were added and reacted at room temperature for 48 hours. The reaction solution was extracted with ethyl acetate-water, the organic layer was dehydrated with sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (dichloromethane) to obtain 107 g (165 mmol) of a protected alcohol represented by the following chemical formula (39).

[0109]

Embedded image To 333 ml of a methanol solution of 107 g (165 mmol) of the protected alcohol was added 2.07 g (8.24 mmol) of pyridinium-p-toluenesulfonate.
The reaction was performed at room temperature for 24 hours. The reaction solution was concentrated under reduced pressure, and the obtained residue was extracted with ethyl acetate-water.
The organic layer was dehydrated with sodium sulfate, concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (dichloromethane-methanol 100: 1) to give 89.5 g (158) of MONO-3.
mmol).

Purity (liquid chromatography): 9
9.7% Mass spectrum (FAB method, matrix-nitrobenzyl alcohol - le) M ⁺ +1: (as _{C 29 H 40 O 3 S 4} ) 565 Elemental analysis: C H S measured value (%) 61.63 7. 16 22.66 Calculated value (%) 61.66 7.14 22.71 Infrared absorption spectrum (cm ^-1 , CHCl ₃ ): 3492
_{(-OH), 1632,1604 (CH 2} = CH-Ph-) 1 H- nuclear magnetic resonance spectrum _{(ppm, CDCl 3): 7} .
37-7.25 (8H), 6.75-6.66 (2
H) 5.77-5.71 (2H), 5.25-5.2
2 (2H), 4.52 (4H), 3.70 (1H),
3.65-3.62 (4H), 2.93 (1H), 2.
78 to 2.57 (16H) (Example 4, synthesis of MONO-4) 93.5 g of bis (2-hydroxyethyl) sulfide (76) under a nitrogen atmosphere.
5mmol) and 93.5 g (613 mmol) of vinylbenzyl chloride (a 6: 4 mixture of meta- and para-forms)
Sodium hydride (65% oily product) (49.6 g, 1.34 mol) was added to 935 ml of dimethylformamide, and reacted at 0 ° C. for 3 hours.

The reaction solution was added to ice water and extracted with ethyl acetate. The organic layer was washed five times with water, dehydrated with sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (dichloromethane-methanol 100: 1) to give 5-
(Vinylbenzyloxy) -3-thia-1-pentano-
75.9 g (318 mmol) were obtained. This alcohol
The compound is represented by the following chemical formula (40).

[0112]

Embedded image To a solution of 75.9 g (318 mmol) of the alcohol compound in 250 ml of pyridine solution, 63.6 g (3
34 mmol) and reacted at 0 ° C. for 6 hours and at room temperature for 2 hours. The reaction solution was extracted with ethyl acetate-2N aqueous hydrochloric acid. The organic layer was washed with water, dehydrated with sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (dichloromethane-hexane 4: 1) to give 77.4 g (197 mmol) of a tosylated compound represented by the following chemical formula (41).
l) obtained.

[0113]

Embedded image 45.0 g (394 mmol) of a potassium salt of thioacetate was added to 1550 ml of a dimethylformamide solution of 77.4 g (197 mmol) of the tosyl compound, and the mixture was reacted at 0 ° C. for 1 hour and at room temperature for 4 hours. The reaction solution was extracted with ethyl acetate-water, the organic layer was washed five times with water, dehydrated with sodium sulfate, and concentrated under reduced pressure. By purifying the obtained residue by silica gel column chromatography (dichloromethane-hexane 2: 1),
54.9 g of an acetylthio compound represented by the following chemical formula (42)
(185 mmol) obtained.

[0114]

Embedded image Epichlorohydrin 8.15 was added to a solution of 54.9 g (185 mmol) of this acetylthio compound in 296 ml of toluene.
g (88.1 mmol), 5.96 g (18.5 mmol) of tetrabutylammonium bromide, and 296 m of an aqueous solution of 74.0 g (1.85 mol) of sodium hydroxide
1 was added and reacted at room temperature for 24 hours. The reaction solution was extracted with toluene-water, the organic layer was dehydrated with sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (dichloromethane-methanol 100: 1) to give MO.
43.3 g (76.7 mmol) of NO-4 was obtained.

Purity (liquid chromatography): 9
9.6% Mass spectrum (FAB method, matrix-nitrobenzyl alcohol - le) M ⁺ +1: (as _{C 29 H 40 O 3 S 4} ) 565 Elemental analysis: C H S measured value (%) 61.61 7. 18 22.75 Calculated value (%) 61.66 7.14 22.71 Infrared absorption spectrum (cm ^-1 , CHCl ₃ ): 3490
_{(-OH), 1630,1605 (CH 2} = CH-Ph-) 1 H- nuclear magnetic resonance spectrum _{(ppm, CDCl 3): 7} .
40-7.24 (8H), 6.77-6.66 (2
H) 5.79-5.71 (2H), 5.27-5.2
2 (2H), 4.53-4.52 (4H), 3.68
(1H), 3.66 to 3.62 (4H), 2.89 (1
H) 2.79 to 2.55 (16H) (Example 5, synthesis of MONO-5)
25.4 g of 3-dichloro-2-propanol (197 m
mol) and 1,6.6 g of 3,4-dihydro-2H-pyran
(197 mmol) in a 22 ml solution of dichloromethane in 0.050 g of pyridinium-p-toluenesulfonate
(0.20 mmol) was added and reacted at room temperature for 24 hours.

The reaction solution was concentrated under reduced pressure, and 8-
Mercapto-3,6-dithia-1-octanol 80.
1 g (404 mmol), 176 ml of ethanol and 31.5 g (788 mmol) of sodium hydroxide were added, and reacted at 80 ° C. for 16 hours under a nitrogen atmosphere. The reaction solution was extracted with ethyl acetate-10% saline, and the organic layer was concentrated under reduced pressure. The residue was subjected to silica gel column chromatography (dichloromethane-methanol 20:
By purifying in 1), 82.5 g (154 mmol) of a diol compound represented by the following chemical formula (43) was obtained.

[0117]

Embedded image 52.7 g (316 mmol) of 4-isopropenylbenzyl chloride and 123 ml of a toluene solution of 82.5 g (154 mmol) of this diol form were added to 123 ml of a toluene solution.
1.6 g (1.54 mol), 123 ml of water, 4.96 g (15.4 mm) of tetrabutylammonium bromide
ol) and reacted at room temperature for 48 hours. The reaction solution was extracted with ethyl acetate-water, the organic layer was dehydrated with sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (dichloromethane) to obtain 101 g (127 mmol) of a protected alcohol represented by the following chemical formula (44).

[0118]

Embedded image Pyridinium-p-toluenesulfonate (1.60 g, 6.37 mmol) was added to 256 ml of a methanol solution containing 101 g (127 mmol) of the protected alcohol.
The reaction was performed at room temperature for 24 hours. The reaction solution was concentrated under reduced pressure, and the obtained residue was extracted with ethyl acetate-water.
The organic layer was dehydrated with sodium sulfate, concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (dichloromethane-methanol 100: 1) to give 84.2 g (118) of MONO-5.
mmol).

Purity (liquid chromatography): 9
9.6% Mass spectrum (FAB method, matrix-nitrobenzyl alcohol - le) M ⁺ +1: (as _{C 35 H 52 O 3 S 6} ) 713 Elemental analysis: C H S measured value (%) 58.88 7. 40 26.91 Calculated value (%) 58.94 7.35 26.98 Infrared absorption spectrum (cm ^-1 , CHCl ₃ ): 3485
_{(-OH), 1629,1603 (CH 2} = CCH 3 -Ph-) 1 H- nuclear magnetic resonance spectrum _{(ppm, CDCl 3): 7} .
51-7.22 (8H), 5.37 (2H), 5.20
(2H), 4.56 (4H), 3.71 (1H), 3.
64 (4H), 2.91 to 2.52 (25H), 2.1
6 (6H) (Example 6, synthesis of MONO-6)
31.9 g of 5-dichloro-3-propanol (203 m
mol) and 14.7 g of ethyl vinyl ether (204 m
mol) in 0.05 ml of a pyridinium-p-toluenesulfonate (0.20 mol) in a 22 ml solution of dichloromethane.
mmol) and reacted at room temperature for 24 hours.

The reaction solution was concentrated under reduced pressure, and 2-D was added to the residue.
33.0 g (422 mmol) of mercaptoethanol,
185 ml of ethanol, 33.1 g of sodium hydroxide
(828 mmol) and reacted at 80 ° C. for 16 hours under a nitrogen atmosphere. The reaction solution was extracted with ethyl acetate-10% saline, and the organic layer was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (dichloromethane-methanol 20: 1) to give 55.8 g of a diol derivative represented by the following chemical formula (45).
(179 mmol) were obtained.

[0121]

Embedded image To 143 ml of a toluene solution containing 55.8 g (179 mmol) of the diol form was added vinylbenzyl chloride [m-p
Mixture of bodies (6: 4)] 56.0 g (367 mmol)
l), 71.6 g of sodium hydroxide (1.79 mol)
l), 143 ml of water and 5.77 g (17.9 mmol) of tetrabutylammonium bromide were added and reacted at room temperature for 48 hours. The reaction solution was extracted with ethyl acetate-water, the organic layer was dehydrated with sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (dichloromethane) to obtain 90.7 g (166 mmol) of a protected alcohol represented by the following chemical formula (46).

[0122]

Embedded image To 335 ml of a methanol solution of 90.7 g (166 mmol) of the protected alcohol was added 2.09 g (8.32 mmol) of pyridinium-p-toluenesulfonate, and the mixture was reacted at room temperature for 24 hours. The reaction solution was concentrated under reduced pressure, and the obtained residue was extracted with ethyl acetate-water. The organic layer was dehydrated with sodium sulfate, concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (dichloromethane-methanol 100: 1) to obtain 75.3 g (15%) of MONO-6.
9 mmol).

Purity (liquid chromatography): 9
9.8% Mass spectrum (FAB method, matrix-nitrobenzyl alcohol - le) M ⁺ +1: (as _{C 27 H 36 O 3 S 2} ) 473 Elemental analysis: C H S measured value (%) 68.64 7. 71 13.51 Calculated value (%) 68.60 7.68 13.57 Infrared absorption spectrum (cm ^-1 , CHCl ₃ ): 3462
_{(-OH), 1630,1605 (CH 2} = CH-Ph-) 1 H- nuclear magnetic resonance spectrum _{(ppm, CDCl 3): 7} .
38 to 7.22 (8H), 6.76 to 6.65 (2
H) 5.79-5.70 (2H), 5.27-5.2
0 (2H), 4.53-4.52 (4H), 3.71-
3.60 (5H), 2.92 to 2.55 (9H), 1.
96 to 1.80 (4H) (Example 7, Synthesis of MONO-7)
33.2 g of 3-dichloro-2-propanol (257 m
mol) and 25.8 g (258 m) of butyl vinyl ether
mol) in 0.028 g of pyridinium-p-toluenesulfonate (0.26 mol).
mmol) and reacted at room temperature for 24 hours.

The reaction solution was concentrated under reduced pressure, and 3-D was added to the residue.
48.6 g of mercapto-1-propanol (527 mm
ol), 230 ml of ethanol, sodium hydroxide 4
1.1 g (1.03 mol) was added and reacted at 80 ° C. for 16 hours under a nitrogen atmosphere. The reaction solution was ethyl acetate-
An extraction operation was performed with 10% saline, and the organic layer was concentrated under reduced pressure. The residue is purified by silica gel column chromatography.
By purifying with (dichloromethane-methanol 20: 1), 75.3 g (221 mmol) of a diol derivative represented by the following chemical formula (47) was obtained.

[0125]

Embedded image To 177 ml of a toluene solution containing 75.3 g (221 mmol) of the diol form, vinylbenzyl chloride [m-p
Mixture of bodies (6: 4)] 69.2 g (453 mmo)
l), 88.4 g of sodium hydroxide (2.21 mol)
l), water (177 ml) and tetrabutylammonium bromide (7.12 g, 22.1 mmol) were added, and the mixture was reacted at room temperature for 48 hours. The reaction solution was extracted with ethyl acetate-water, the organic layer was dehydrated with sodium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (dichloromethane) to obtain 118 g (206 mmol) of a protected alcohol represented by the following chemical formula (48).

[0126]

Embedded image To 416 ml of a methanol solution containing 118 g (206 mmol) of the protected alcohol was added 2.59 g (10.3 mmol) of pyridinium-p-toluenesulfonate.
The reaction was performed at room temperature for 24 hours. The reaction solution was concentrated under reduced pressure, and the obtained residue was extracted with ethyl acetate-water.
The organic layer was dehydrated with sodium sulfate, concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (dichloromethane-methanol 100: 1) to give 92.5 g (196) of MONO-7.
mmol).

Purity (liquid chromatography): 9
9.7% Mass spectrum (FAB method, matrix-nitrobenzyl alcohol - le) M ⁺ +1: (as _{C 27 H 36 O 3 S 2} ) 473 Elemental analysis: C H S measured value (%) 68.56 7. 65 13.62 Calculated value (%) 68.60 7.68 13.57 Infrared absorption spectrum (cm ^-1 , CHCl ₃ ): 3466
_{(-OH), 1630,1605 (CH 2} = CH-Ph-) 1 H- nuclear magnetic resonance spectrum _{(ppm, CDCl 3): 7} .
39 to 7.22 (8H), 6.77 to 6.65 (2
H) 5.79-5.70 (2H), 5.27-5.2
0 (2H), 4.53-4.52 (4H), 3.83-
3.60 (5H), 3.26 (1H), 2.87-2.
58 (8H), 1.94 to 1.78 (4H) Next, polymerization was performed using each of the monomers synthesized above,
A plastic optical material having a predetermined shape was prepared. This will be described in the following examples.

The physical properties of the plastic optical material were measured and evaluated by the following methods. Refractive index and Abbe number: The refractive index and Abbe number of the molded article were measured using an Abbe refractometer [trade name 2T manufactured by Atago Co., Ltd.].

Specific gravity: The specific gravity of the molded product was measured using a specific gravity measuring device [SGM-300P (trade name, manufactured by Shimadzu Corporation)]. Impact resistance: A steel ball of 45 g was dropped from a height of 127 cm onto a molded product (diameter: 8 cm, thickness: 1.8 mm).

Heat resistance: After the molded product was left in a dryer at 130 ° C. for 2 hours, it was visually observed and “film orientation viewer”.
The molded product was observed under a trade name (trade name of Unitika Risa-Chilabo).も の indicates no change in deformation, cracking, surface deterioration, coloring, etc., and × indicates any of them.

Solvent resistance: After leaving the molded article in acetone for 2 hours, the molded article was evaluated as ○ when no deformation, cracking, or change in color was observed, and was evaluated as × when observed. Stainability: 2 g of Seiko-Plax Diamond Coat Brown D was dispersed in 1 liter of water at 90 ° C. to prepare a stain solution. This dyeing solution was immersed in the dyeing solution for 10 minutes to perform dyeing. There was no unevenness in dyeing, and the difference between before and after staining was 4 in luminous transmittance (measurement instrument: MODEL304 manufactured by Asahi Spectroscopy Co., Ltd.).
Those with 0% or more were rated as ○, and those with less than 40% were rated as x. (Example 8) 20 g of MONO-1 and 0.2 g of t-butyl peroxy-2-ethylhexanoate as a polymerization initiator were mixed and deaerated. Then, two pieces of glass having a diameter of 8 cm and silica were mixed. And into a lens casting mold consisting of a gasket made of-. Place them in a constant temperature bath purged with nitrogen.
Heat from 0 ° C to 110 ° C over 15 hours, then add
Heated at 10 ° C. for 2 hours. After the heat curing, the cured molded product was taken out of the mold and annealed at 120 ° C. for 4 hours.

For the molded product, the refractive index, Abbe number,
The specific gravity, impact resistance, heat resistance, solvent resistance and physical properties of the dyeing property were measured, and the results are shown in Table 1. (Examples 9 to 86) In Example 8, MONO-2, 3, 4, 6, and 7 alone and MONO-1 were substituted for MONO-1.
Thermosetting molding and annealing were performed in the same manner as in Example 8 except that each of NO-2 and 5 mixed with another monomer was used. For the molded product, the refractive index, Abbe number, specific gravity, impact resistance, heat resistance, solvent resistance, and dyeing properties were measured, and the results are shown in Tables 1 to 7. (Comparative Examples 1 and 2) ST and BZ (20 g each) and t-butyl peroxy-2-ethylhexanoate (0.2 g) as a polymerization initiator were mixed and degassed. It was poured into a lens casting mold consisting of glass and a silicone gasket. They were heated from 40 ° C. to 80 ° C. over 15 hours in a constant temperature bath purged with nitrogen, and further heated at 80 ° C. for 2 hours. After the heat curing, the cured molded product was taken out of the mold and annealed at 80 ° C. for 4 hours. The refractive index, Abbe number, specific gravity,
The physical properties of impact resistance, heat resistance, solvent resistance and dyeability were measured, and the results are shown in Table 7. (Comparative Example 3) Thermosetting molding and annealing were performed in the same manner as in Example 8, except that only REFE-1 was used as the monomer. For the molded product, the refractive index, Abbe number, specific gravity, impact resistance, heat resistance, solvent resistance and dyeing properties were measured,
Table 7 shows the results.

No coloring was observed in any of the molded products of Examples 8 to 86 and Comparative Examples 1, 2 and 3, and the molded products were colorless and transparent.

[0134]

[Table 1]

[0135]

[Table 2]

[0136]

[Table 3]

[0137]

[Table 4]

[0138]

[Table 5]

[0139]

[Table 6]

[0140]

[Table 7] As shown in Tables 1 to 7, in the homopolymers of Examples 8 to 86, the refractive index is 1.59 or more, the Abbe number is high, and the impact resistance is excellent. Moreover, it has excellent heat resistance, solvent resistance, and dyeability, and has a small specific gravity of 1.21 or less.

On the other hand, as shown in Table 7, Comparative Examples 1 and 2, which are homopolymers outside the scope of the present invention, had a refractive index of 1.59 or less and were inferior in impact resistance and dyeability. ing. In addition, heat resistance and solvent resistance are poor. Also,
Comparative Example 3, which is a polymer outside the scope of the present invention, is also inferior in impact resistance and dyeability.

The technical idea grasped from the above embodiment will be described below. (A) The styrene monomer according to claim 1 or 2, wherein R in the general formula (1) is an alkylene group having a total carbon number of 3 to 7 including a sulfur atom.

In the case of such a constitution, physical properties such as impact resistance and dyeability of the obtained styrenic polymer are improved,
The refractive index can be reliably increased. (B) The styrene monomer according to claim 1 or 2, wherein R in the general formula (1) has a ratio of the number of carbon atoms to the number of sulfur atoms of 2 to 5.

With such a constitution, the refractive index of the obtained styrenic polymer can be effectively increased. (C) CH ₂ = CX- group styrene monomer according to claim 1 or 2 in meta or para position of the benzene ring in the general formula (1).

With such a constitution, the styrene monomer represented by the general formula (1) can be obtained efficiently. (D) a compound obtained by reacting a dihydroxy compound having a protected hydroxyl group and containing a sulfur atom with a vinyl or isopropenyl benzyl halide in the presence of a catalyst, followed by deprotection. A styrene-based monomer represented by the general formula (1).

According to this configuration, the styrene-based monomer represented by the general formula (1) can be easily obtained with a high yield. (E) The styrene-based polymer according to claim 3 or 4, wherein only the styrene-based monomer is polymerized.

In the case of such a constitution, the physical properties such as the refractive index and the impact resistance of the styrene-based polymer can be reliably exhibited based on the styrene-based monomer. (F) The styrene-based polymer according to claim 3 or 4, wherein the styrene-based monomer is a main component, and a monomer copolymerizable therewith is copolymerized.

With such a constitution, physical properties such as the refractive index and impact resistance of the styrenic polymer can be effectively exhibited. (G) The styrene-based polymer according to claim 3, wherein a monomer containing a styrene-based monomer represented by the general formula (1) is polymerized with a polymerization initiator under an inert gas atmosphere. Production method.

According to this method, it is possible to prevent a reduction in the polymerization rate and a coloring of the polymer during the polymerization of the styrene monomer. (H) a styrene monomer represented by the general formula (1):
The styrenic polymer according to claim 3 or 4, wherein the styrenic polymer is mixed with a compound having a functional group that reacts with the hydroxyl group of the styrenic monomer and polymerized by a heat curing method.

With such a constitution, it is possible to improve physical properties such as impact resistance and heat resistance of the obtained polymer. (I) The styrene polymer according to (h), wherein the compound having a functional group that reacts with the hydroxyl group of the styrene monomer is an isocyanate compound.

In the case of such a constitution, physical properties such as impact resistance and heat resistance of the obtained polymer can be surely improved. (V) The plastic optical material according to claim 5, further subjected to a heat treatment.

With such a configuration, the internal distortion of the plastic optical material can be removed. (11) The styrene-based polymer according to claim 10, wherein the styrene-based monomer is a main component, and a monomer copolymerizable therewith is copolymerized.

With such a constitution, physical properties such as the refractive index and impact resistance of the styrenic polymer can be effectively exhibited.

[0154]

As described above, according to the present invention, the following excellent effects can be obtained. According to the novel styrene monomer of the first invention and the novel styrene polymer of the third invention, the polymer obtained from the styrene monomer has good physical properties such as heat resistance and solvent resistance. , The refractive index and Abbe number can be increased, and the impact resistance and the dyeability can be improved.

According to the styrene monomer of the second invention,
The effect of the first invention can be more reliably exerted. According to the styrenic polymer for a plastic optical material of the fourth invention, in addition to the effects of the third invention, an optical material having a predetermined shape can be easily obtained by a heat-curing method, and an active energy ray can be obtained. An optical material having a predetermined shape can be quickly obtained by a curing method. According to the plastic optical material of the fifth invention, the optical material maintains good physical properties such as heat resistance and solvent resistance, can increase the refractive index and Abbe number, and can improve impact resistance and dyeability. It can be suitably used as a plastic lens for eyeglasses and the like. Further, since the sulfur atom is not directly bonded to the benzyl position or the benzene ring, it is excellent in light resistance and weather resistance. In addition, since it has a hydroxyl group, it has excellent hard coat adhesion. Therefore, the present invention is extremely useful industrially.

According to the novel styrene-based monomer composition of the sixth invention, in addition to the effects of the first invention, the refractive index of the obtained styrene-based polymer is determined based on the properties of the monomer having a vinyl group. It is possible to further improve physical properties such as a rate, an Abbe number, and impact resistance and dyeability.

According to the styrene-based monomer composition of the seventh invention, in addition to the effects of the sixth invention, the resulting polymer has an abbe based on the properties of the monomer having a (meth) acryloyl group. The number can be improved.

According to the styrenic monomer composition of the eighth invention, in addition to the effect of the seventh invention, the polymer obtained is crosslinked by a monomer having a bifunctional (meth) acryloyl group. It has a structure and can improve impact resistance and heat resistance.

According to the styrenic monomer composition of the ninth aspect, in addition to the effects of the sixth aspect, it is possible to maintain a high refractive index based on the properties of the monomer having a specific vinyl group. Can be.

According to the styrenic polymers for plastic optical materials of the tenth and eleventh aspects, in addition to the effects of the sixth to ninth aspects, an optical material having a predetermined shape can be easily obtained by a heat curing method. Active energy
An optical material having a predetermined shape can be promptly obtained by the line curing method.

According to the plastic optical material of the twelfth aspect, the effects of the sixth aspect can be further improved according to the purpose.

Claims (12)

[Claims] 1. A styrene monomer represented by the following general formula (1). Embedded image (Wherein, R is an alkylene group having a total of 2 to 11 carbon atoms including a sulfur atom, and X is a hydrogen atom or a methyl group.) 2. The styrene monomer according to claim 1, wherein R in the general formula (1) is an alkylene group represented by the following general formula (2). − (CH ₂ CH ₂ S) _m − (CH ₂ ) _n − (2) (where m and n are each an integer of 1 to 5) 3. A styrene polymer obtained by polymerizing a monomer containing the styrene monomer according to claim 1. 4. A method for curing a monomer containing the styrenic monomer according to claim 1 or 2 using a heat curing method or an active energy method.
Styrene-based polymer for plastic optical materials obtained by polymerization by the line curing method. 5. A plastic optical material obtained by molding the styrenic polymer according to claim 3 into a predetermined shape. 6. A styrene monomer composition comprising the styrene monomer according to claim 1 and at least one monomer having a vinyl group. 7. The styrene monomer composition according to claim 6, wherein the monomer having a vinyl group is a monomer having a (meth) acryloyl group. 8. The styrene monomer composition according to claim 7, wherein the monomer having a (meth) acryloyl group is a monomer represented by the following general formula (3). Embedded image (Where Y is a hydrogen atom or a methyl group, and A is C 2
An alkylene group of 6 to 6, p represents an integer of 1 to 25; ) 9. The styrene monomer composition according to claim 6, wherein the monomer having a vinyl group is a monomer represented by the following general formula (4). Embedded image (Where α represents a hydrogen atom or a methyl group, β represents a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 6 carbon atoms or a vinyl group). 10. A styrenic polymer obtained by polymerizing the styrenic monomer composition according to any one of claims 6 to 9. 11. A styrene polymer for a plastic optical material obtained by polymerizing the styrene monomer composition according to claim 6 by a heat curing method or an active energy ray curing method. . 12. A plastic optical material obtained by molding the styrene-based polymer according to claim 10 into a predetermined shape.