JP2003128668A - New polythiol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new polythiol compound with which resin having an improved refractive index can be produced compared to the resin made from 2,5-bis(mercaptomethyl)-1,4-dithiane. SOLUTION: A new polythiol represented by formula (I) is used.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to various raw materials and additives such as polyurethane resin raw materials, coating raw materials, (thio) epoxy resin curing agents, vulcanizing agents for synthetic resins, and sulfur-containing (meth) compounds. Regarding a polythiol useful as a raw material for various sulfur-containing compounds such as an acrylic compound, a sulfur-containing epoxy compound, and a sulfur-containing episulfide compound, a polythiol particularly suitable as a monomer for plastic lenses and a polymerizable composition using the same, and polymerizing the same The present invention relates to an optical resin thus obtained and a plastic lens made of the resin.

[0002]

2. Description of the Prior Art Thiourethane plastic lenses are
Due to its tough properties and excellent optical properties, it is now widely used in plastic lens applications for eyeglasses. Above all, urethane plastic lenses using 2,5-bis (mercaptomethyl) -1,4-dithiane (Japanese Patent Publication No.
No. 5585 and Japanese Patent Publication No. 6-5323) are characterized in that they are superior in heat resistance to other urethane-based plastic lenses using polythiols.

[0003]

However, even if this 2,5-bis (mercaptomethyl) -1,4-dithiane is used, a polycondensate giving a high refractive index typified by, for example, xylylene diisocyanate. Even when polymerized with isocyanate, the refractive index was still insufficient.

[0004]

Means for Solving the Problems The inventors of the present invention have made extensive studies to solve the above-mentioned problems, and as a result, the following formula (I)

[0005]

[Chemical 2] When a novel polythiol represented by the formula is created and the compound is used, 2,5-bis (mercaptomethyl) -1,4
-The present invention was found by finding that the refractive index is further improved as compared with the case of using dithiane.

That is, the present invention is: 1) A polythiol represented by the above formula (I). 2) A polymerizable composition containing the polythiol according to 1. 3) The polymerizable composition according to 2 containing the polythiol according to 1 and polyiso (thio) cyanate. 4) An optical resin obtained by polymerizing the polymerizable composition according to 2 or 3. 5) An optical element made of the optical resin described in 4. 6) A lens comprising the optical element described in 5. It is about.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
The polythiol of formula (I) according to the present invention has 4-mercapto-3-mercaptomethyl-2- with a dithiolane skeleton.
It is a novel compound having a thiabutyl group bonded.

The polythiol represented by the formula (I) according to the present invention can be produced, for example, by the following method.

Acetylthiomethyldialkylacetal is synthesized by reacting halomethyldialkylacetal with thioacetic acid metal salt.

The metal salt of thioacetic acid to be reacted is not particularly limited, but potassium thioacetate, sodium thioacetate, calcium thioacetate and magnesium thioacetate are preferably used, and sodium thioacetate and potassium thioacetate are particularly preferably used. To be done.

The reaction temperature is approximately -10 ° C to 100 ° C.
C., preferably 20 to 70.degree.

In the present invention, the reaction is preferably carried out in a solvent, and the solvent used is not particularly limited as long as it does not inhibit the reaction, but water, alcohols such as methanol, ethanol and methoxyethanol, toluene,
Aromatic hydrocarbon solvents such as xylene, dimethylformamide, dimethylsulfoxide, N, N-dimethylimidazolidinone and the like are preferably used.

Then, acetal exchange with ethanedithiol is carried out to synthesize 2-acetylthio-1,3-dithiolane.

The acetal exchange is preferably carried out in a solvent, which does not adversely affect the quality of the product obtained,
A solvent having good liquid separation property and high yield is preferably used. For example, aromatic hydrocarbon solvents such as toluene and xylene, and halogenated hydrocarbon solvents such as dichloromethane, dichloroethane and chlorobenzene are preferably used.

When the acetal is exchanged, an acidic catalyst for accelerating the reaction is optionally used. Examples thereof include sulfuric acid, hydrochloric acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid and dibutyltin oxide.

The reaction temperature for acetal exchange is 20 ° C to 1 ° C.
The temperature is in the range of 50 ° C, preferably 40 ° C to 100 ° C.

Next, 2-mercaptomethyl-1,3-dithiolane is synthesized by thiolating 2-acetylthio-1,3-dithiolane.

The thiolation method can be carried out by hydrolysis, alcoholysis or the like. As a specific method, an acid or a base is added to water or an alcohol solvent such as methanol or ethanol.

As the acid to be added, a mineral acid such as hydrochloric acid or sulfuric acid, an organic acid such as benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid or dibutyltin oxide is used under acidic conditions.

As the base to be added, aqueous sodium hydroxide, aqueous potassium hydroxide, aqueous ammonia, hydrazine water,
Examples include bases such as aqueous sodium carbonate.

Next, 2-mercaptomethyl-1,3-dithiolane is reacted with epihalohydrin to give 2- (1-
Halogeno-2-hydroxy-4-thiapentyl) -1,
3-Dithiolane is synthesized.

The reaction with epihalohydrin is preferably carried out in a solvent, and the solvent used is not particularly limited as long as it does not inhibit the reaction, but water, alcohols such as methanol, ethanol and methoxyethanol, toluene Aromatic hydrocarbon solvents such as, xylene and the like are preferably used.

The reaction temperature is approximately -10 ° C to 100 ° C.
It is in the range of 0 ° C, preferably in the range of 0 ° C to 50 ° C.

The epihalohydrin used is preferably 1.0 equivalent to 1.5 equivalents, particularly preferably 1.0 equivalent to 1.2 equivalents, based on 2-mercaptomethyl-1,3-dithiolane. It

The resulting 2- (1-halogeno-2-hydroxy-4-thiapentyl) -1,3-dithiolane is reacted with thiourea to form an isothiuronium salt,
It is hydrolyzed to synthesize the polythiol represented by the formula (I) according to the present invention.

The isothiuronium chloride is preferably reacted in a solvent, and the solvent used in this case is water, alcohols or halogenated hydrocarbons.

As the alcohol, methanol, ethanol, isopropanol, butanol and the like are preferably used.

Examples of halogenated hydrocarbons include dichloromethane, dichloroethane, chloroform, chlorobenzene and the like.

The reaction temperature cannot be strictly limited depending on the solvent used, but is generally in the range of 0 ° C to 200 ° C,
It is preferably in the range of 20 ° C to 120 ° C.

An acidic catalyst is optionally used to promote isothiuronium chloride. Examples thereof include sulfuric acid, hydrochloric acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid and dibutyltin oxide.

Subsequent hydrolysis is carried out using normal basic water. Examples of the type of basic water used include bases such as sodium hydroxide water, potassium hydroxide water, ammonia water, hydrazine water, and sodium carbonate water. Among them, ammonia water gives preferable results. .

The amount of the base used is 2- (1-halogeno-2).
-Hydroxy-4-thiapentyl) -1,3-dithiolane in the range of 2 to 6 equivalents, preferably 2.4 to 4.8 equivalents.

The reaction temperature for hydrolysis varies considerably depending on the type of basic water used, so it is difficult to limit it, but it is generally in the range of 0 ° C to 100 ° C, preferably 20 ° C to 70 ° C.
It is in the range of ° C.

The solvent used for hydrolysis is water or alcohols such as methanol, ethanol, isopropanol, butanol, etc., aromatic hydrocarbon solvents such as toluene, xylene, etc., halogenated hydrocarbons such as dichloromethane, dichloroethane, chlorobenzene, etc. A system solvent is preferably used.

The isothiuronium chloride reaction in the previous step
When performing hydrolysis with water and alcohols without removing the reaction product, it is better to add aromatic hydrocarbon solvents such as toluene and xylene and perform hydrolysis in a two-layer system after that. This is relatively preferable because the washing operation and the like that are performed can be performed efficiently and in a short time.

The formula (I) relating to the present invention thus obtained
The reaction solution containing is usually subjected to various washings such as acid washing, base washing, and water washing as necessary, and after removing the solvent, the product is obtained by filtration. Further, it is purified by a commonly used known purification method such as distillation and column chromatography.

The polythiol according to the present invention thus obtained is used as a raw material for polyurethane resin, a raw material for coating material, an epoxy curing agent, a synthetic resin vulcanizing agent, etc., in addition to being used as a monomer for optical resins, particularly as a monomer for plastic lenses. It can be suitably used for various raw materials and additives, and for a wide variety of uses such as raw materials for various sulfur-containing compounds such as sulfur-containing (meth) acrylic compounds, sulfur-containing epoxy compounds, and sulfur-containing episulfide compounds.

Next, the production of the plastic lens according to the present invention will be described. The polythiol represented by the formula (I) according to the present invention is a compound having a group that reacts with a mercapto group, for example, a polyiso (thio) cyanate, a (thio) epoxy group, a compound having an unsaturated group, and if necessary, added. After mixing evenly with the agent, defoaming by stirring under reduced pressure,
The defoaming liquid is injected into the molding mold and cured mainly by heating or radiation to obtain the plastic lens of the present invention.

The heating conditions are such that the temperature is gradually raised from a low temperature to a high temperature within a temperature range of approximately 0 ° C. to 200 ° C., and the heating is completed in approximately 1 hour to 100 hours.

In the case of polymerizing by radiation, it is mainly 40
Ultraviolet rays of 0 nm or less are often used. The UV irradiation conditions are often 1 mJ / sec to 1000 mJ / sec with an intensity of 1 sec to 7200 sec. In some cases, it is cooled before irradiation for the purpose of removing heat or obtaining an optically uniform molded product. Irradiation may be performed while cooling, or irradiation may be performed several times.

The polyiso (thio) cyanate as the polymerizable composition of the present invention is an organic compound having two or more iso (thio) cyanate groups in the molecule, and examples thereof include the following compounds. Hexamethylene diisocyanate, 2,2-dimethylpentane diisocyanate, 2,
2,4-trimethylhexane diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecanetri Isocyanate, 1,3,6-hexamethylenetriisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, lysine diisocyanatomethyl ester , Lysine triisocyanate, xylylene diisocyanate, bis (isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, α, α, α ', α'-tetramethylxylylene diisocyanate, bis (isocyanatobutyl) Benzene, bis (isocyanatomethy A) naphthalene, bis (isocyanatomethylphenyl) ether, bis (isocyanatoethyl) phthalate, aliphatic polyisocyanate compounds such as 2,6-di (isocyanatomethyl) furan, isophorone diisocyanate, bis (isocyanato) Methyl) cyclohexane, cyclohexane diisocyanate, methyl cyclohexane diisocyanate, 4,4 '
-Methylenebis (cyclohexyl isocyanate),
4,4'-methylenebis (2-methylcyclohexyl isocyanate), 2,5-bis (isocyanatomethyl)
Bicyclo- [2,2,1] -heptane, 2,6-bis (isocyanatomethyl) bicyclo- [2,2,1] -heptane, 3,8-bis (isocyanatomethyl) tricyclodecane, 3, Alicyclic polyisocyanate compounds such as 9-bis (isocyanatomethyl) tricyclodecane, 4,8-bis (isocyanatomethyl) tricyclodecane, 4,9-bis (isocyanatomethyl) tricyclodecane,

1,2-diisocyanatobenzene, 1,3
-Diisocyanatobenzene, 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethylphenylene diisocyanate,
Diethyl phenylene diisocyanate, diisopropyl phenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, biphenyl diisocyanate, toluidine diisocyanate,
4,4′-methylenebis (phenyl isocyanate),
4,4'-methylenebis (2-methylphenylisocyanate), bibenzyl-4,4'-diisocyanate,
Aromatic polyisocyanate compounds such as bis (isocyanatophenyl) ethylene,

Bis (isocyanatomethyl) sulfide,
Bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, bis (isocyanatohexyl) sulfide, bis (isocyanatomethyl) sulfone, bis (isocyanatomethyl) disulfide, bis (isocyanatoethyl) disulfide, bis ( Isocyanatopropyl) disulfide, bis (isocyanatomethylthio) methane, bis (isocyanatoethylthio) methane, bis (isocyanatoethylthio) ethane, bis (isocyanatomethylthio) ethane, 1,5-diisocyanato-2-isocyanato Methyl-3-thiapentane, 1,
2,3-tris (isocyanatomethylthio) propane,
1,2,3-Tris (isocyanatoethylthio) propane, 3,5-dithia-1,2,6,7-heptane tetraisocyanate, 2,6-diisocyanatomethyl-3,
5-dithia-1,7-heptane diisocyanate, 2,
5-diisocyanatomethylthiophene, 4-isocyanatoethylthio-2,6-dithia-1,8-octane diisocyanate, and other sulfur-containing aliphatic isocyanate compounds,

Aromatic sulfide type isocyanate compounds such as 2-isocyanatophenyl-4-isocyanatophenyl sulfide, bis (4-isocyanatophenyl) sulfide, bis (4-isocyanatomethylphenyl) sulfide, bis (4-) Isocyanatophenyl) disulfide, bis (2-methyl-5-isocyanatophenyl) disulfide, bis (3-methyl-5-isocyanatophenyl) disulfide, bis (3-methyl-6-isocyanatophenyl) disulfide, bis ( 4-methyl-5-isocyanatophenyl) disulfide, bis (3
-Methoxy-4-isocyanatophenyl) disulfide, bis (4-methoxy-3-isocyanatophenyl)
Aromatic disulfide-based isocyanate compounds such as disulfide,

2,5-diisocyanatotetrahydrothiophene, 2,5-diisocyanatomethyltetrahydrothiophene, 3,4-diisocyanatomethyltetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, 2,5 -Diisocyanatomethyl-1,4-dithiane, 4,5-diisocyanato-1,3-dithiolane,
4,5-bis (isocyanatomethyl) -1,3-dithiolane, 4,5-diisocyanatomethyl-2-methyl-
Sulfur-containing alicyclic compounds such as 1,3-dithiolane, aliphatic isothiocyanate compounds such as 1,2-diisothiocyanatohexane and 1,6-diisothiocyanatohexane, and fats such as cyclohexanediisothiocyanate A cyclic isothiocyanate compound,

1,2-diisothiocyanatobenzene,
1,3-diisothiocyanatobenzene, 1,4-diisothiocyanatobenzene, 2,4-diisothiocyanatotoluene, 2,5-diisothiocyanato-m-xylene,
4,4'-diisothiocyanatobiphenyl, 4,4'-
Methylenebis (phenylisothiocyanate), 4,
4'-methylenebis (2-methylphenylisothiocyanate), 4,4'-methylenebis (3-methylphenylisothiocyanate), 4,4'-isopropylidenebis (phenylisothiocyanate), 4,4'- Aromatic isothiocyanate compounds such as diisothiocyanatobenzophenone, 4,4′-diisothiocyanato-3,3′-dimethylbenzophenone, bis (4-isothiocyanatophenyl) ether,

Further, 1,3-benzenedicarbonyldiisothiocyanate, 1,4-benzenedicarbonyldiisothiocyanate, (2,2-pyridine) -4,4
Carbonylisothiocyanate compounds such as dicarbonyldiisothiocyanate, sulfur-containing aliphatic compounds such as thiobis (3-isothiocyanatopropane), thiobis (2-isothiocyanatoethane), dithiobis (2-isothiocyanatoethane) Isothiocyanate compound, 1-isothiocyanato-4-[(2-isothiocyanato) sulfonyl]
Sulfur-containing aromatic isothiocyanate compounds such as benzene, thiobis (4-isothiocyanatobenzene), sulfonylbis (4-isothiocyanatobenzene), dithiobis (4-isothiocyanatobenzene), 2,5-diisothiocyanana Sulfur-containing alicyclic compounds such as tothiophene and 2,5-diisothiocyanato-1,4-dithiane,

1-isocyanato-6-isothiocyanatohexane, 1-isocyanato-4-isothiocyanatocyclohexane, 1-isocyanato-4-isothiocyanatobenzene, 4-methyl-3-isocyanato-1-isothiocyanatobenzene , 2-isocyanato-4,6-diisothiocyanato-1,3,5-triazine, 4-isocyanatophenyl-4-isothiocyanatophenyl sulfide, 2-isocyanatoethyl-2-isothiocyanatoethyl disulfide and the like. And a compound having an isothiocyanato group and an isothiocyanato group.

The present invention is not limited to these listed compounds. Further, these chlorine-substituted compounds, halogen-substituted compounds such as bromine-substituted compounds, alkyl-substituted compounds, alkoxy-substituted compounds, nitro-substituted compounds and prepolymer modified products with polyhydric alcohols, carbodiimide modified products, urea modified products, and burette modified products. Body, dimerization or trimerization reaction products can also be used.

The polymerizable composition according to the present invention may contain a (thio) epoxy compound and a compound having an unsaturated group described below. The (thio) epoxy compound is a compound containing one or more (thio) epoxy groups in the molecule, and examples thereof include bis (1,2-epithioethyl) sulfide and bis (2,3-epithiopropyl) disulfide. , Bis (2,3-epithiopropyl) sulfide, bis (2,3-epithiopropylthio) methane,
1,2-bis (2,3-epithiopropylthio) ethane, 1,2-bis (2,3-epithiopropylthio) propane, 1,3-bis (2,3-epithiopropylthio) propane , 1,3-bis (2,3-epithiopropylthio) -2-methylpropane, 1,4-bis (2,3
-Epithiopropylthio) butane, 1,4-bis (2,2
3-epithiopropylthio) -2-methylbutane, 1,
3-bis (2,3-epithiopropylthio) butane,
1,5-bis (2,3-epithiopropylthio) pentane, 1,5-bis (2,3-epithiopropylthio)-
2-methylpentane, 1,5-bis (2,3-epithiopropylthio) -3-thiapentane, 1,6-bis (2,3-epithiopropylthio) hexane, 1,6-
Bis (2,3-epithiopropylthio) -2-methylhexane, 3,8-bis (2,3-epithiopropylthio) -3,6-dithiaoctane, 1,2,3-tris (2,3 -Epithiopropylthio) propane, 2,2-
Bis (2,3-epithiopropylthiomethyl) -1,3
-Bis (2,3-epithiopropylthio) propane,
2,2-bis (2,3-epithiopropylthiomethyl)
-1- (2,3-epithiopropylthio) butane, 1,
5-bis (2,3-epithiopropylthio) -2-
(2,3-Epithiopropylthiomethyl) -3-thiapentane, 1,5-bis (2,3-epithiopropylthio) -2,4-bis (2,3-epithiopropylthiomethyl) -3 -Thiapentane, 1- (2,3-epithiopropylthio) -2,2-bis (2,3-epithiopropylthiomethyl) -4-thiahexane, 1,5,6-tris (2,3-epi) Thiopropylthio) -4- (2,3-
Epithiopropylthiomethyl) -3-thiahexane,
1,8-bis (2,3-epithiopropylthio) -4-
(2,3-Epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropylthio) -4,5-bis (2,3-epithiopropylthiomethyl) -3,6-Dithiaoctane, 1,8-bis (2,3-epithiopropylthio) -4,4-bis (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8- Bis (2,3-epithiopropylthio) -2,5-bis (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropylthio) -2,4,5-Tris (2,3-epithiopropylthiomethyl) -3,6-
Dithiaoctane, 1,1,1-tris [{2- (2,3
-Epithiopropylthio) ethyl} thiomethyl] -2-
(2,3-Epithiopropylthio) ethane, 1,1,
2,2-Tetrakis [{2- (2,3-epithiopropylthio) ethyl} thiomethyl] ethane, 1,11-bis (2,3-epithiopropylthio) -4,8-bis (2,3 -Epithiopropylthiomethyl) -3,6,9
-Trithiaundecane, 1,11-bis (2,3-epithiopropylthio) -4,7-bis (2,3-epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1, 11-bis (2,3-epithiopropylthio)
A chain aliphatic 2,3-epithiopropylthio compound such as -5,7-bis (2,3-epithiopropylthiomethyl) -3,6,9-trithiaundecane, and

1,3-bis (2,3-epithiopropylthio) cyclohexane, 1,4-bis (2,3-epithiopropylthio) cyclohexane, 1,3-bis (2,2)
3-epithiopropylthiomethyl) cyclohexane,
1,4-bis (2,3-epithiopropylthiomethyl)
Cyclohexane, 2,5-bis (2,3-epithiopropylthiomethyl) -1,4-dithiane, 2,5-bis [{2- (2,3-epithiopropylthio) ethyl} thiomethyl] -1 , 4-dithiane, 2,5-bis (2,3
-Epithiopropylthiomethyl) -2,5-dimethyl-
A cycloaliphatic 2,3-epithiopropylthio compound such as 1,4-dithiane, and

1,2-bis (2,3-epithiopropylthio) benzene, 1,3-bis (2,3-epithiopropylthio) benzene, 1,4-bis (2,3-epithiopropyl) Thio) benzene, 1,2-bis (2,3-epithiopropylthiomethyl) benzene, 1,3-bis (2,3-epithiopropylthiomethyl) benzene,
1,4-bis (2,3-epithiopropylthiomethyl)
Benzene, bis {4- (2,3-epithiopropylthio) phenyl} methane, 2,2-bis {4- (2,3-)
Epithiopropylthio) phenyl} propane, bis {4
-(2,3-Epithiopropylthio) phenyl} sulfide, bis {4- (2,3-epithiopropylthio) phenyl} sulfone, 4,4'-bis (2,3-epithiopropylthio) biphenyl Aromatic 2,3-epithiopropylthio compounds and the like, and further mercapto group-containing epithio compounds such as 3-mercaptopropylene sulfide and 4-mercaptobutene sulfide.
The present invention is not limited to these listed compounds.

As the compound having an unsaturated group,
For example, the following compounds may be mentioned. Benzyl (meth) acrylate, butoxyethyl (meth) acrylate, butoxymethyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate,
Thioglycidyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, bisphenol A di (meth) acrylate, 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2 -Bis (4- (meth) acryloyloxyethoxyethoxyphenyl) propane, bisphenol F di (meth) acrylate, bis (4- (meth) acryloyloxyethoxyphenyl) methane, 1 1-bis (4- (meth) acryloxyethoxyphenyl) methane, trimethylolpropane tri (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, etc. (Meth) acrylate compound,

(Meth) acryloylthioethane, (meth) acryloylthiomethylbenzene, 1,2-bis {(meth) acryloylthio} ethane, 1,3-bis {(meth) acryloylthio} propane, 1,4- Bis {(meth) acryloylthio} butane, 1,6-bis {(meth) acryloylthio} hexane, bis {2-
(Meth) acryloylthioethyl} ether, bis {2
-(Meth) acryloylthioethyl} sulfide, bis {2- (meth) acryloylthioethylthio} methane,
1,2-bis {2- (meth) acryloylthioethylthio} -3- (meth) acryloylthiopropane, thioglycidylthio (meth) acrylate, glycidylthio (meth) acrylate 1,2-bis {(meth) acryloyl Thio} benzene, 1,3-bis {(meth) acryloylthio} benzene, 1,4-bis {(meth) acryloylthio} benzene, 1,2-bis {(meth) acryloylthiomethyl} benzene, 1,3 -Bis {(meth) acryloylthiomethyl} benzene, 1,4-bis {(meth) acryloylthiomethyl} benzene, 1,2-bis {2- (meth) acryloylthioethylthiomethyl} benzene, 1,3- Bis {2- (meth) acryloylthioethylthiomethyl} benzene, 1,4-bis {2- (meth) acryloylchi Ethylthiomethyl} thio such as benzene (meth) acrylate compound,

Allyl compounds such as allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, diethylene glycol bisallyl carbonate, diallyl sulfide, diallyl disulfide, styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinyl. Examples thereof include benzene, vinyl compounds such as 3,9-divinylspirobi (m-dioxane), diisopropenylbenzene, and the like, but are not limited to these exemplified compounds.

If necessary, a polythiol compound other than the polythiol compound represented by the formula (I) may be used in combination.

For example, methanedithiol, ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiol, 1,
2,3-propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol,
2,2-dimethylpropane-1,3-dithiol, 3,
4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, 1,1-bis (mercaptomethyl) cyclohexane, thiomalic acid bis (2-mercaptoethyl ester), 2,3-dimercapto- 1-propanol (2-mercaptoacetate), 2,3-dimercapto-1-propanol (3-
Mercaptopropionate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2- Bis (mercaptomethyl) -1,3-propanedithiol, bis (2-
Mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane bis (2-mercaptoacetate), trimethylolpropane bis (3-mercaptopropionate) , Pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3
-Mercaptopropionate), tetrakis (mercaptomethyl) methane, 1,2,7-trimercapto-4,
6-dithiaheptane, 1,2,9-trimercapto-
4,6,8-trithianonane, 1,2,11-trimercapto-4,6,8,10-tetrathiaundecane,
1,2,13-Trimercapto-4,6,8,10,1
2-pentathiatridecane, 1,2,8,9-tetramercapto-4,6-dithianonane, 1,2,10,11
-Tetramercapto-4,6,8-trithiaundecane, 1,2,12,13-tetramercapto-4,6
Aliphatic polythiol compounds such as 8,10-tetrathiatridecane, bis (2,5-dimercapto-4-thiapentyl) disulfide, bis (2,7-dimercapto-4,6-dithiaheptyl) disulfide,

1,2-dimercaptobenzene, 1,3-
Dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,
3-bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl) benzene, 1,2-bis (mercaptoethyl) benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene ) Benzene, 1,2,3-trimercaptobenzene, 1,2,
4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris ( Mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, 2,5-toluenedithiol , 3,4-
Toluenedithiol, 1,3-di (p-methoxyphenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-
Aromatic polythiols such as 1,1-dithiol and 2,4-di (p-mercaptophenyl) pentane,

1,2-bis (mercaptoethylthio) benzene, 1,3-bis (mercaptoethylthio) benzene, 1,4-bis (mercaptoethylthio) benzene,
1,2,3-Tris (mercaptomethylthio) benzene, 1,2,4-tris (mercaptomethylthio) benzene, 1,3,5-tris (mercaptomethylthio) benzene, 1,2,3-tris (mercaptoethylthio) benzene )
Benzene, 1,2,4-tris (mercaptoethylthio) benzene, 1,3,5-tris (mercaptoethylthio) benzene, etc., and aromatic compounds containing a sulfur atom in addition to the mercapto group such as alkylated products thereof. Polythiol compound,

Bis (mercaptomethyl) sulfide, bis (mercaptoethyl) sulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio)
Methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropylthio) methane, 1,2-bis (mercaptomethylthio) ethane, 1,2-bis (2
-Mercaptoethylthio) ethane, 1,2-bis (3-
Mercaptopropyl) ethane, 1,3-bis (mercaptomethylthio) propane, 1,3-bis (2-mercaptoethylthio) propane, 1,3-bis (3-mercaptopropylthio) propane, 1,2,3- Tris (mercaptomethylthio) propane, 1,2,3-tris (2
-Mercaptoethylthio) propane, 1,2,3-tris (3-mercaptopropylthio) propane, 1,2-
Bis [(2-mercaptoethyl) thio] -3-mercaptopropane, 4,8-dimercaptomethyl-1,11-
Mercapto-3,6,9-trithiaundecane, 4,7
-Dimercaptomethyl-1,11-mercapto-3,
6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane, tetrakis (mercaptomethylthiomethyl)
Methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3-dimercaptopropyl) sulfide, bis (1,3-dimercaptopropyl) sulfide, 2, 5-dimercapto-1,4-dithiane, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-
1,4-dithiane, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) disulfide and the like, and esters of these thioglycolic acid and mercaptopropionic acid,

Hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate) , Hydroxypropyl sulfide bis (2-mercaptoacetate), hydroxypropyl sulfide bis (3-mercaptopropionate), hydroxymethyl disulfide bis (2-mercaptoacetate),
Hydroxymethyl disulfide bis (3-mercaptopropionate), hydroxyethyl disulfide bis (2-mercaptoacetate), hydroxyethyl disulfide bis (3-mercaptopropionate), hydroxypropyl disulfide bis (2-mercaptoacetate), hydroxypropyl Disulfide bis (3-
Mercaptopropionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate), 1,4-dithiane-2,5-diol bis (2-
Mercaptoacetate), 1,4-dithiane-2,5-
Diol bis (3-mercaptopropionate), thiodiglycolic acid bis (2-mercaptoethyl ester), thiodipropionic acid bis (2-mercaptoethyl ester), 4,4-thiodibutyric acid bis (2-mercaptoethyl ester) , Bis (dithiodiglycolic acid) (2
-Mercaptoethyl ester), dithiodipropionic acid bis (2-mercaptoethyl ester), 4,4-dithiodibutyric acid bis (2-mercaptoethyl ester),
Thiodiglycolic acid bis (2,3-dimercaptopropyl ester), thiodipropionic acid bis (2,3-dimercaptopropyl ester), dithioglycolic acid bis (2,3-dimercaptopropyl ester), dithiodipropion An aliphatic polythiol compound containing a sulfur atom in addition to a mercapto group such as acid bis (2,3-dimercaptopropyl ester),

3,4-thiophenedithiol, 2,5-
A heterocyclic compound containing a sulfur atom in addition to a mercapto group such as dimercapto-1,3,4-thiadiazole,

2-mercaptoethanol, 3-mercapto-1,2-propanediol, glycerin di (mercaptoacetate), 1-hydroxy-4-mercaptocyclohexane, 2,4-dimercaptophenol, 2-
Mercaptohydroquinone, 4-mercaptophenol, 3,4-dimercapto-2-propanol, 1,3
-Dimercapto-2-propanol, 2,3-dimercapto-1-propanol, 1,2-dimercapto-1,
3-butanediol, pentaerythritol tris (3
-Mercaptopropionate), pentaerythritol mono (3-mercaptopropionate), pentaerythritol bis (3-mercaptopropionate), pentaerythritol tris (thioglycolate), dipentaerythritol pentakis (3-mercaptopropionate) Pionate), hydroxymethyl-tris (mercaptoethylthiomethyl) methane, 1-hydroxyethylthio-3
-A compound containing a hydroxy group in addition to the mercapto group such as mercaptoethylthiobenzene. Further, halogen-substituted products of these chlorine-substituted products and bromine-substituted products may be used.

These polythiol compounds may be used alone or in combination of two or more.

Among the compounds having a group capable of reacting with the polythiol represented by the formula (I) of the present invention, polyisocyanate which gives a resin excellent in impact resistance is preferably used for spectacle lens applications. . Also, thio (epoxy)
When a compound having a group or an unsaturated group is used to form a spectacle lens, a polyisocyanate can be partially contained.

The polymerizable composition of the present invention is mainly used for adjusting the optical properties such as the refractive index of the resin to be obtained.
In order to adjust various physical properties such as specific gravity, the viscosity of the polymerizable composition,
A resin modifier can be added for the purpose of improving the monomer system and the resin, such as adjusting the handling property.

Further, in the production of the plastic lens of the present invention, if necessary, a thermal catalyst, a photocatalyst, an ultraviolet absorber, an internal mold release agent, an antioxidant, a polymerization inhibitor, an oil soluble dye, a filler, a plasticizer. You may add well-known additives, such as.

The obtained plastic lens of the present invention or the resin thereof can be used to obtain molded products of various forms by changing the molding mold at the time of casting polymerization, such as a spectacle lens, a camera lens, a light emitting diode (LED). ) Etc., and various uses as a transparent resin. Among them, it is particularly useful as a spectacle lens.

Further, the plastic lens of the present invention has a surface for improving antireflection, high hardness, abrasion resistance, chemical resistance, cloud resistance, fashionability, etc., if necessary. Physical and chemical treatments such as polishing, antistatic treatment, hard coat treatment, antireflection coat treatment, and light control treatment can be performed.

[0070]

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples. The refractive index, Abbe number, and
The heat resistance was measured by the following method. Refractive index (nd), Abbe number (νd); measured at 20 ° C. using a Pulfrich refractometer. Heat resistance: Tg was measured by the TMA penetration method (load 50 g, pin tip 0.5 mmφ, temperature rise 10 ° C./min).

Example 1 2- (1-mercapto-2-me)
Lucaptomethyl-3-thiabutyl) -1,3-dithiola
Synthesis 500ml reaction flask down 2-mercapto-methyl-1,
3-Dithiolane 109.3 g (0.72 mol), 49
% Aqueous sodium hydroxide solution 2.9 g (35.7 mmo
1) and 200 ml of methanol were charged, and 69.0 g (0.75 mol) of epichlorohydrin was added dropwise at 10 ° C. over 2 hours. After completion of dropping, the mixture was aged at 10 ° C. for 1 hour. The reaction mass was concentrated under reduced pressure to give crude 2- (1-chloro-2-
Hydroxy-3-thiabutyl) -1,3-dithiolane 1
80.6 g was obtained. Subsequently, after charging 200 ml of toluene, 128.0 g of thionyl chloride (1.0
(8 mol) was added dropwise over 1 hour. 70 after the dropping
Aged at ℃ for 2 hours. The reaction mass was concentrated under reduced pressure to give a crude 2-
There were obtained 217.9 g of (1,2-dichloro-3-thiabutyl) -1,3-dithiolane. Subsequently, thiourea 163.
8 g (2.15 mol), 98% sulfuric acid 3.6 g (35.
9 mmol) and 200 ml of ethanol are charged, and the temperature is 75 ° C.
Then, it was aged for 11 hours. After aging, toluene 300m
1, 24% ammonia water 229.2 g (3.23 mo)
1) was added dropwise at 20 ° C. over 30 minutes. After completion of dropping, the mixture was aged at 60 ° C. for 5 hours. After completion of the aging, the solution was neutralized and separated with 336.5 g (3.23 mol) of 35% hydrochloric acid water, washed with water and then desolvated to give the target compound 2-
(1-Mercapto-2-mercaptomethyl-3-thiabutyl) -1,3-dithiolane 41.1 g (0.16 mo
l) was obtained.

The obtained compound was identified by the following identification method. As a result, the desired compound {2- (1-mercapto-2
-Mercaptomethyl-3-thiabutyl) -1,3-dithiolane}. -IR spectrum (Fig. 1), mass spectrum (Fig. 2), ¹ H-NMR (Fig. 3, attribution of each hydrogen is as follows), ¹³ C-NMR.
(Fig. 4).

Example 2 Production of Plastic Lens Compound {2- (1-mercapto-2-mercaptomethyl-3-thiabutyl) -synthesized according to Example 1
1,3-dithiolane} 13.7 g (0.053 mo
1), 4- (mercaptomethyl) -3,6-dithiaoctane-1,8-dithiol 13.8 g (0.053 mo)
1), xylylene diisocyanate 24.9 g (0.1
32 mol), 10.4 mg (200 ppm) of dibutyltin dichloride as a curing catalyst, and 2 as an ultraviolet absorber.
-(2-hydroxy-5-t-octylphenyl) benzotriazole 26.2 mg (500 ppm), internal release agent di (1- (1- (1-n-butoxy-2-propoxy) -2-propoxy)- 2-Propyl) phosphoric acid 78.6
mg (1500 ppm) was uniformly mixed and dissolved under reduced pressure while being mixed and defoamed, and then poured into a mold composed of a glass mold and a gasket. Then, from 40 ℃ to 13
While gradually raising the temperature to 0 ° C., it was heated and cured for 20 hours. After the polymerization was completed, the polymer was slowly cooled and the polymer was taken out from the mold.

The obtained thiourethane plastic lens was transparent and had a refractive index of 1.670, an Abbe number of 32 and a heat resistance of 95 ° C. The results are shown in Table 1.

Comparative Examples 1 and 2 {2- (1-mercapto-) of the present invention used in Example 2
Instead of 2-mercaptomethyl-3-thiabutyl) -1,3-dithiolane}, another polythiol shown in Table 1 was used, and a thiourethane-based plastic lens was produced in the same manner as in Example 2. The results are shown in Table 1.

[0076]

[Table 1]

[0077]

The polythiol according to the present invention is suitable as a monomer for plastic lenses, and the obtained lenses can enjoy a high refractive index, as can be seen from Examples and Comparative Examples.

[Brief description of drawings]

1 is an IR spectrum of the compound obtained in Example 1. FIG.

2 is a mass spectrum of the compound obtained in Example 1. FIG.

FIG. 3 is a ¹ H-NMR spectrum of the compound obtained in Example 1.

FIG. 4 is a ¹³ C-NMR spectrum of the compound obtained in Example 1.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Munehito Funaya             30 Asamu-cho, Omuta City, Fukuoka Prefecture             In the company (72) Inventor Seiichi Kobayashi             30 Asamu-cho, Omuta City, Fukuoka Prefecture             In the company F-term (reference) 4C023 NA01                 4J034 CA32 CC39 CD08 HA07 HB02                       HB03 HC12 HC42 HC73 RA13

Claims (6)

[Claims] 1. Formula (I): Polythiol represented by. 2. A polymerizable composition containing the polythiol according to claim 1. 3. The polymerizable composition according to claim 2, which contains the polythiol according to claim 1 and polyiso (thio) cyanate. 4. An optical resin obtained by polymerizing the polymerizable composition according to claim 2. 5. An optical element comprising the optical resin according to claim 4. 6. A lens comprising the optical element according to claim 5.