JP2003138016A - Manufacturing method of cured resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To control white turbiness of a (thio)epoxy cured resin having excellent optical properties and an extremely high refractive index. SOLUTION: In a manufacturing method of a cured resin comprising producing a polymerizable composition containing a (thio)epoxy compound having at least one of a structure represented by formula (1) (wherein R1 , R2 , and R3 are each a 1-10C hydrocarbon group or a hydrogen atom; and X is an oxygen atom or a sulfur atom), and curing the composition to obtain the cured resin, the method includes a purification process which comprises washing the (thio) epoxy compound with a polar organic solvent selected from among alcohols, ethers, ketones and esters before the polymerizable composition is produced.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a plastic lens, prism, optical fiber, substrate for information recording medium, filter, which is required to have high refractive index and high transparency.
The present invention relates to a resin preferably used in the field of resin such as an optical material such as a light emitting diode and a polymerizable composition as a raw material of the resin, and particularly to an episulfide compound preferably used as a raw material of a plastic lens for eyeglasses.

[0002]

2. Description of the Related Art Plastic lenses are lighter in weight, less prone to cracking, and more dyeable than inorganic lenses, and have recently become rapidly popular in optical elements such as spectacle lenses and camera lenses. The performances required of these plastic lenses are high refractive index and high Abbe number as optical performance, and high heat resistance and low specific gravity as physical properties.

Among these performances, high heat resistance and low specific gravity have been realized at a high level even with the present high refractive index plastic lenses. Currently, as a resin widely used for these purposes, there is a resin obtained by radical polymerization of diethylene glycol bis (allyl carbonate) (hereinafter referred to as DAC). This resin has various features such as excellent impact resistance, light weight, excellent dyeability, and good workability such as machinability and abrasiveness. . However, this resin has a low refractive index nd of about 1.50, which increases the center thickness and edge thickness of the lens, and thus a resin for lenses having a higher refractive index has been desired.

D. A. A polyurethane resin (Patent Document 1 or the like) or a sulfur-containing O- (meth) acrylate resin (Patent Document 2 or Patent Document 3, in which a sulfur atom is introduced into the resin, which has a higher refractive index than that of C resin, Patent Document 4, etc.) and thio (meth) acrylate resin (Patent Document 5, Patent Document 6)
Etc.) are known. The polythiourethane resin is a well-balanced resin having a high refractive index and good impact resistance.

However, it is very difficult to improve both of the refractive index and the Abbe number at the same time because of the contradictory physical properties that the Abbe number becomes lower as the refractive index rises. Therefore, while suppressing the decrease in Abbe number,
There are many active studies for increasing the refractive index.

The most typical proposal among these examinations is
It is a method of using a (thio) epoxy compound in Patent Document 7, Patent Document 8, Patent Document 9, Patent Document 10, Patent Document 11, Patent Document 12, and Patent Document 13.

However, the above-mentioned (thio) epoxy compound may cause quality fluctuation even if the same production method is used. The cured resin obtained by polymerizing the (thio) epoxy compound may cause white turbidity, and may not be suitable for optical materials such as plastic lenses, prisms, optical fibers, information recording substrates, filters, and light emitting diodes that require high transparency. is there.

[0008]

[Patent Document 1] JP-A-63-46213

[Patent Document 2] JP-A-1-128966

[Patent Document 3] Japanese Unexamined Patent Publication No. H3-217412

[Patent Document 4] Japanese Patent Laid-Open No. 4-161410

[Patent Document 5] JP-A-63-188660

[Patent Document 6] Japanese Patent Laid-Open No. 3-59060

[Patent Document 7] WO-89 / 10575

[Patent Document 8] JP-A-9-110979

[Patent Document 9] Japanese Patent Laid-Open No. 9-71580

[Patent Document 10] Japanese Patent Laid-Open No. 9-255781

[Patent Document 11] Japanese Unexamined Patent Publication No. 11-183702

[Patent Document 12] Japanese Patent Application Laid-Open No. 11-189592

[Patent Document 13] Japanese Patent Application No. 11-068448

[0009]

The present invention is to find a method for purifying a (thio) epoxy compound for suppressing clouding of a (thio) epoxy resin having excellent optical properties and having a very high refractive index. It is intended.

[0010]

Means for Solving the Problems The inventors of the present invention have made extensive studies to solve the above problems. As a result, (Thio)
The inventors have found a good method for purifying an epoxy compound and have reached the present invention.

That is, the present invention is (!) The following formula (1) in one molecule

[0012]

[Chemical 4] (In the formula, R ₁ , R ₂ and R ₃ each represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and X represents an oxygen atom or a sulfur atom). In a method of preparing a polymerizable composition containing a thio) epoxy compound and curing the polymerizable composition to obtain a cured resin,
Prior to the preparation of the polymerizable composition, there is a purification step of washing the (thio) epoxy compound with a polar organic solvent selected from alcohols, ethers, ketones and esters, and the production of a cured resin. Method,

(2) A (thio) epoxy compound is represented by the following formula (2) in one molecule.

[Chemical 5]

(In the formula, R ₄ , R ₅ , and R ₆ are each a hydrocarbon group or hydrogen atom having 1 to 10 carbon atoms, R ₇ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and X is Is an oxygen atom or a sulfur atom.) The method for producing a cured resin according to (1), which is a (thio) epoxy compound having one or more structures represented by the formula (3), wherein (3) the (thio) epoxy compound is The method for producing a cured resin as described above, which is a compound represented by formula (3)

[0015]

[Chemical 6] (In the formula, X represents an oxygen atom or a sulfur atom.).

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

The polar solvent used for washing the (thio) epoxy compound in the present invention includes methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol,
Undecanol, dodecanol, cyclohexanol,
Alcohols such as benzyl alcohol or ethers such as ethyl ether, dichloroethyl ether, isopropyl ether, butyl ether, hexyl ether, methylphenyl ether, ethylphenyl ether, butylphenyl ether, dioxane, trioxane, tetrahydrofuran or acetone, methylacetone, ethyl Ketones such as methyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl hexyl ketone, diethyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, cyclohexanone or ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate , Pentyl acetate, hexyl acetate, octyl acetate, cyclohexyl acetate, methyl propionate, propion Ethyl, butyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, esters such as benzyl benzoate and the like.

These may be used alone or in admixture of two or more.

Among those used alone, alcohols are preferable, and more preferable examples include methanol, ethanol, isopropanol, isobutanol and the like.

The weight of the polar solvent used for washing is (thio)
0.001 to 50. based on the total weight of the epoxy compound.
It is used in a weight ratio range of 0 times, preferably 0.1 to
It is used in the range of 1.0 times the weight ratio. In the range of 0.001 times or less by weight, the effect of preventing clouding is not sufficiently obtained, and in the range of 50.0 times or more (thio)
The recovery rate of the epoxy compound deteriorates.

The polar solvent described above is mixed with the (thio) epoxy compound and stirred. The washing temperature is -10 ° C to 50 ° C, preferably 10 ° C to 30 ° C. In the range of −10 ° C. or lower, the extraction efficiency may be poor and a sufficient cleaning effect may not be obtained. In the range of 50 ° C. or higher, the deterioration of the (thio) epoxy compound may be promoted, and the yield and purity may decrease. The cleaning time varies depending on various factors such as the cleaning temperature, the composition of the compound, and impurities, but it is about 1 minute to 2 minutes.
4 hours. After standing, the polar solvent layer is removed, and the dissolved polar solvent is distilled off from the (thio) epoxy compound to obtain a (thio) epoxy compound in which the cured resin does not become cloudy.

The (thio) epoxy compound purified according to the present invention provides an optical resin having excellent optical properties and a very high refractive index. Examples of the (thio) epoxy compound include bis (β-epithiopropyl) sulfide, bis (β-epithiopropyl) disulfide, bis (β-epithiopropylthio) methane, and 1,2-bis (β-epi). Thiopropylthio) ethane, 1,2-bis (β-epithiopropylthio) propane, 1,3-bis (β-epithiopropylthio) propane, 1,3-bis (β-epithiopropylthio)- 2-methylpropane,
1,4-bis (β-epithiopropylthio) butane,
1,4-bis (β-epithiopropylthio) -2-methylbutane, 1,3-bis (β-epithiopropylthio) butane, 1,5-bis (β-epithiopropylthio) pentane, 1,5 -Bis (β-epithiopropylthio) -2
-Methylpentane, 1,5-bis (β-epithiopropylthio) -3-thiapentane, 1,6-bis (β-epithiopropylthio) hexane, 1,6-bis (β-epithiopropylthio) 2-methylhexane, 3,8-bis (β-epithiopropylthio) -3,6-dithiaoctane, 1,2,3-tris (β-epithiopropylthio) propane, 2,2-bis (β -Epithiopropylthio) -1,3-bis (β-epithiopropylthiomethyl) propane, 2,2-bis (β-epithiopropylthiomethyl) -1- (β-epithiopropylthio) butane, 1,5-bis (β-epithiopropylthio) -2-
(Β-epithiopropylthiomethyl) -3-thiapentane, 1,5-bis (β-epithiopropylthio) -2,
4-bis (β-epithiopropylthiomethyl) -3-thiapentane, 1- (β-epithiopropylthio) -2,
2-bis (β-epithiopropylthiomethyl) -4-thiahexane, 1,5,6-tris (β-epithiopropylthio) -4- (β-epithiopropylthiomethyl)-
3-thiahexane, 1,8-bis (β-epithiopropylthio) -4- (β-epithiopropylthiomethyl)-
3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -4,5-bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epi Thiopropylthio) -4,4-bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -2,
5-bis (β-epithiopropylthiomethyl) -3,6
-Dithiaoctane, 1,8-bis (β-epithiopropylthio) -2,4,5-tris (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,1,1-
Tris [{2- (β-epithiopropylthio) ethyl}
Thiomethyl] -2- (β-epithiopropylthio) ethane, 1,1,2,2-tetrakis [{2- (β-epithiopropylthio) ethyl} thiomethyl] ethane, 1,1
1-bis (β-epithiopropylthio) -4,8-bis (β-epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropylthio) -4,7-bis (β-epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1,11
-Chain aliphatic β-epithiopropylthio compounds such as bis (β-epithiopropylthio) -5,7-bis (β-epithiopropylthiomethyl) -3,6,9-trithiaundecane, And 1,3-bis (β-epithiopropylthio) cyclohexane, 1,4-bis (β-epithiopropylthio) cyclohexane, 1,3-bis (β-
Epithiopropylthiomethyl) cyclohexane, 1,4
-Bis (β-epithiopropylthiomethyl) cyclohexane, 2,5-bis (β-epithiopropylthiomethyl) -1,4-dithiane, 2,5-bis [{2- (β-
Epithiopropylthio) ethyl} thiomethyl] -1,4
-Cycloaliphatic β-epithiopropylthio compounds such as dithiane, and 1,3-bis (β-epithiopropylthio) benzene, 1,4-bis (β-epithiopropylthio) benzene, 1, 3-bis (β-epithiopropylthiomethyl) benzene, 1,4-bis (β-epithiopropylthiomethyl) benzene, bis {4- (β-epithiopropylthio) phenyl} methane, 2,2- Screw {4-
(Β-Epithiopropylthio) phenyl} propane, bis {4- (β-epithiopropylthio) phenyl} sulfide, bis {4- (β-epithiopropylthio) phenyl} sulfone, 4,4′-bis Examples thereof include aromatic β-epithiopropylthio compounds such as (β-epithiopropylthio) biphenyl, but the compounds are not limited to these exemplified compounds. These compounds may be used alone or in combination of two or more.

A compound in which a part or all of the epithio group of the above episulfide compound is substituted with an epoxy group can also be used.

The polymerizable composition containing a (thio) epoxy compound according to the present invention is a composition containing at least one (thio) epoxy compound having one or more (thio) epoxy groups in the molecule. . In the polymerizable composition of the present invention, in order to develop a high refractive index and a high Abbe number, the epithio group in the (thio) epoxy compound is an average relative to the sum of epithio and epoxy groups in the composition. In 5
It is blended so as to be 0% or more. These compositions include
Polysulfide oligomers such as dimers, trimers, and tetramers of these compounds, inorganic acids and organic acids added as polymerization inhibitors, organic compounds such as solvents and by-products, and inorganic compounds within a range not causing a problem. included.

The polymerizable composition containing the (thio) epoxy compound according to the present invention is mainly used for controlling optical properties such as a refractive index of a resin obtained and for controlling physical properties such as impact resistance and specific gravity. A resin modifier can be added for the purpose of improving the resin such as adjusting the viscosity of the monomer and other handling properties.

Examples of the resin modifier include epoxy compounds other than the (thio) epoxy compound according to the present invention, epoxy resin, thiol compound, mercapto organic acids, organic acids and anhydrides, amino acids and mercaptoamines,
Examples include olefins including amines and (meth) acrylates.

Specific examples of preferred amine compounds that can be added as resin modifiers include ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, pentylamine and hexylamine. , Heptylamine, octylamine, decylamine, laurylamine, myristylamine, 3-pentylamine, 2-ethylhexylamine, 1,2-dimethylhexylamine,
Allylamine, aminomethylbicycloheptane, cyclopentylamine, cyclohexylamine, 2,3-dimethylcyclohexylamine, aminomethylcyclohexane, aniline, benzylamine, phenethylamine,
2,3-, or 4-methylbenzylamine, o-,
m- or p-methylaniline, o-, m- or p-ethylaniline, aminomorpholine, naphthylamine, furfurylamine, α-aminodiphenylmethane, toluidine, aminopyridine, aminophenol,
Aminoethanol, 1-aminopropanol, 2-aminopropanol, aminobutanol, aminopentanol, aminohexanol, methoxyethylamine, 2-
(2-aminoethoxy) ethanol, 3-ethoxypropylamine, 3-propoxypropylamine, 3-butoxypropylamine, 3-isopropoxypropylamine, 3-isobutoxypropylamine, 2,2-diethoxyethylamine, etc. Functional primary amine compound, ethylenediamine, 1,2-, or 1,3-diaminopropane, 1,2-, 1,3-, or 1,4-diaminobutane, 1,5-diaminopentane, 1,6- Diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,10-diaminodecane, 1,2-,
1,3- or 1,4-diaminocyclohexane,
o-, m- or p-diaminobenzene, 3,4- or 4,4'-diaminobenzophenone, 3,4- or 4,4'-diaminodiphenyl ether, 4,
4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-, or 4,4 '
-Diaminodiphenyl sulfone, 2,7-diaminofluorene, 1,5-, 1,8-, or 2,3-diaminonaphthalene, 2,3-, 2,6-, or 3,4
-Diaminopyridine, 2,4-, or 2,6-diaminotoluene, m- or p-xylylenediamine, isophoronediamine, diaminomethylbicycloheptane, 1,3-, or 1,4-diaminomethylcyclohexane, 2 -Or 4-aminopiperidine, 2
-, Or 4-aminomethylpiperidine, 2- or 4-aminoethylpiperidine, N-aminoethylmorpholine, N-aminopropylmorpholine, and other primary polyamine compounds, diethylamine, dipropylamine, di-n-butylamine, di- -Sec-butylamine, diisobutylamine, di-n-pentylamine, di-3-pentylamine, dihexylamine, dioctylamine,
Di (2-ethylhexyl) amine, methylhexylamine, diallylamine, N-methylallylamine, piperidine, pyrrolidine, diphenylamine, N-methylamine, N-ethylamine, dibenzylamine, N-methylbenzylamine, N-ethylbenzylamine, Monofunctional secondary amine compounds such as dicyclohexylamine, N-methylaniline, N-ethylaniline, dinaphthylamine, 1-methylpiperazine and morpholine, N, N'-dimethylethylenediamine, N, N'-dimethyl-1,2- Diaminopropane, N, N'-dimethyl-1,3-diaminopropane, N, N'-dimethyl-1,2-diaminobutane, N, N'-dimethyl-1,3-diaminobutane,
N, N'-dimethyl-1,4-diaminobutane, N,
N'-dimethyl-1,5-diaminopentane, N, N '
-Dimethyl-1,6-diaminohexane, N, N'-dimethyl-1,7-diaminoheptane, N, N'-diethylethylenediamine, N, N'-diethyl-1,2-diaminopropane, N, N ' -Diethyl-1,3-diaminopropane, N, N'-diethyl-1,2-diaminobutane, N, N'-diethyl-1,3-diaminobutane,
N, N'-diethyl-1,4-diaminobutane, N,
N'-diethyl-1,5-diaminopentane, N, N '
-Diethyl-1,6-diaminohexane, N, N'-diethyl-1,7-diaminoheptane, piperazine, 2-
Methylpiperazine, 2,5-dimethylpiperazine, 2,
6-dimethylpiperazine, homopiperazine, 1,1-di- (4-piperidyl) methane, 1,2-di- (4-piperidyl) ethane, 1,3-di- (4-piperidyl) propane, 1,4 Examples thereof include secondary polyamine compounds such as -di- (4-piperidyl) butane and tetramethylguanidine, but the compounds are not limited to these exemplified compounds. These may be used alone or in combination of two or more. Among these exemplified compounds, benzylamine and piperazines are more preferable.

Specific examples of preferred epoxy compounds that can be added as resin modifiers include phenolic epoxy compounds obtained by condensation reaction of polyhydric phenol compounds such as bisphenol A glycidyl ether and epihalohydrin compounds, Alcohol-based epoxy compound obtained by condensation of polyhydric alcohol compound such as hydrogenated bisphenol A glycidyl ether and epihalohydrin compound, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate and 1,2-hexa Glycidyl ester-based epoxy compounds obtained by condensation of polyvalent organic acid compounds such as diglycidyl hydrophthalate with epihalohydrin compounds, and condensation of primary and secondary diamine compounds with epihalohydrin compounds Ri resulting amine based epoxy compounds, etc. and, there may be mentioned vinyl cyclohexene diepoxide and an aliphatic polyhydric epoxy compound such as, but not limited to only these exemplified compounds. Also,
These may be used alone or in combination of two or more.

Specific examples of preferred thiol compounds include methyl mercaptan, ethyl mercaptan, 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1, 4-butanedithiol, 1,2,3
-Trimercaptopropane, tetrakis (mercaptomethyl) methane, 1,2-dimercaptocyclohexane,
Bis (2-mercaptoethyl) sulfide, 2,3-dimercapto-1-propanol, ethylene glycol bis (3-mercaptopropionate), diethylene glycol bis (3-mercaptopropionate), diethylene glycol bis (2-mercaptoglycolate) ),
Pentaerythritol tetrakis (2-mercapto thioglycolate), pentaerythritol tetrakis (3
-Mercaptopropionate), trimethylolpropane tris (2-mercaptothioglycolate), trimethylolpropane tris 3-mercaptopropionate), 1,1,1-trimethylmercaptoethane, 1,
1,1-trimethylmercaptopropane, 2,5-dimercaptomethylthiophane, 4-mercaptomethyl-
1,8-dimercapto-3,6-dithiaoctane, 2,
5-dimercaptomethyl-1,4-dithiane, 2,5-
Bis {(2-mercaptoethyl) thiomethyl} -1,4
-Dithiane, 1,3-cyclohexanedithiol, 1,
4-cyclohexanedithiol, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11
-Dimercapto-3,6,9-trithiaundecane,
Aliphatic thiols such as 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and benzylmercaptan, thiophenol,
1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4- Bis (mercaptomethyl) benzene, 2,2′-dimercaptobiphenyl,
4,4'-dimercaptobiphenyl, bis (4-mercaptophenyl) methane, bis (4-mercaptophenyl) sulfide, bis (4-mercaptophenyl) sulfone, 2,2-bis (4-mercaptophenyl) propane, 1 , 2,3-Trimercaptobenzene, 1, 2,
Examples thereof include aromatic thiols such as 4-trimercaptobenzene and 1,2,5-trimercaptobenzene, but are not limited to these exemplified compounds. Also,
These may be used alone or in combination of two or more.

Specific examples of preferable mercapto organic acid compounds include thioglycolic acid, 3-mercaptopropionic acid, thioacetic acid, thiolactic acid, thiomalic acid, and thiosalicylic acid, but the compounds are not limited to these exemplified compounds. Not a thing. Also, these can be used alone or 2
You may mix and use more than one kind.

Specific examples of preferable organic acids and their anhydrides include thiodiglycolic acid, thiodipropionic acid, dithiodipropionic acid, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride and methyltetrahydro. Examples thereof include phthalic anhydride, methylnorbornene anhydride, methylnalbornane anhydride, maleic anhydride, trimellitic anhydride, and pyromellitic anhydride, but are not limited to these exemplified compounds. These may be used alone or in combination of two or more.

Specific examples of preferable olefins include benzyl acrylate, benzyl methacrylate, butoxyethyl acrylate, butoxymethyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxymethyl methacrylate, glycidyl acrylate, glycidyl methacrylate. , Phenoxyethyl acrylate, phenoxyethyl methacrylate, phenyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate,
Tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethylene glycol bisglycidyl acrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A diacrylate , Bisphenol A dimethacrylate,
2,2-bis (4-acryloxyethoxyphenyl) propane, 2,2-bis (4-methacryloxyethoxyphenyl) propane, 2,2-bis (4-acryloxydiethoxyphenyl) propane, 2,2- Bis (4-methacryloxydiethoxyphenyl) propane, bisphenol F diacrylate, bisphenol F dimethacrylate,
1,1-bis (4-acryloxyethoxyphenyl) methane, 1,1-bis (4-metacryloxyethoxyphenyl) methane, 1,1-bis (4-acryloxydiethoxyphenyl) methane, 1,1- Bis (4-methacryloxydiethoxyphenyl) methane, dimethylol tricyclodecane diacrylate, trimethylol propane triacrylate, trimethylol propane trimethacrylate, glycerol diacrylate, glycerol dimethacrylate, pentaerythritol triacrylate,
Pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, methylthioacrylate, methylthiomethacrylate, phenylthioacrylate, benzylthiomethacrylate, xylylenedithiol diacrylate, xylylenedithiol dimethacrylate, mercaptoethyl sulfide diacrylate, mercaptoethyl sulfide dimethacrylate, etc. (Meth) acrylate compounds, allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, allyl compounds such as diethylene glycol bis allyl carbonate, styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinylbenzene,
Examples thereof include vinyl compounds such as 3,9-divinylspirobi (m-dioxane), diisopropenylbenzene, and the like, but are not limited to these exemplified compounds. These may be used alone or in combination of two or more.

These several types of resin modifiers may be used alone or in combination of two or more.

The polymerizable composition of the present invention can be polymerized by heating or standing at room temperature in the presence or absence of a curing catalyst to produce a resin. However, in the absence of a curing catalyst, the polymerization may not proceed satisfactorily, resulting in poor polymerization or no polymerization. As the curing catalyst used in the present invention, amines other than the resin modifier of the present invention, phosphines, Lewis acids, radical polymerization catalysts, cationic polymerization catalysts and the like are usually used.

Specific examples of preferable curing catalysts include triethylamine, tri-n-butylamine and tri-n-amine.
-Hexylamine, N, N-diisopropylethylamine, triethylenediamine, triphenylamine, N,
N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dibutylethanolamine, triethanolamine, N-ethyldiethanolamine,
N, N-dimethylbenzylamine, N, N-diethylbenzylamine, tribenzylamine, N-methyldibenzylamine, N, N-dimethylcyclohexylamine,
N, N-diethylcyclohexylamine, N, N-dimethylbutylamine, N-methyldicyclohexylamine, N-methylmorpholine, N-isopropylmorpholine, pyridine, quinoline, N, N-dimethylaniline,
N, N-diethylaniline, α-, β-, or γ-
Picoline, 2,2'-bipyridyl, 1,4-dimethylpiperazine, dicyandiamide, tetramethylethylenediamine, hexamethylenetetramine, 1,8-diazabicyclo (5.4.0) -7-undecene, 2,4,6-
Aliphatic and aromatic tertiary amines such as tris (N, N-dimethylaminomethyl) phenol, trimethylphosphine, triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine , Tribenzylphosphine, 1,2-bis (diphenylphosphino)
Phosphines such as ethane and 1,2-bis (dimethylphosphino) ethane, dimethyltin dichloride, dibutyltin dichloride, dibutyltin dilaurate, tetrachlorotin, dibutyltin oxide, zinc chloride, zinc acetylacetone, aluminum chloride, aluminum fluoride Lewis acids such as triphenylaluminum, tetrachlorotitanium and calcium acetate, 2,2′-azobis (2-cyclopropylpropionitrile), 2,2′-azobis (4-methoxy-2,
4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), t-butylperoxy-2-ethylhexanoate, n-butyl-4,
4'-bis (t-butylperoxy) valerate, t-
Radical polymerization catalyst such as butyl peroxybenzoate,
Examples include cationic polymerization catalysts such as diphenyliodonium hexafluorophosphoric acid, diphenyliodonium hexafluoroarsenic acid, diphenyliodonium hexafluoroantimony, triphenylsulfonium tetrafluoroboric acid, triphenylsulfonium hexafluorophosphoric acid, and triphenylsulfonium hexafluoroarsenic acid. However, the present invention is not limited to these exemplified compounds.

These curing catalysts may be used alone or in combination of two or more.

The amount of the curing catalyst added is in the range of 0.001 to 10.0% by mass, preferably the total amount of the composition containing the (thio) epoxy compound represented by the formula (1). It is used in the range of 0.01 to 1.0 mass%.
If the addition amount of the curing catalyst is less than 0.001% by mass, the effect is small, which may cause poor polymerization. On the other hand, although it is possible to exceed 10.0% by mass, inconveniences such as shortening of pot life and deterioration of transparency, optical properties, or weather resistance may occur.

The polymerization method, polymerization conditions and the like for obtaining the resin of the present invention cannot be unconditionally limited depending on the type and amount of the curing catalyst used and the type and ratio of the monomers, but typical polymerization Examples of the method include cast polymerization.
That is, the decompressed polymerizable composition of the present invention is injected between molding molds held by a gasket or tape. Here, the polymerizable composition may be mixed with a curing catalyst and a resin modifier, if necessary. Then, the resin can be taken out by curing by heating in an oven or in a heatable device such as water.

The heat-polymerization conditions of the polymerizable composition of the present invention injected into a molding mold are as follows: the compound of the above formula (1) and the kind of the resin modifier, which have been subjected to a reduced pressure treatment for a certain time of the present invention. It cannot be limited because the conditions vary greatly depending on the type of curing catalyst and the shape of the molding mold.
It is carried out at a temperature of 0 to 200 ° C. for 0.1 to 100 hours.

In some cases, it may be preferable to maintain the temperature in the range of 10 ° C. to 150 ° C. or gradually raise the temperature and polymerize in 1 to 80 hours.

Further, the polymerizable composition of the present invention can be shortened in polymerization time by irradiation with ultraviolet rays or the like. At this time, a curing catalyst such as a radical polymerization catalyst may be added.

[0042]

EXAMPLES The present invention will be described below with reference to examples. Regarding Examples and Comparative Examples, the results based on bis (β-epithiopropyl) disulfide represented by the following formula (4) (hereinafter, abbreviated as compound A) are shown.

[0043]

[Chemical 7]

Example 1 100 g of compound A (94.0% by mass, 0.45 mol)
12.5 g of isopropanol was added to and stirred for 15 minutes. After standing, the isopropanol layer is removed, and the dissolved polar solvent is distilled off from the (thio) epoxy compound,
99.7 g of compound A (purified product) having a purity of 94.0% by mass
(0.45 mol) was obtained. To 20 g of the obtained compound A (purified product), 0.02 g of N, N-dicyclohexylmethylamine and 0.008 g of N, N-dimethylcyclohexylamine as a curing catalyst were added and stirred. This mixed solution is poured into a molding mold and heated from 30 ° C to 120 ° C.
The temperature was gradually raised to 24 hours, and the polymerization was completed over 24 hours.
After cooling, the plastic lens obtained by releasing the mold was not clouded when observed with a slide projector.

Compound A (50
The above cleaning treatment was performed for each batch.
None of the resins obtained by curing the obtained compound A (purified product) had cloudiness.

COMPARATIVE EXAMPLE 1 Compound A (50 batches) in different production batches was resinified in the same manner as in Example 1 without washing with a polar solvent. After cooling, the plastic lens obtained by releasing the mold was observed with a slide projector. As a result, 19 of the 50 lenses had cloudiness.

Comparative Example 2 For each of the different production batches of compound A (for 50 batches), n was used instead of isopropanol as the washing solvent.
Using hexane, the resin was washed and resinified in the same manner as in Example 1. After cooling, the plastic lens obtained by releasing the mold was observed with a slide projector. As a result, 17 of the 50 lenses were clouded.

[0048]

Industrial Applicability According to the present invention, it is possible to prevent clouding of the (thio) epoxy cured resin caused by the fluctuation of the quality of the (thio) epoxy compound, and a plastic lens, a prism, which requires a high refractive index and high transparency. It contributes to the field of resins such as optical materials, substrates for information recording media, filters, optical materials such as light emitting diodes, and particularly the field of eyeglass lenses.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Chitose Shimakawa             30 Asamu-cho, Omuta-shi, Fukuoka Mitsui Chemicals             Within the corporation (72) Inventor Akinori Ryu             30 Asamu-cho, Omuta-shi, Fukuoka Mitsui Chemicals             Within the corporation (72) Inventor Seiichi Kobayashi             30 Asamu-cho, Omuta-shi, Fukuoka Mitsui Chemicals             Within the corporation (72) Inventor Yoshinobu Kanamura             30 Asamu-cho, Omuta-shi, Fukuoka Mitsui Chemicals             Within the corporation F-term (reference) 4J030 BA03 BA05 BA18 BB03 BC21                       BG25                 4J036 AJ19 BA06 JA15

Claims (3)

[Claims] 1. A compound represented by the following formula (1) in one molecule: (In the formula, R ₁ , R ₂ and R ₃ each represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and X represents an oxygen atom or a sulfur atom). In a method of preparing a polymerizable composition containing a thio) epoxy compound and curing the polymerizable composition to obtain a cured resin,
Prior to the preparation of the polymerizable composition, there is a purification step of washing the (thio) epoxy compound with a polar organic solvent selected from alcohols, ethers, ketones and esters, and the production of a cured resin. Method. 2. A (thio) epoxy compound is represented by the following formula (2): (In the formula, R ₄ , R ₅ , and R ₆ are each a hydrocarbon group or hydrogen atom having 1 to 10 carbon atoms, and R ₇ is 2 having 1 to 10 carbon atoms.
Represents a valent hydrocarbon group, and X represents an oxygen atom or a sulfur atom. The method for producing a cured resin according to claim 1, which is a (thio) epoxy compound having one or more structures represented by the formula (1). 3. The method for producing a cured resin according to claim 1, wherein the (thio) epoxy compound is a compound represented by the following formula (3). [Chemical 3] (In the formula, X and Y each represent an oxygen atom or a sulfur atom.)