JP2001163877A - (thio)epoxy compound removed from high molecular material and its purifying method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the stability with time of a (thio)epoxy compound, capable of giving an optical resin excellent in physical properties and having a very high refractivity. SOLUTION: This method for obtaining a (thio)epoxy compound having an improved stability with time is provided by mixing and agitating an inert hydrocarbon-based solvent with the (thio)epoxy compound having >=1 structures expressed by the following formula (1), wherein, R1, R2, R3 are each a 1-10C hydrocarbon group or H; and X is O or S or (2), wherein, R4, R5, R6 are each a 1-10C hydrocarbon group or H; R7 is a 1-10C divalent hydrocarbon group; and X is O or S) in its molecule, separating it to the hydrocarbon-based solvent layer and the high molecular weight material layer after standing still, removing the high molecular weight material layer and then distilling off the solvent from the hydrocarbon-based solvent layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is suitably used in the resin field of optical materials such as plastic lenses, prisms, optical fibers, information recording substrates, filters, light emitting diodes, etc., which require high refractive index and high transparency. The present invention relates to a (thio) epoxy compound suitably used as a raw material for a polymerizable composition, particularly a plastic lens for spectacles, and a method for purifying the same.

[0002]

2. Description of the Related Art Plastic lenses are light weight, hard to break, and can be dyed compared to inorganic lenses. Therefore, plastic lenses have recently been rapidly used 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, high heat resistance and low specific gravity as physical properties.

[0003] Among these performances, high heat resistance and low specific gravity have been realized at a high level even with current high refractive index plastic lenses. At present, 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 being excellent in impact resistance, being lightweight, being excellent in dyeability, being excellent in workability such as cutting property and polishing property, and the like. . However, this resin has a refractive index nd as low as about 1.50, and the center thickness and the edge thickness of the lens are increased. Therefore, a lens resin having a higher refractive index has been desired.

D. A. As a resin having a higher refractive index than the C resin, a polyurethane resin (Japanese Patent Application Laid-Open No. 63-46213) or a sulfur-containing O-
(Meth) acrylate resin (JP-A-1-128966, JP-A-3-217412, JP-A-4-16)
No. 1410) and thio (meth) acrylate resins (JP-A-63-188660, JP-A-3-590).
No. 60 publication) is known. The polythiourethane resin is a resin having an excellent balance, such as a high refractive index and good impact resistance.

However, it is very difficult to improve both the refractive index and the Abbe number at the same time because they have conflicting physical properties such that the Abbe number decreases as the refractive index increases. Therefore, while suppressing the decrease in Abbe number,
Investigations to increase the refractive index have been actively conducted.

The most typical proposal in these studies is:
WO-89 / 10575, JP-A-9-111079, JP-A-9-71580, and JP-A-9-105580
This is a method in which a (thio) epoxy compound is used in Japanese Patent Application Laid-Open Nos. 2557581, 11-183702, 11-189592, and 11-068448.

[0007] Incidentally, the (thio) epoxy compounds produced by the methods disclosed therein may self-polymerize and cause deterioration over time, which may make it difficult to store them for a long period of time. Further, when deterioration occurs with time, the viscosity increases and the viscosity increases, and the workability may be significantly reduced. For example, in the case of a plastic lens, it is generally said that if the viscosity at room temperature is not less than 100 Pa · s, the operation of injecting a monomer into a molding mold will be hindered. (Thio) epoxy compounds are required to have high refractive index, low specific gravity and transparency, plastic lenses, prisms, optical fibers,
Since it is a raw material of (thio) epoxy-cured resin which is greatly expected in the field of resins such as information recording substrates, filters, and optical materials such as light-emitting diodes, it was necessary to immediately resolve the problem of deterioration over time.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to improve the temporal stability of a (thio) epoxy compound which gives an optical resin having excellent optical properties and a very high refractive index. It is.

[0009]

The present inventors have intensively studied to solve the above-mentioned problems. As a result, (thio)
It has been found that the impurities present in the epoxy compound, which have a high molecular weight, cause deterioration of the (thio) epoxy compound with time and impair its stability. The inventors have found that by extracting with a hydrogen-based solvent, the high molecular weight impurities can be removed from the (thio) epoxy compound, and the present invention has been accomplished.

That is, the present invention provides the following formula (1) or (2) in one molecule.

[0011]

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(Wherein, 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.)

[0013]

Embedded image

(Wherein R ₄ , R ₅ and R ₆ each represent a hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms, R ₇ represents a divalent hydrocarbon group having 1 to 10 carbon atoms; Represents an oxygen atom or a sulfur atom.) (Thio) epoxy compound having at least one structure represented by the formula: wherein the content of the high molecular weight compound derived from the (thio) epoxy compound is 20% by mass or less. By extracting a (thio) epoxy compound, a (thio) epoxy compound having at least one structure represented by the above formula (1) or (2) with a hydrocarbon-based solvent, a high molecular weight compound is obtained. A method for purifying a (thio) epoxy compound, characterized in that the compound is removed.
The present invention relates to the above-mentioned (thio) epoxy compound, wherein the epoxy compound is a compound represented by the following formula (3), and a purification method thereof.

[0015]

Embedded image (In the formula, X represents an oxygen atom or a sulfur atom.)

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The "high molecular weight compound" in the present invention is a high molecular weight compound derived from the (thio) epoxy compound of the present invention, and cannot be said unconditionally depending on the structure of the (thio) epoxy compound. It can be defined in such a manner. That is, first, the obtained (thio) epoxy compound is measured under the following liquid chromatography analysis conditions. Next, after identifying the peak of the target (thio) epoxy compound, the purity is calculated by the internal standard method. Other peaks are low molecular weight by-products other than the desired (thio) epoxy compound. Therefore, all other residues that cannot be detected as peaks correspond to “high molecular weight compounds” in the present invention.

Analysis conditions ・ HPLC pump: Shimadzu “LC-10AD” ・ Detector: Shimadzu “SPD-10A” UV-254 nm ・ Oven: Shimadzu “CTO-10A” 40 ° C. ・ Column: YMC “A-312 S-5” ODS "・ Eluent: acetonitrile-water mixed solvent ・ Flow rate: 1 ml / min ・ Analytical sample: (thio) epoxy compound (about 40 mg) +
Diisobutyl phthalate (about 30 mg, for internal standard) / acetonitrile (5 ml)

The hydrocarbon solvent used for extracting the (thio) epoxy compound in the present invention includes n-pentane, n-hexane, isohexane, n-heptane,
aliphatic hydrocarbon compounds such as n-octane, isooctane, n-nonane, n-decane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, or benzene, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, naphthalene,
Aromatic hydrocarbon compounds such as tetralin and biphenyl,
Or methylene chloride, chloroform, carbon tetrachloride, ethylene chloride, trichloroethane, tetrachloroethane, pentachloroethane, hexachloroethane, dichloroethylene, trichloroethylene, tetrachloroethylene, dichloropropane, trichloropropane, isopropyl chloride, butyl chloride, hexyl chloride, chlorobenzene, dichlorobenzene, Trichlorobenzene, chlorotoluene,
Halogenated hydrocarbon compounds such as chloronaphthalene.

Although it cannot be said unconditionally depending on the structure of the (thio) epoxy compound, these solvents can be used alone or in combination of two or more. Among those used alone, preferred are aliphatic hydrocarbon compounds, and more preferred are cyclopentane, cyclohexane, cycloheptane and the like. Among the compounds used in combination of two or more, a compound obtained by mixing an aromatic hydrocarbon compound or a halogenated hydrocarbon compound with an aliphatic hydrocarbon compound is preferable.

The amount of the hydrocarbon solvent to be used is 0.1 to 100 with respect to the total weight of the (thio) epoxy compound.
It is used in the range of twice the weight ratio, preferably 0.5 to 20 times.
It is used in the range of twice the weight ratio. When the weight ratio is 0.1 times or less, the extraction efficiency of the (thio) epoxy compound is poor. When the weight ratio is 100 times or more, workability and economy are poor.

As a purification method for removing high molecular weight compounds using a hydrocarbon-based solvent, the following method can be mentioned.
The hydrocarbon solvent described above is mixed with the (thio) epoxy compound and stirred. The stirring temperature is from -20C to 50C, preferably from 10C to 30C. In the range of −20 ° C. or lower, the extraction efficiency of the (thio) epoxy compound is poor, and in the range of 50 ° C. or higher, the deterioration of the (thio) epoxy compound is promoted, and the yield and the purity may decrease. The stirring time varies depending on various factors such as temperature, compound composition, impurities and the like, but is about 1 minute to 24 hours. After standing, liquid is separated into a hydrocarbon solvent layer and a high molecular weight compound layer,
The layer of high molecular weight compound is removed. By distilling off the solvent from the hydrocarbon solvent layer, a (thio) epoxy compound with further improved stability can be obtained.

The (thio) epoxy compound purified according to the present invention has excellent optical properties and gives an optical resin having 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-epithio). 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-epithio Propylthio) -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-epithio 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
Linear 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, 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 And aromatic β-epithiopropylthio compounds such as (β-epithiopropylthio) biphenyl. It is not limited only to these exemplified compounds. These compounds may be used alone or in combination of two or more.

Further, a compound in which part or all of the epithio group of the 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 a molecule. . In the polymerizable composition of the present invention, in order to exhibit a high refractive index and a high Abbe number, the epithio group in the (thio) epoxy compound is averaged with respect to the total of the epithio and epoxy groups in the composition. At 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 and organic acids added as polymerization inhibitors, organic compounds such as solvents and other by-products, and inorganic compounds are also within a range that does not pose 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 the refractive index of the obtained resin and for controlling various 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 resins, thiol compounds, mercapto organic acids, organic acids and anhydrides, amino acids and mercaptoamines,
Olefins including amines, (meth) acrylates and the like can be mentioned.

Specific examples of preferred amine compounds which can be added as a resin modifier 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-aminoethoxy) ethanol, 3-ethoxypropylamine, 3-propoxypropylamine, 3-butoxypropylamine, 3-isopropoxypropylamine, 3-isobutoxypropylamine, 2,2-diethoxyethylamine and the like 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'-diaminodiphenylsulfide, 3,3'-, or 4,4 '
-Diaminodiphenylsulfone, 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, -Or 4-aminopiperidine, 2
A primary polyamine compound such as-or 4-aminomethylpiperidine, 2- or 4-aminoethylpiperidine, N-aminoethylmorpholine, N-aminopropylmorpholine, diethylamine, dipropylamine, di-n-butylamine, -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, 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 are not limited to these exemplified compounds. These may be used alone or in combination of two or more. Among these exemplified compounds, more preferred are benzylamine and piperazines.

Specific examples of preferred epoxy compounds which can be added as a resin modifier include phenolic epoxy compounds obtained by a condensation reaction of a polyhydric phenol compound such as bisphenol A glycidyl ether and an epihalohydrin compound, Alcohol-based epoxy compounds obtained by condensation of a polyhydric alcohol compound such as hydrogenated bisphenol A glycidyl ether and an epihalohydrin compound; 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate; For condensation of glycidyl ester epoxy compounds, primary and secondary diamine compounds and epihalohydrin compounds obtained by condensation of polyhalogenated organic acid compounds such as hydrophthalic acid diglycidyl ester and 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 preferable thiol compounds include methyl mercaptan, ethyl mercaptan, 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 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-mercaptothioglycolate), pentaerythritol tetrakis (3
-Mercaptopropionate), trimethylolpropane tris (2-mercaptothioglycolate), trimethylolpropanetris 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, , 2,3-trimercaptobenzene, 1,2,2
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 preferred mercapto organic acid compounds include thioglycolic acid, 3-mercaptopropionic acid, thioacetic acid, thiolactic acid, thiomalic acid, and thiosalicylic acid, but are not limited to these exemplified compounds. Not something. In addition, these may be used alone or 2
More than one kind may be mixed and used.

Specific examples of preferred organic acids and anhydrides thereof include thiodiglycolic acid, thiodipropionic acid, dithiodipropionic acid, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydroacid. Examples thereof include phthalic anhydride, methylnorbornene anhydride, methylnalbornanoic 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 preferred olefins include benzyl acrylate, benzyl methacrylate, butoxyethyl acrylate, butoxymethyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxymethyl methacrylate, glycidyl acrylate, and 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-methacryloxyethoxyphenyl) methane, 1,1-bis (4-acryloxydiethoxyphenyl) methane, 1,1- Bis (4-methacryloxydiethoxyphenyl) methane, dimethylol tricyclodecane diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, glycerol diacrylate, glycerol dimethacrylate, pentaerythritol triacrylate,
Such as 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 bisallyl 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 as a mixture of two or more types.

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 well, resulting in poor polymerization or no polymerization. As the curing catalyst used in the present invention, amines, phosphines, Lewis acids, radical polymerization catalysts, cationic polymerization catalysts and the like other than the resin modifier of the present invention are usually used.

Specific examples of preferable curing catalysts include triethylamine, tri-n-butylamine, tri-n-butylamine and tri-n-butylamine.
-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, and others, 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 , Triphenylaluminum, tetrachlorotitanium, Lewis acids such as 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 catalysts such as butyl peroxybenzoate,
Cationic polymerization catalysts such as diphenyliodonium hexafluorophosphoric acid, diphenyliodonium hexafluoroarsenate, diphenyliodonium hexafluoroantimony, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroarsenate, and the like. However, the present invention is not limited only to these exemplified compounds.

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

The curing catalyst is used in an amount of 0.001 to 10.0% by mass based on the total weight of the composition containing the (thio) epoxy compound represented by the formula (1), and is preferably used. It is used in the range of 0.01 to 1.0% by 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, even if the content exceeds 10.0% by mass, the pot life may be shortened, or inconveniences such as reduction in 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 unequivocally limited by the type and amount of the curing catalyst and the like, and the type and ratio of the monomer used. The method includes, for example, cast polymerization.
That is, the decompressed polymerizable composition of the present invention is injected between molding molds held by gaskets or tapes. Here, the polymerizable composition may be mixed with a curing catalyst and a resin modifier as necessary. Next, the resin is cured by heating in a heatable device such as an oven or water, and the resin can be taken out.

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

In some cases, preferable results may be obtained by maintaining the temperature in the range of 10 ° C. to 150 ° C. or by gradually increasing the temperature and polymerizing for 1 to 80 hours.

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

[0043]

The present invention will be described below with reference to examples. In Examples and Comparative Examples, results based on bis (β-epithiopropyl) disulfide (hereinafter, abbreviated as compound A) represented by the following formula (4) are described. In the stability test of the (thio) epoxy compound, the (thio) epoxy compound was stored at 35 ° C for 2 months, and then the stability was evaluated by measuring the viscosity at 25 ° C using a B-type viscometer.

[0044]

Embedded image

Example 1 100 g of compound A (72.0% by mass, 0.34 mol;
Content of high molecular weight compound: 25.0% by mass)
l of cyclohexane was added and stirred for 30 minutes. After standing still
By removing components insoluble in cyclohexane and distilling cyclohexane from the cyclohexane solution under reduced pressure,
80.5 g of compound A (purified product) having a purity of 86.3% by mass
(0.33 mol) was obtained (content of high molecular weight compound: 10.7% by mass). The viscosity of the obtained compound A (purified product) was 40 Pa · s (25 ° C.). Compound A (purified product) was sealed in a glass container under nitrogen and stored at 35 ° C. The viscosity after 2 months is 42 Pa · s (25 ° C.)
There was almost no increase in viscosity, and no deterioration with time was observed.

Example 2 100 g of compound A (72.0% by mass, 0.34 mol;
Content of high molecular weight compound: 25.0% by mass)
1 of a mixed solvent of hexane and toluene (hexane: toluene = 5: 1) was added, and the mixture was stirred for 30 minutes. After standing, components insoluble in cyclohexane are removed, and cyclohexane is distilled off from the cyclohexane solution under reduced pressure to give a purity of 8%.
81.3 g (0.3 mass%) of compound A (purified product)
1 mol) (content of high molecular weight compound: 16).
9% by mass). The viscosity of the obtained compound A (purified product) is 41.
Pa · s (25 ° C.). Compound A (purified product) was sealed in a glass container under nitrogen and stored at 35 ° C. The viscosity after 2 months was 44 Pa · s (25 ° C.), there was almost no increase in viscosity, and no deterioration with time was observed.

Example 3 20 g of the compound A (purified product) obtained in Example 1 was added to 0.2 g of N, N-dicyclohexylmethylamine as a curing catalyst.
02g and N, N-dimethylcyclohexylamine 0.0
08 g was added and stirred. This mixed solution was poured into a molding mold, and the temperature was gradually raised from 30 ° C to 120 ° C.
The polymerization was completed over 4 hours. After cooling, the mold was released to obtain a highly transparent plastic lens.

COMPARATIVE EXAMPLE 1 100 g of Compound A without extraction with a hydrocarbon solvent
(Viscosity 57 Pa · s) was sealed in a glass container under nitrogen and stored at 35 ° C. The viscosity after 2 months is 171 Pa · s
(25 ° C.), the viscosity increased greatly, and there was no stability over time.

Comparative Example 2 The same treatment as in Example 1 was performed by using methanol instead of cyclohexane as the hydrocarbon-based extraction solvent, and the purity was 7%.
90.7 g (0.3%) of 2.7% by mass of compound A (purified product)
2 mol) (content of high molecular weight compound: 24.)
3% by mass). 100 g of the obtained compound A (purified product) (viscosity: 52 Pa · s) was sealed in a glass container under nitrogen, and then sealed.
Stored at ° C. The viscosity after 2 months is 157 Pa · s (25
° C), the viscosity increased greatly, and there was no stability over time.

Comparative Example 3 Compound A of Comparative Example 1 was resinified in the same manner as in Example 3. The viscosity of the (thio) epoxy compound was increased, and the workability at the time of injecting the monomer into the molding mold was significantly reduced.

[0051]

According to the present invention, it is possible to improve the stability over time of a (thio) epoxy compound which gives an optical resin having excellent optical properties and a very high refractive index, and has a high refractive index and high transparency. Resin fields such as plastic lenses, prisms, optical fibers, substrates for information recording media, filters, optical materials such as light-emitting diodes,
In particular, it contributes to the field of spectacle lenses.

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[Procedure amendment]

[Submission date] February 22, 2000 (200.2.2
2)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction contents]

Example 2 100 g of compound A (72.0% by mass, 0.34 mol;
Content of high molecular weight compound: 25.0% by mass)
1 of a mixed solvent of hexane and toluene (hexane: toluene = 5: 1) was added, and the mixture was stirred for 30 minutes. After standing still, hexa
The components insoluble in the mixed solvent of toluene and toluene were removed, and the solvent was distilled off from the mixed solution under reduced pressure to give a purity of 80.1.
81.3 g (0.31 mol) of Compound A (purified product)
1) was obtained (content of high molecular weight compound: 16.9% by mass). The viscosity of the obtained compound A (purified product) is 41 Pa ·
s (25 ° C.). Compound A (purified product) was sealed in a glass container under nitrogen and stored at 35 ° C. The viscosity after 2 months was 44 Pa · s (25 ° C.), there was almost no increase in viscosity, and no deterioration with time was observed.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Chinori Shimakawa 30 Asamuta-cho, Omuta-shi, Fukuoka Prefecture Mitsui Chemicals, Inc. 72) Inventor Seiichi Kobayashi 30 Asamuta-cho, Omuta-shi, Fukuoka, Japan Mitsui Chemicals, Inc. (72) Inventor Yoshinobu Kanamura 30 Asamata-cho, Omuta-shi, Fukuoka, Japan Mitsui Chemicals, Inc. KK05 UU03 UU05 XX03 XX04 4J030 BA05 BA42 BA47 BA48 BA49 BB03 BB67 BG25

Claims (8)

[Claims] 1. The following formula (1) in one molecule: (Wherein, 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). A (thio) epoxy compound, wherein the content of the high molecular weight compound derived from the (thio) epoxy compound is 20% by mass or less. 2. The following formula (2) in one molecule: (Wherein, R ₄ , R ₅ , and R ₆ each represent a hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms, and R ₇ represents 2 to 2 carbon atoms having 1 to 10 carbon atoms.
X represents a monovalent hydrocarbon group, and X represents an oxygen atom or a sulfur atom. (Thio) epoxy compounds having at least one structure represented by the formula (I), wherein the content of the high molecular weight compound derived from the (thio) epoxy compound is 20% by mass or less. . 3. The (thio) epoxy compound according to claim 1, wherein the (thio) epoxy compound is a compound represented by the following formula (3). Embedded image (In the formula, X represents an oxygen atom or a sulfur atom.) 4. The following formula (1) in one molecule: (Wherein, 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). A method for purifying a (thio) epoxy compound, comprising removing a high molecular weight compound by extracting the thio) epoxy compound with a hydrocarbon-based solvent. 5. The following formula (2) in one molecule: (Wherein, R ₄ , R ₅ , and R ₆ each represent a hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms, and R ₇ represents 2 to 2 carbon atoms having 1 to 10 carbon atoms.
X represents a monovalent hydrocarbon group, and X represents an oxygen atom or a sulfur atom. By extracting a (thio) epoxy compound having one or more structures represented by the formula) with a hydrocarbon-based solvent,
A method for purifying a (thio) epoxy compound, comprising removing a high molecular weight compound. 6. The method for purifying a (thio) epoxy compound according to claim 4, wherein the (thio) epoxy compound is a compound represented by the following formula (3). Embedded image (In the formula, X represents an oxygen atom or a sulfur atom.) 7. A (thio) epoxy resin composition containing the (thio) epoxy compound according to any one of claims 1 to 3. 8. A polysulfide resin obtained by polymerizing the (thio) epoxy resin composition according to claim 7.