JP2001220444A - Polymerizable composition and method for producing optical resin by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymerizable composition capable of ensuring a pot life of a monomer, depressing heat generation when polymerized, enabling the formed polymer to attain a high refractive index and a high Abbe's number, capable of reducing yellowing of the polymer caused by heating, improving color of the polymer, preventing striae from generating inside a lens when mass-produced, and capable of preventing decrease in yield caused by the striae. SOLUTION: This polymerizble composition contains (a) a compound having one or more structures expressed by formula (1) (R1 is a 1-10C divalent hydrocarbon residue; R2, R3, and R4 are each H or a 1-10C hydrocarbon residue; X is S or O; and X' is S or O) in the molecule, two or more kinds of (b) aliphatic and/or aromatic group-substituted compounds having tertiary amino groups each of which has a catalytic activity different from the others as polymerization catalysts, wherein the functional group mol ratio of the tertiary amino groups in the compound (b) to episulfide groups in the compound (a) is in a range of 0.0001-0.02.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin used for an optical material such as a plastic lens, a prism, an optical fiber, an information recording substrate, a filter, a light-emitting diode, and a polymerizable composition serving as a raw material of the resin. More particularly, the present invention relates to a polymerizable composition suitably used as a raw material for plastic lenses for glasses.

[0002]

2. Description of the Related Art In recent years, plastic lenses have been rapidly spread to optical materials such as spectacle lenses and camera lenses because plastic lenses are lighter and harder to break than inorganic lenses and can be dyed. The performances required of these plastic lenses are high refractive index and high Abbe number as optical performance, and high heat resistance, low specific gravity and workability as physical properties.

Among these performances, high heat resistance and low specific gravity have been realized at a high level even with the current high refractive index plastic lens. 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 characteristics such as being excellent in impact resistance, being lightweight, being excellent in dyeing properties, 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 edge thickness of the lens becomes large. Therefore, a lens resin having a higher refractive index has been desired.

D. A. As those having a higher refractive index than the C resin, polythiourethane resins (Japanese Patent Publication No. 4-58489, etc.) and sulfur-containing O- (meth) acrylate resins (Japanese Patent Application Laid-Open No. 4-161410, etc.) having a sulfur atom introduced into the resin. ) Or thio (meth) acrylate resin (Japanese Patent Publication No. 3-59060)
Etc.) are 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, studies for increasing the refractive index while suppressing a decrease in the Abbe number have been actively conducted.

The most typical proposal in these studies is:
JP-A-9-110979 and JP-A-9-715
No. 80, Japanese Unexamined Patent Publication No. 9-255781, Japanese Unexamined Patent Publication No.
0-2982878, JP-A-11-166037
JP, WO89 / 10575, JP-A-11-1400
No. 70, JP-A-11-183702, JP-A-11-189592, Japanese Patent Application No. 11-68448, and the like are proposals for a resin for a high refractive index lens using an episulfide compound.

According to these methods, a high refractive index can be realized while having a relatively high Abbe number. However, when attempting to obtain a resin by these methods, when polymerizing the resin, the pot life of the monomer cannot be sufficiently ensured, resulting in inferior workability, or the heat generated during the polymerization becomes extremely large, and the heat generated during the polymerization of the resin. In some cases, yellowing, resin kogation, or polymerization runaway occurred. In some cases, the resin turned yellow in a post-heating step such as annealing.
Further, it is generally desired that the yield in industrial lens production be 90% or more. However, when producing lenses using episulfide compounds, it is comparatively difficult to suppress heat generation during polymerization in a small amount of production. However, when mass-producing lenses, it is difficult to completely control the polymerization of all the lenses. Optical non-uniformity (hereinafter referred to as striae) may occur, which may lead to a decrease in yield due to striae.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to ensure a sufficient pot life of the monomer, suppress heat generation during polymerization, and maintain a high refractive index and a high Abbe number in the obtained resin. A polymerizable composition having the effect of reducing yellowing due to heating, improving the hue of the resin, and suppressing the occurrence of striae inside the lens when mass-producing the lens, and preventing the yield from being reduced due to the striae. It is to provide.

[0009]

Means for Solving the Problems In view of such circumstances, the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, the polymerizable composition of the present invention has a sufficient pot life. The resulting resin has the effect of reducing yellowing due to heating, suppressing heat generation during polymerization, improving the hue of the resin, and maintaining mass production of lenses while maintaining a high refractive index and a balanced Abbe number. It has been found that when this is done, it is possible to suppress the occurrence of striae inside the lens and to prevent the yield from being reduced due to the striae, thereby leading to the present invention.

That is, the present invention provides: (A): In one molecule, the following formula (1)

[0011]

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(In the formula, R ¹ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ² , R ³ and R ⁴ each represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. X represents Represents an S or O atom, and the number of the S atoms is 50% or more on average with respect to the total of the S atom and the O atom constituting the three-membered ring.
Represents -S- or -O-. A) having one or more structures represented by the following formulas) and a compound (b) having a tertiary amino group substituted with an aliphatic and / or aromatic group and having different catalytic activities as a polymerization catalyst. Including the above, the ratio of the tertiary amino group in the compound (b) and the episulfide group in the compound (a) is within the range of 0.0001 to 0.02 as amino group / episulfide group (functional group molar ratio). A polymerizable composition, comprising: (B): the compound (a) has the following formula (2) in one molecule:

[0013]

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(In the formula, R ⁵ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ⁶ , R ⁷ and R ⁸ each represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. X represents Represents an S or O atom, and the number of S atoms is 50% or more on average with respect to the sum of the S atom and the O atom constituting the three-membered ring.) (A)
Polymerizable composition. (C): The polymerizable composition of the above (A), wherein the compound (a) is a compound represented by the following formula (3).

[0015]

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(Wherein R ^{9 to} R ¹⁴ each have 1 to 1 carbon atoms)
Indicate 10 hydrocarbon groups or hydrogen atoms. Y is a substituted or unsubstituted linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted 1,4-dithiane group,
Represents an arylene group. m represents an integer of 0 to 2;
Represents an integer of 0 to 4. X represents an S or O atom. (D): The polymerizable composition of the above (A), wherein the compound (a) is a compound represented by the following formula (4).

[0017]

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(Wherein R ^{15 to} R ²⁰ each have 1 to 1 carbon atoms)
Represents 10 hydrocarbon groups or hydrogen atoms. X represents an S or O atom. (E): The compound (b) having a tertiary amino group having a different catalytic activity and used as a polymerization catalyst is selected from N, N-dimethylcyclohexylamine, N, N
-The polymerizable composition of the above (A), which is two or more types selected from diethylethanolamine and N, N-diisopropylethylamine and N-methyldicyclohexylamine each having low catalytic activity. (F): a resin obtained by heating and curing the polymerizable composition of (A) to (E). (G): A method for producing a resin, comprising heating and curing the polymerizable composition of (A) to (E). (H): an optical material comprising the resin of (F). (I): A method for producing an optical material, wherein the polymerizable composition of (A) to (E) is cast-polymerized. (J): The following formula (5)

[0019]

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(Wherein X represents an S or O atom and may be the same or different), and a compound substituted with an aliphatic and / or aromatic 3
A tertiary amino group in compound (d) containing one or more compounds (d) having a tertiary amino group and a compound (c)
The ratio of episulfide groups in the composition is 0.0001 to 0.02 as amino group / episulfide group (functional group molar ratio).
A polymerizable composition characterized by being within the range. (K): the compound (d) having a tertiary amino group is N,
The polymerizable composition according to the above (J), which is one or more selected from N-diisopropylethylamine, N, N-dimethylcyclohexylamine, and N-methyldicyclohexylamine. (L): a resin obtained by heating and curing the polymerizable composition of (J) or (K). (M): A method for producing a resin, comprising heating and curing the polymerizable composition of (J) or (K). (N): an optical material comprising the resin of (L). (O): A method for producing an optical material, comprising casting-polymerizing the polymerizable composition of (J) or (K). It is about.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION Whether or not the compounds (b) having two or more tertiary amino groups of the present invention have different catalytic activities can be determined, for example, by the following method. (1): Bis (β-epithiopropyl) disulfide is selected as the reference compound (a), and a compound (b) having one kind of tertiary amino group is added to the amino group / episulfide group (functional group). (Molar ratio) was 0.0025, and the viscosity of the mixture immediately after the completion of mixing at 20 ° C. and the viscosity of the mixture 3 hours after mixing were measured to determine the amount of change in viscosity. The resulting mixture is heated from 30 ° C. to 80 ° C. over 10 hours, and the exothermic onset time and exothermic maximum temperature are examined. (2): For the compound (b) having various tertiary amino groups, the amount of change in viscosity is examined in the same manner as in (1). (3): An arbitrary two kinds of compounds (b) having a tertiary amino group are selected, and a change in viscosity, an exothermic onset time and an exothermic maximum attainment temperature of the two kinds of compounds (b) are compared. The difference is 50 mPa · s or more,
When one or more of the conditions of heat generation time of 2 hours or more and maximum heat generation temperature of 30 ° C. or more are met,
The two compounds (b) have different catalytic activities.

Hereinafter, the present invention will be described in detail.

In the present invention, the compound (b) contains two or more compounds (a) and a compound (b) substituted with an aliphatic group and / or an aromatic group and having a tertiary amino group having different catalytic activities. )) And the ratio of the tertiary amino group in the compound (a) to the episulfide group in the amino group / episulfide group (functional group molar ratio) is 0.0001 to 0.02, preferably 0.0002 to 0.01. Within the range, the polymerizable composition can sufficiently secure the pot life of the monomer, suppress heat generation during polymerization, and improve the hue of the obtained resin while maintaining a high refractive index and a high Abbe number. At the same time, yellowing due to post-heating can be reduced. In addition, the occurrence of striae inside the lens when the lens is mass-produced can be suppressed, and a decrease in the yield due to the striae can be prevented.

The present invention also includes the compound (c) and one or more compounds (d) having a tertiary amino group substituted with an aliphatic and / or aromatic group. The polymerizable composition in which the ratio of the tertiary amino group to the episulfide group in the compound (c) is in the range of 0.0001 to 0.02 as amino group / episulfide group (molar ratio of functional group), The pot life can be sufficiently ensured, heat generation during polymerization can be suppressed, and in the obtained resin, the hue of the resin can be improved while yellowing due to post-heating can be reduced while maintaining a high refractive index and a high Abbe number.

Specific examples of the compound having a tertiary amino group of the compound (b) or (d) of the present invention include triethylamine, tri-n-butylamine, tri-n-hexylamine,
N, N-diisopropylethylamine, triethylenediamine, triphenylamine, N, N-dimethylethanolamine, N, N-diethylethanolamine,
N-dibutylethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-dimethylbenzylamine, N, N-diethylbenzylamine, tribenzylamine, N-methyldibenzylamine,
N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N, N-dimethylbutylamine, N-methyldicyclohexylamine, N-methylmorpholine, N-isopropylmorpholine, pyridine, quinoline, N, N-dimethylaniline, 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-tris (N,
Examples thereof include aliphatic and aromatic tertiary amines such as (N-dimethylaminomethyl) phenol, but are not limited to these exemplified compounds. Among these exemplified compounds, preferred compounds include N, N-diisopropylethylamine, N-methyldicyclohexylamine,
N, N-dimethylcyclohexylamine and N, N-diethylethanolamine; as compound (b), 3
Good results can be obtained by mixing and using two or more types of secondary amines having different catalytic activities.

Preferred examples of the combination of tertiary amines having different catalytic activities of compound (b) include compound (a)
, And the type of the resin modifier described below, but it cannot be limited unconditionally, but N, N-dimethylcyclohexylamine, N, N-diethylethanolamine having high catalytic activity, and N, N having low catalytic activity as N, N-diethylethanolamine N, N-dimethylcyclohexylamine and N-methyldicyclohexylamine each selected from N-diisopropylethylamine and N-methyldicyclohexylamine, N, N
-Dimethylcyclohexylamine and N, N-diisopropylethylamine; and N, N-diethylethanolamine and N-methyldicyclohexylamine.

Specific examples of the compound (a) used as a raw material in the present invention include bis (β-epithiopropyl) sulfide, bis (β-epithiopropyl) disulfide, bis (β-epithiopropylthio) methane ,
1,2-bis (β-epithiopropylthio) 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-epi Thiopropylthiomethyl) -3
-Thiapentane, 1,5-bis (β-epithiopropylthio) -2,4-bis (β-epithiopropylthiomethyl) -3-thiapentane, 1- (β-epithiopropylthio) -2,2 -Bis (β-epithiopropylthiomethyl) -4-thiahexane, 1,8-bis (β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 8-bis (β-epithiopropylthio) -4,5-bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8
-Bis (β-epithiopropylthio) -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-tris [｛2- (β-epithiopropylthio)
Ethyl @ thiomethyl] -2- (β-epithiopropylthio) ethane, 1,1,2,2-tetrakis [{2- (β
-Epithiopropylthio) ethyl {thiomethyl] ethane, 1,11-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-bis (β-epithiopropylthio)-
5,7-bis (β-epithiopropylthiomethyl)-
Linear aliphatic β- such as 3,6,9-trithiaundecane
Epithiopropylthio compound 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 Cycloaliphatic β-epithiopropylthio compounds such as 2,5-bis [{2- (β-epithiopropylthio) ethyl} thiomethyl] -1,4-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-bis {4- (β-epithiopropylthio) phenyl} propane, bis {4- (β-epithiopropylthio) phenyl} sulfide, bis {4- (β-epithiopropylthio) phenyl} sulfone, Aromatic β such as 4,4′-bis (β-epithiopropylthio) biphenyl
-Epithiopropylthio compounds, etc., and further 3-mercaptopropylene sulfide, 4-mercaptobutene sulfide, etc., mercapto group-containing epithio compounds, furthermore, bis (β-epithiopropyl) ether, bis (β-epithiopropyloxy) Methane, 1,2-bis (β-epithiopropyloxy) ethane, 1,3-bis (β-epithiopropyloxy) propane, 1,2-bis (β-epithiopropyloxymethyl) propane, 1- (Β-epithiopropyloxy) -2- (β-epithiopropyloxymethyl) propane, 1,4-bis (β-epithiopropyloxy) butane, 1,3-bis (β-epithiopropyloxy) Butane, 1- (β-epithiopropyloxy) -3- (β-epithiopropyloxymethyl) butane, 1,5-bis (β- Pichi O propyloxy) pentane, 1-(beta-epithiopropyl) -4-
(Β-epithiopropyloxymethyl) pentane, 1,
6-bis (β-epithiopropyloxy) hexane, 1
-(Β-epithiopropyloxy) -4- (β-epithiopropyloxymethyl) hexane, 1- (β-epithiopropyloxy) -2-[(2-β-epithiopropyloxyethyl) oxy] Ethane, 1- (β-epithiopropyloxy) -2-[[2- (2-β-epithiopropyloxyethyl) oxyethyl] oxy] ethane,
Tetrakis (β-epithiopropyloxymethyl) methane, 1,1,1-tris (β-epithiopropyloxymethyl) propane, 1,5-bis (β-epithiopropyloxy) -2- (β-epi Thiopropyloxymethyl) -3-thiapentane, 1,5-bis (β-epithiopropyloxy) -2,4-bis (β-epithiopropyloxymethyl) -3-thiapentane, 1- (β-epithio Propyloxy) -2,2-bis (β-epithiopropyloxymethyl) -4-thiahexane, 1,5,6
-Tris (β-epithiopropyloxy) -4- (β-
Epithiopropyloxymethyl) -3-thiahexane,
1,8-bis (β-epithiopropyloxy) -4-
(Β-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropyloxy) -4,5-bis (β-epithiopropyloxymethyl) -3,6-dithiaoctane 1,8-bis (β-epithiopropyloxy) -4,4-bis (β-epithiopropyloxymethyl) -3,6-dithiaoctane,
1,8-bis (β-epithiopropyloxy) -2,
4,5-tris (β-epithiopropyloxymethyl)
-3,6-dithiaoctane, 1,8-bis (β-epithiopropyloxy) -2,5-bis (β-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,9
-Bis (β-epithiopropyloxy) -5- (β-epithiopropyloxymethyl) -5-[(2-β-epithiopropyloxyethyl) oxymethyl] -3,7-
Dithianonane, 1,10-bis (β-epithiopropyloxy) -5,6-bis [(2-β-epithiopropyloxyethyl) oxy] -3,6,9-trithiadecane, 1,11-bis ( β-epithiopropyloxy)-
4,8-bis (β-epithiopropyloxymethyl)-
3,6,9-trithiaundecane, 1,11-bis (β
-Epithiopropyloxy) -5,7-bis (β-epithiopropyloxymethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropyloxy) -5,7- Bis [(2-β-epithiopropyloxyethyl) oxymethyl] -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropyloxy) -4,7-bis (β-epi Thiopropyloxymethyl) -3,6,9-trithiaundecane, 1,3- and 1,4-bis (β-epithiopropyloxy) cyclohexane, 1,3- and 1,4-bis (β-epi Thiopropyloxymethyl) cyclohexane, bis [4-
(Β-epithiopropyloxy) cyclohexyl] methane, 2,2-bis [4- (β-epithiopropyloxy) cyclohexyl] propane, bis [4- (β-epithiopropyloxy) cyclohexyl] sulfide,
2,5-bis (β-epithiopropyloxymethyl)-
1,4-dithiane, 2,5-bis (β-epithiopropyloxyethyloxymethyl) -1,4-dithiane,
Examples thereof include 1,3- and 1,4-bis (β-epithiopropyloxy) benzene, 1,3- and 1,4-bis (β-epithiopropyloxymethyl) benzene, and the like. It is not limited only to the exemplified compounds. These compounds may be used alone or in combination of two or more.

The polymerizable composition of the present invention includes not only a mixture of these episulfide compounds, but also other polysulfide oligomers such as dimers, trimers, and tetramers of these compounds, and the synthesis of episulfide resins. Episulfide resins having a mercapto group generated when epihalohydrin is deficient, as well as organic and inorganic compounds such as inorganic acids and organic acids, solvents, unreacted raw materials and other by-products and impurities used in the synthesis of episulfide, and impurities. It may be included in a range that does not result in

In the polymerizable composition for a lens of the present invention, mainly adjustment of optical properties such as refractive index of the obtained lens, adjustment of various physical properties such as specific gravity, adjustment of viscosity of the polymerizable composition and other handling. For example, a resin modifier may be added for the purpose of improving the resin.

Examples of the resin modifier include episulfide compounds, epoxy compounds, olefins including (meth) acrylates, primary and secondary amine compounds, other than those contained in the polymerizable composition according to the present invention. Thiol compounds, polyphenols, amino acids and mercaptoamines, organic acids and anhydrides, and mercapto organic acids.

Specific examples of preferred epoxy compounds as the 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, hydrogenated bisphenol A glycidyl. Alcohol-based epoxy compounds obtained by condensation of a polyhydric alcohol compound such as ether and an epihalohydrin compound,
3,4-epoxycyclohexylmethyl-3 ', 4'-
Condensation of glycidyl ester-based epoxy compounds, primary and secondary diamine compounds with epihalohydrin compounds obtained by condensation of polyhalogenated organic acid compounds such as epoxycyclohexanecarboxylate and 1,2-hexahydrophthalic acid diglycidyl ester with epihalohydrin compounds And other aliphatic polyepoxy compounds such as vinylcyclohexene diepoxide, but are not limited to these exemplified compounds. Also, these alone,
A mixture of two or more types may be used.

Specific examples of preferable olefins as the resin modifier include benzyl acrylate, benzyl methacrylate, butoxyethyl acrylate, butoxymethyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate and 2-hydroxyethyl acrylate. Methyl 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 diacrylate Methacrylate, 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-methacryloyl ethoxy phenyl) propane, 2,2-bis (4
-Acroxydiethoxyphenyl) 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, trimethylol Propane trimethacrylate, glycerol diacrylate,
Glycerol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate,
Methylthioacrylate, methylthiomethacrylate,
(Meth) acrylate compounds such as phenylthioacrylate, benzylthiomethacrylate, xylylenedithiol diacrylate, xylylenedithiol dimethacrylate, mercaptoethyl sulfide diacrylate, mercaptoethyl sulfide dimethacrylate, allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl Allyl compounds such as isophthalate, diallyl carbonate and diethylene glycol bisallyl carbonate, vinyl compounds such as styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinylbenzene, 3,9-divinylspirobi (m-dioxane), diisopropenyl Examples include benzene, but are not limited to only these exemplified compounds. These may be used alone or in combination of two or more. Any of the above resin modifiers can be used alone or in combination of two or more.

Specific examples of preferred primary or secondary amine compounds as the resin modifier include ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, pentylamine, and the like. 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 preferable thiol compounds include methyl mercaptan, ethyl mercaptan, 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,4-butanedithiol, 1,2,2
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),
Trimethylolpropane tris 3-mercaptopropionate), 1,1,1-trimethylmercaptoethane,
1,1,1-trimethylmercaptopropane, 2,5-
Dimercaptomethylthiophene, 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-
Aliphatic thiols such as 1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and benzylmercaptan and thiol Phenol,
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 polyphenols include a phenolic hydroxyl group on the aromatic ring.
Monophenols such as phenol, o-cresol, m-cresol, p-cresol, 3-methoxyphenol, 4-ethoxyphenol, 4-n-propoxyphenol, 3-butoxyphenol, nonylphenol, -N-propylphenol, 2,3,4,6-tetrachlorophenol, 2,
3,5,6-tetrafluorophenol, 2,4,6-
Tribromophenol, 2,6-dichloro-4-fluorophenol, 2,6-dichloro-4-nitrophenol, 2,3,4-trichlorophenol, 4-bromo-
2-chlorophenol, 2,4-dibromophenol,
2-chloro-4-nitrophenol, 2,3-dichlorophenol, 2-fluoro-4-nitrophenol,
3,5-xylenol, 2,3-difluorophenol, 2,4-dinitrophenol, 2-bromophenol, 2-amino-4-chloro-5nitrophenol, 2
-Chlorophenol, 4-amino-2,6-dichlorophenol, 2-nitrophenol, 2-amino-4-nitrophenol, thymol, carvacrol, α-naphthol, 2-aminophenol and the like. , Catechol, 3-chlorocatechol,
Resorcin, hydroquinone, chlorohydroquinone,
Examples include pyrogallol and phloroglucin, but are not limited to these exemplified compounds. These polyphenol compounds may be used alone or in combination of two or more.

Specific examples of preferred mercapto organic acids include thioglycolic acid, 3-mercaptopropionic acid, thioacetic acid, thiolactic acid, thiomalic acid, and thiosalicylic acid, but are not limited to these exemplified compounds. is not. These may be used alone or in combination of two or more.

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.

In addition to these resin modifiers, an internal release agent, a light stabilizer, an ultraviolet absorber,
Known additives such as an antioxidant, a dye, and a filler may be added.

A typical polymerization method for obtaining the resin (eg, a plastic lens) of the present invention includes cast polymerization. That is, the polymerizable composition of the present invention is injected into a molding mold held by a gasket or a tape after mixing a resin modifier as necessary. At this time, before the injection or after the injection, if necessary, a treatment such as defoaming may be performed.

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 polymerization method, polymerization conditions and the like for obtaining the resin of the present invention vary depending on the type and amount of the curing catalyst used and the type and ratio of the monomer, and therefore cannot be unconditionally limited.

The conditions for the heat polymerization of the polymerizable composition of the present invention injected into the molding mold depend on the type of the compound (a) and the compound (b) of the present invention, the type of the resin modifier, the shape of the molding mold, and the like. Although the conditions cannot be limited because the conditions are largely different, the reaction is performed at a temperature of about −50 to 200 ° C. for 0.1 to 100 hours. Preferably, good results are obtained by maintaining the temperature in the range of 10 ° C. to 150 ° C. or by gradually raising 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.

When molding the resin of the present invention, a chain extender, a crosslinking agent,
Light stabilizers, ultraviolet absorbers, antioxidants, anti-coloring agents other than the present invention, dyes, fillers, internal and / or external release agents,
Various substances such as a compound having a hydroxyl group may be added as an internal and / or external adhesion improver and a dyeability improver.

Further, with respect to the resin molded body taken out,
If necessary, a process such as annealing may be performed.

Further, the resin of the present invention can be obtained as molded articles of various forms by changing a molding mold at the time of casting polymerization, and can be used for optical materials such as spectacle lenses, camera lenses, light emitting diodes (LED), and the like. It can be used for various applications as a transparent resin. In particular, it is suitable as an optical material for eyeglass lenses, camera lenses, and the like.

In the lens using the optical material of the present invention, anti-reflection, high hardness, high abrasion resistance, high chemical resistance, high anti-fogging property, high fashionability, etc. are improved as required. Therefore, physical or chemical treatment such as surface polishing, antistatic treatment, hard coat treatment, non-reflective coat treatment, and dyeing treatment can be performed.

[0048]

The present invention will be described below in more detail with reference to examples. In the performance test of the obtained resin, the refractive index, Abbe number, heat resistance, resin hue, pot life, and heat generation during polymerization were evaluated by the following test methods.

Refractive index (nd), Abbe number (νd):
It was measured at 20 ° C. using a Pulfrich refractometer. Heat resistance: TMA penetration method (load 50g,
Pin tip 0.5mmφ, temperature rise 10 ° C / min, 150 ° C /
max) was measured for Tg. Hue: A resin flat plate having a thickness of 9 mm was prepared, and its yellowness (hereinafter abbreviated as YI) was measured using a colorimeter (manufactured by Minolta). Note that ΔYI in the example table is 12
This is a value obtained by subtracting the resin hue at the time of completion of polymerization from the resin hue after performing the heat treatment at 0 ° C. for 3 hours, and represents a change amount of the hue. Pot life: The polymerizable composition was kept warm in a water bath at a temperature of 30 ° C., and the viscosity after 7 hours was measured by a B-type viscometer. The evaluation method was such that the viscosity after 7 hours was 100 mPa ·
s or less was rated as 、, 150 mPa · s or less as Δ, and gelled and resinized as ×. -Measurement of heat generation during polymerization: The temperature of the resin during polymerization was measured using a thermocouple thermometer equipped with a recorder, and the value obtained by subtracting the temperature of the resin from the temperature of the polymerization oven was defined as the heat generation. Stria judgment: 100 sheets of resin were prepared, the obtained resin was exposed to a high-pressure mercury lamp, and the presence or absence of stria was visually observed.
The yield was calculated.

In Examples and Comparative Examples, bis (2,3-epithiopropyl) disulfide (hereinafter abbreviated as compound (A)) was used as compound (a) or (c), and compound (A) was added as a resin modifier. Represents benzylamine (hereinafter abbreviated as modifier (A)) or 4,8-dimercaptomethyl-1,
11-mercapto-3,6,9-trithiaundecane (hereinafter abbreviated as modifier (B)) was used.

Example 1 7000 g of compound (A) as compound (a), 1.4 g of N, N-dimethylcyclohexylamine (hereinafter referred to as DCA) as compound (b) and N, N-dicyclohexylmethylamine (hereinafter referred to as DCH) 7 g and 700 g of a modifier (B) as a resin modifier were added, stirred, and defoamed for 1 hour under reduced pressure. After filtration through a 3 μm Teflon (registered trademark) filter, the mixture was divided into equal amounts and poured into 100 molded molds each composed of a glass mold and a gasket over 4 hours.
After keeping the mold at 30 ° C. for 10 hours, the temperature was gradually raised from 30 ° C. to 80 ° C., and polymerization was performed for 20 hours.
After completion of the polymerization, the resin was gradually cooled and the resin was taken out of the mold. The obtained resin is annealed at 120 ° C. for 3 hours,
100 sheets of resin were obtained. Table 1 shows the physical properties and hue, the pot life of the polymer composition, and the yield due to striae.

Example 2 7000 g of compound (A) as compound (c), 14 g of DCA as compound (d), and 700 g of modifier (B) as a resin modifier were stirred, degassed for 1 hour under reduced pressure. . After filtration through a 3 μm Teflon filter, the mixture was divided into equal amounts and poured into 100 molded molds each composed of a glass mold and a gasket over 4 hours. This mold is
After keeping the temperature at 10 ° C. for 10 hours, the temperature was gradually raised from 30 ° C. to 80 ° C., and polymerization was carried out for 20 hours. After completion of the polymerization, the resin was gradually cooled and the resin was taken out of the mold. Obtained resin 1
Annealing was performed at 20 ° C. for 3 hours to obtain 100 sheets of resin. Table 1 shows the physical properties and hue, the pot life of the polymer composition, and the yield due to striae.

Example 3 7000 g of compound (A) as compound (c), 14 g of DCA as compound (d), and 350 g of modifier (B) as a resin modifier were stirred and degassed for 1 hour under reduced pressure. . After filtration through a 3 μm Teflon filter, the mixture was divided into equal amounts and poured into 100 molded molds each composed of a glass mold and a gasket over 4 hours. This mold is
After keeping the temperature at 10 ° C. for 10 hours, the temperature was gradually raised from 30 ° C. to 80 ° C., and polymerization was carried out for 20 hours. After completion of the polymerization, the resin was gradually cooled and the resin was taken out of the mold. Obtained resin 1
Annealing was performed at 20 ° C. for 3 hours to obtain 100 sheets of resin. Table 1 shows the physical properties and hue, the pot life of the polymer composition, and the yield due to striae.

[0054]

[Table 1]

Example 4 100 g of the compound (A) as the compound (a), 0.02 g of DCA and 0.1 g of DCH as the compound (b), and 5 g of the modifying agent (A) as a resin modifying agent were stirred, and the mixture was stirred under reduced pressure. Degas for 0.4 hours under. After filtration through a 3 μm Teflon filter, the mixture was poured into a molding mold composed of a glass mold and a gasket. After keeping the mold at 30 ° C. for 10 hours, the temperature was gradually raised from 30 ° C. to 80 ° C., and polymerization was performed for 20 hours. After completion of the polymerization, the resin was gradually cooled and the resin was taken out of the mold. The obtained resin is heated at 120 ° C. for 3 hours.
Annealed for a time and measured for physical properties. Table 2 shows the physical properties and hue, and the pot life of the polymerization composition.

Example 5 The same operation as in Example 4 was carried out except that 0.02 g of DCA and 0.5 g of N, N-diisopropylethylamine (hereinafter DIPEA) were used as compound (b). Table 2 shows the physical properties and hue, and the pot life of the polymerizable composition.

Example 6 As compound (b), 0.02 g of DCA and 0.5 of DCH were used.
The same operation as in Example 4 was performed except that g was used.
Table 2 shows the physical properties and hue, and the pot life of the polymerizable composition.

Example 7 The same operation as in Example 4 was carried out except that 0.05 g of N, N-diethylethanolamine (hereinafter referred to as DEEA) and 0.5 g of DCH were used as the compound (b). Table 2 shows the physical properties and hue, and the pot life of the polymerizable composition.

Example 8 The same operation as in Example 4 was performed except that 10 g of the modifier (B) was used as the resin modifier. Table 2 shows the physical properties and hue, and the pot life of the polymerizable composition.

Example 9 The same operation as in Example 5 was performed except that 10 g of the modifier (B) was used as the resin modifier. Table 2 shows the physical properties and hue, and the pot life of the polymerizable composition.

Example 10 The same operation as in Example 6 was carried out except that 10 g of the modifier (B) was used as the resin modifier. Table 2 shows the physical properties and hue, and the pot life of the polymerizable composition.

Example 11 The same operation as in Example 7 was carried out except that 10 g of the modifier (B) was used as the resin modifier. Table 2 shows the physical properties and hue, and the pot life of the polymerizable composition.

[0063]

[Table 2]

Example 12 100 g of the compound (A) as the compound (c), 0.5 g of DIPEA as the compound (d), and 5 g of the modifier (A) as a resin modifier were stirred, and the mixture was stirred under reduced pressure. Degassed for hours. After filtration through a 3 μm Teflon filter, the mixture was poured into a molding mold composed of a glass mold and a gasket. After keeping the mold at 30 ° C. for 10 hours,
The temperature was gradually raised from 80 ° C. to 80 ° C., and polymerization was performed in 20 hours. After completion of the polymerization, the resin was gradually cooled and the resin was taken out of the mold. The obtained resin was annealed at 120 ° C. for 3 hours, and physical properties were measured. Table 3 shows the physical properties and hue, and the pot life of the polymer composition.

Example 13 The same operation as in Example 12 was carried out except that 0.5 g of DCH was used instead of DIPEA as compound (d). Table 3 shows the physical properties and hue, and the pot life of the polymerizable composition.

Example 14 The same operation as in Example 12 was carried out except that 0.5 g of DEEA was used instead of DIPEA as compound (d). Table 3 shows the physical properties and hue, and the pot life of the polymerizable composition.

Example 15 As a compound (d), DCA was used instead of DIPEA.
The same operation as in Example 12 was performed except that 0.2 g was used. Table 3 shows the physical properties and hue, and the pot life of the polymerizable composition.

Example 16 The same operation as in Example 12 was performed except that 10 g of the modifier (B) was used as the resin modifier. Table 3 shows the physical properties and hue, and the pot life of the polymerizable composition.

Example 17 The same operation as in Example 13 was performed except that 10 g of the modifier (B) was used as the resin modifier. Table 3 shows the physical properties and hue, and the pot life of the polymerizable composition.

Example 18 The same operation as in Example 14 was carried out except that 10 g of the modifier (B) was used as the resin modifier. Table 3 shows the physical properties and hue, and the pot life of the polymerizable composition.

Example 19 The same operation as in Example 15 was performed except that 10 g of the modifier (B) was used as the resin modifier. Table 3 shows the physical properties and hue, and the pot life of the polymerizable composition.

[0072]

[Table 3]

Comparative Example 1 100 g of compound (A) as compound (a), 1.5 g of DCA and 3.0 g of DCH as a catalyst, and 10 g of modifier (B) as a resin modifier were stirred, and stirred under reduced pressure. Degassed for 4 hours. After filtration through a 3 μm Teflon filter, the mixture was poured into a molding mold composed of a glass mold and a gasket. After keeping the mold at 30 ° C. for 10 hours,
The temperature was gradually raised from 0 ° C. to 80 ° C., and polymerization was performed in 20 hours. After completion of the polymerization, the resin was gradually cooled and the resin was taken out of the mold. The obtained resin was annealed at 120 ° C. for 3 hours, and physical properties were measured. The physical properties and hue, and the pot life of the polymerizable composition are shown in Table 4. The obtained resin was remarkably yellowed, and the pot life was converted into a resin in about 3 hours with severe heat generation.

Comparative Example 2 Compound (A) (100 g), DCA alone as catalyst (2.5 g)
g and 5 g of a modifier (A) as a resin modifier were stirred and defoamed under reduced pressure for 0.4 hours. After filtration through a 3 μm Teflon filter, the mixture was poured into a molding mold composed of a glass mold and a gasket. This mold is
After keeping the temperature for 0 hour, the temperature was gradually raised from 30 ° C. to 80 ° C., and polymerization was carried out for 20 hours. After completion of the polymerization, the resin was gradually cooled and the resin was taken out of the mold. The obtained resin is 12
Annealing was performed at 0 ° C. for 3 hours, and physical properties were measured. The physical properties and hue, and the pot life of the polymerizable composition are shown in Table 4. The refractive index and the heat resistance are reduced, and the pot life is short. Could not be obtained.

Comparative Example 3 The same operation as in Comparative Example 2 was performed except that 0.001 g of DCA alone was used as a catalyst. The physical properties and hue, and further, the pot life are shown in Table 4, but the polymerization did not proceed sufficiently and the optical physical properties were reduced.

Comparative Example 4 Triethylamine (hereinafter referred to as “catalyst”) was used instead of DCA as a catalyst.
Comparative Example 2 except that TEA) alone was used in an amount of 2.0 g.
The same operation was performed. The physical properties, hue, and pot life are shown in Table 4. The obtained resin was remarkably yellowed, and the pot life was violently heated and turned into a resin in about 4 hours.

Comparative Example 5 TEA was used alone as a catalyst instead of DCA in an amount of 0.009.
The same operation as in Comparative Example 2 was performed except that g was used. The physical properties and hue, and further, the pot life are shown in Table 4, but the polymerization did not proceed sufficiently and the optical physical properties were reduced.

Comparative Example 6 Modifier (B) instead of Modifier (A) as a resin modifier
Was performed in the same manner as in Comparative Example 2 except that 10 g was used. The physical properties, hue, and pot life are shown in Table 4. The obtained resin was significantly yellowed, and the pot life gelled with heat generation after 5 hours, and no satisfactory results were obtained. Comparative Example 7 Modifier (B) in place of Modifier (A) as a resin modifier
Was carried out in the same manner as in Comparative Example 3 except that 10 g was used. The physical properties and hue, and further, the pot life are shown in Table 4, but the polymerization did not proceed sufficiently and the optical physical properties were reduced.

Comparative Example 8 Modifier (B) was used in place of modifier (A) as a resin modifier.
Was performed in the same manner as in Comparative Example 4 except that 10 g was used. The physical properties, hue, and pot life are shown in Table 4. The obtained resin was remarkably yellowed, and the pot life was changed to resin in about 5 hours with intense heat generation.

Comparative Example 9 A modifier (B) was used instead of the modifier (A) as a resin modifier.
Was performed in the same manner as in Comparative Example 5 except that 10 g was used. The physical properties and hue, and further, the pot life are shown in Table 4, but the polymerization did not proceed sufficiently and the optical physical properties were reduced.

[0081]

[Table 4]

[0082]

According to the polymerizable composition of the present invention and the resin obtained by curing by polymerization, the pot life of the polymerizable composition, which was difficult in the prior art, can be sufficiently ensured, and the heat generation during polymerization can be suppressed. In the obtained resin, while maintaining a high refractive index and a balanced Abbe number, the hue of the resin can be improved and yellowing due to post-heating can be reduced.
Further, it is possible to suppress the occurrence of striae inside the lens when the lens is mass-produced, and to provide an effect of preventing a decrease in the yield due to the striae. In particular, the effect of preventing the yield from lowering due to striae is remarkable when two or more compounds having a tertiary amino group (b) having different catalytic activities are used as the polymerization catalyst.

As a result, a long pot life of the polymerizable composition can be ensured, yellowing due to heating is reduced, and heat generation during polymerization is suppressed while maintaining a high refractive index. Can be obtained, and a decrease in the yield due to striae can be prevented. Prolonging the pot life leads to an improvement in workability during resin production, and the obtained resin contributes to the thinness and fashionability of the lens particularly in the field of spectacle lenses.

Continued on the front page (72) Inventor Hiroyuki Morishiri 30 Asamuta-cho, Omuta-shi, Fukuoka Prefecture Mitsui Chemicals, Inc. (72) Inventor Chitose Shimakawa 30 Asamuta-cho, Omuta-shi, Fukuoka Mitsui Chemicals, Inc. (72) Invention Person Mitsuki Okazaki 580-32 Nagaura, Sodegaura-shi, Chiba Prefecture Mitsui Chemicals Co., Ltd. 30-cho, Mitsui Chemicals, Inc. F-term (reference) 4J030 BA04 BA42 BB03 BC21 BG25

Claims (15)

[Claims] 1. The following formula (1) in one molecule: (Wherein, R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ² , R ³ and R ⁴ each represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. X represents S or O atoms, and the number of S atoms is 50% or more on average with respect to the total of S atoms and O atoms constituting the three-membered ring. X ′ represents —S— or —O—. A) having one or more structures represented by the following formulas) and a compound (b) having a tertiary amino group substituted with an aliphatic and / or aromatic group and having different catalytic activities as a polymerization catalyst. Including the above, the ratio of the tertiary amino group in the compound (b) to the episulfide group in the compound (a) is within the range of 0.0001 to 0.02 as amino group / episulfide group (functional group molar ratio). A polymerizable composition, comprising: 2. The compound (a) has the following formula (2) in one molecule: (Wherein, R ⁵ is a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ⁶ , R ⁷ and R ⁸ each represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. X represents S or O atoms, and the number of S atoms is 50% or more on average with respect to the total of S atoms and O atoms constituting the three-membered ring. 2. The polymerizable composition according to claim 1, which is a compound having at least one structure represented by the formula: 3. The polymerizable composition according to claim 1, wherein the compound (a) is a compound represented by the following formula (3). Embedded image (Wherein, R ^{9 to} R ¹⁴ each represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. Y is a substituted or unsubstituted linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms. ,
Represents a substituted or unsubstituted 1,4-dithiane group or an arylene group. m represents an integer of 0 to 2; n represents an integer of 0 to 4; X represents an S or O atom. ) 4. The polymerizable composition according to claim 1, wherein the compound (a) is a compound represented by the following formula (4). Embedded image (In the formula, R ^{15 to} R ²⁰ each represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. X represents an S or O atom.) 5. A compound (b) having a tertiary amino group having a different catalytic activity, which is used as a polymerization catalyst, is selected from N, N-dimethylcyclohexylamine,
2. The polymerizable composition according to claim 1, wherein the polymerizable composition is at least two members selected from N, N-diethylethanolamine and N, N-diisopropylethylamine and N-methyldicyclohexylamine each having low catalytic activity. 6. A resin obtained by heating and curing the polymerizable composition according to claim 1. 7. A method for producing a resin, comprising curing the polymerizable composition according to claim 1 by heating. 8. An optical material comprising the resin according to claim 6. 9. A method for producing an optical material, comprising subjecting the polymerizable composition according to claim 1 to casting polymerization. 10. The following formula (5): (Wherein X represents S or O atoms, and may be the same or different), and a compound having an aliphatic and / or aromatic substituted tertiary amino group (D), wherein the ratio of the tertiary amino group in the compound (d) and the episulfide group in the compound (c) is 0.0001 as amino group / episulfide group (functional group molar ratio). A polymerizable composition characterized by being in the range of 0.02 to 0.02. 11. A compound (d) having a tertiary amino group
11. The polymerizable composition according to claim 10, wherein is at least one member selected from N, N-diisopropylethylamine, N, N-dimethylcyclohexylamine, and N-methyldicyclohexylamine. 12. A resin obtained by curing the polymerizable composition according to claim 10 by heating. 13. A method for producing a resin, comprising heating and curing the polymerizable composition according to claim 10. 14. An optical material comprising the resin according to claim 12. 15. A method for producing an optical material, comprising casting the polymerizable composition according to claim 10 or 11.