JP4595706B2 - Polymerizable composition - Google Patents

Description

  The present invention relates to a polymerizable composition for producing an optical material, a plastic lens, a prism, an optical film, an optical fiber, an information recording substrate, an optical material used as an LED sealing material, a coating material, and the like, and for spectacles. The present invention relates to an optical lens such as a plastic lens.

  Plastic optical materials generally have advantages such as being lighter, easier to mold and dyeable than inorganic optical materials such as glass. Therefore, in recent years, it has been widely used in the manufacture of various optical products, particularly spectacle lenses.

  The main performance required for optical materials for eyeglass lenses is colorless and transparent with a high refractive index and a high Abbe number from an optical point of view, and high strength from a physical point of view. . A high refractive index enables thinning of the lens, and a high Abbe number reduces bleeding. As for strength, it is necessary to satisfy the strength standards of each country at least, and from a practical point of view, it is required to be more difficult to break and to have good drilling workability. However, various optical materials for spectacle lenses have been developed so far, but no material has been developed that balances the performance of high refractive index, high Abbe number, and high strength.

  A polyurethane material containing an aliphatic linear oligomer has been proposed as an optical material having high impact resistance (see Patent Document 1 and Patent Document 2). Although the Abbe number is as high as 46 and the falling ball impact energy is as high as 12 J or more, it has a disadvantage that the refractive index is as low as about 1.53.

  An optical material having a higher refractive index is polycarbonate resin, which is used mainly in the United States. The refractive index is as high as 1.60, and the falling ball impact energy is as high as 12 J or more. However, since the polycarbonate resin contains many benzene rings in its structure, the Abbe number is as low as 30. For this reason, the polycarbonate resin has a drawback that bleeding occurs.

  A thermosetting optical material having a thiourethane structure obtained by a reaction between a polythiol compound and a polyisocyanate compound has been proposed and commercialized as an optical material having a balanced refractive index and Abbe number. Specific examples include EYAS manufactured by HOYA and MR-90 manufactured by Mitsui Chemicals. Both have a refractive index of 1.60 and are balanced with an Abbe number of 42, which is the mainstream of high refractive lenses in Japan. However, in both cases, the falling ball impact energy is as low as 3.6 J or less, which is not satisfactory in terms of strength.

  As an optical material having a balanced refractive index, Abbe number, and strength, a composite material composed of polyurethane urea and an episulfide compound is disclosed (see Patent Document 3). It has a balanced optical characteristic with a refractive index / Abbe number of 1.63 / 37 to 1.58 / 44, and exhibits very high impact resistance. However, when the reaction of polyisocyanate prepolymer of long chain aliphatic diol, aromatic diamine and episulfide compound is actually carried out, the reaction of polyisocyanate prepolymer and aromatic diamine is much faster than the polymerization of episulfide. However, there is a problem when considering industrial production.

US Pat. No. 5,962,617 US Pat. No. 6,127,505 International Publication No. 03/020786

  An object of the present invention is to provide a polymerizable composition that provides an optical material having a refractive index of around 1.60 and an Abbe number of around 40 and having high strength (impact resistance).

  As a result of intensive studies, the present inventors have found that the above-mentioned optical material obtained by polymerizing and curing a polymerizable composition containing the following four components (A), (B), (C), and (D): Achieved the purpose.

That is, the present invention
(A) a compound having two or more mercapto groups,
(B) a polyurethane prepolymer having an NCO group end;
(C) polyisocyanate, and (D) the following formula (1):

（式中、Ｒ^１は炭素数１〜１０の２価の炭化水素基又は単結合；Ｒ^２、Ｒ^３、及びＲ^４はそれぞれ炭素数１〜１０の炭化水素基又は水素；ＹはＯ又はＳ；ｍは１〜５の整数；および、ｎは０〜５の整数である）で表される構造を１分子中に１個以上有するエピスルフィド化合物を含む重合性組成物、該重合性組成物を重合硬化して得られる光学材料、及び、該光学材料よりなるレンズに関する。

(Wherein R ¹ is a C 1-10 divalent hydrocarbon group or single bond; R ² , R ³ , and R ⁴ are each a C 1-10 hydrocarbon group or hydrogen; Y is O or S; m is an integer of 1 to 5; and n is an integer of 0 to 5), a polymerizable composition comprising an episulfide compound having one or more structures in one molecule, and the polymerizable composition The present invention relates to an optical material obtained by polymerization and curing, and a lens made of the optical material.

  The present invention has found that an optical material having good optical properties and high impact resistance can be produced from a polymerizable composition comprising an episulfide compound represented by the formula (1) and a polyurethane prepolymer having an NCO group terminal. Based on that. In the present invention, a high refractive index is achieved by blending an episulfide compound, and impact resistance is achieved by blending a polyurethane prepolymer having an NCO group end. This is an unparalleled technology that achieves impact resistance and optical properties with a simple system.

  The refractive index / Abbe number of the optical material of the present invention is about 1.60 / Abbe number of about 40, preferably 1.58 to 1.62 / 38 to 42, and is more preferable from the viewpoint of ease of production and preparation. Is 1.59 to 1.61 / 39 to 41.

  In the polymerizable composition of the present invention, the proportions of the components (A), (B), (C), and (D) are in consideration of the refractive index and viscosity of each component, various physical properties of the resulting optical material, and the like. Although determined, the range of (A) component 1 to 40% by weight, (B) component 1 to 70% by weight, (C) component 1 to 50% by weight, and (D) component 1 to 70% by weight is preferable. Within the above range, an optical material having high impact resistance, high refractive index and high Abbe number can be obtained. More preferably, it is in the range of (A) component 5 to 40% by weight, (B) component 15 to 60% by weight, (C) component 1 to 35% by weight, and (D) component 10 to 50% by weight, more preferably Component (A) is in the range of 5 to 25% by weight, component (B) is in the range of 20 to 50% by weight, component (C) is in the range of 1 to 25% by weight, and component (D) is in the range of 20 to 40% by weight.

  The component (A) of the present invention is a compound having two or more mercapto groups per molecule, and its molecular weight is preferably 600 or less. Specific examples thereof include methanedithiol, methanetrithiol, 1,2-dimercaptoethane, 1,2-dimercaptopropane, 1,3-dimercaptopropane, 2,2-dimercaptopropane, 1,4-dimer. Mercaptobutane, 1,6-dimercaptohexane, bis (2-mercaptoethyl) ether, bis (2-mercaptoethyl) sulfide, 1,2-bis (2-mercaptoethyloxy) ethane, 1,2-bis (2 -Mercaptoethylthio) ethane, 2,3-dimercapto-1-propanol, 1,3-dimercapto-2-propanol, 1,2,3-trimercaptopropane, 2-mercaptomethyl-1,3-dimercaptopropane, 2-mercaptomethyl-1,4-dimercaptobutane, 2- (2-mercaptoethylthio) -1, -Dimercaptopropane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,4-dimercaptomethyl-1,5-dimercapto-3-thiapentane, 4,8-dimercaptomethyl-1, 11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11- Dimercapto-3,6,9-trithiaundecane, 1,1,1-tris (mercaptomethyl) propane, tetrakis (mercaptomethyl) methane, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopro Pionate), diethylene glycol bis (2-mercaptoacetate), die Lenglycol bis (3-mercaptopropionate), 1,4-butanediol bis (2-mercaptoacetate), 1,4-butanediol bis (3-mercaptopropionate), trimethylolpropane tris (2-mercapto) Acetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane trismercaptoglycolate, pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakismercapto Glycolate, 1,2-dimercaptocyclohexane, 1,3-dimercaptocyclohexane, 1,4-dimercaptocyclohexane, 1,3-bis (mercaptomethyl) cyclohexane Xane, 1,4-bis (mercaptomethyl) cyclohexane, 2,5-bis (mercaptomethyl) -1,4-dithiane, 2,5-bis (2-mercaptomethyl) -1,4-dithiane, 2,5 -Bis (2-mercaptoethylthiomethyl) -1,4-dithiane, 2,5-bis (mercaptomethyl) -1-thiane, 2,5-bis (2-mercaptoethyl) -1-thiane, 2,5 -Bis (mercaptomethyl) thiophene, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,3-bis (mercaptomethyl) benzene, 1,4-bis (mercapto) Methyl) benzene, 2,2′-dimercaptobiphenyl, 4,4′-dimercaptobiphenyl, bis (4-mercaptophenyl) methane, 2,2-bis (4 Mercaptophenyl) propane, bis (4-mercaptophenyl) ether, bis (4-mercaptophenyl) sulfide, bis (4-mercaptophenyl) sulfone, bis (4-mercaptomethylphenyl) methane, 2,2-bis (4- Mercaptomethylphenyl) propane, bis (4-mercaptomethylphenyl) ether, bis (4-mercaptomethylphenyl) sulfide, 2,5-dimercapto-1,3,4-thiadiazole, 3,4-thiophenedithiol, glyceryl dithioglycol Bis (2-mercaptoethyl) selenide, bis (1,3-dimercapto-2-propyl) selenide, 2,3-bis (mercaptoethylseleno) -1-propanethiol, 2-mercaptomethyl-1,5- Dimercapto-3-selenape Tan, 4,8-bis (mercaptomethyl) -1,11-dimercapto-3,9-dithia-6-selenaundecane, 4,8-bis (mercaptomethyl) -1,11-dimercapto-6-thia-3 , 9-diselenaundecane, 4,8-bis (mercaptomethyl) -1,11-dimercapto-3,6,9-triselenaundecane, bis (hydroxymercaptoethylselenomethyl) benzene, 1,4-dimercapto-2 , 3-bis (mercaptoethylseleno) butane, 1,2,3,4-tetrakis (mercaptoethylseleno) butane, 1,9-dimercapto-5,5-bis (mercaptomethyl) -3,7-diselenanane, tris (Mercaptomethyl) -1,8-dimercapto-6-thia-3-selenaoctane, bis (mercaptoethylselenomethi) Benzene, 2,5-bis (mercaptoethylselenomethyl) -1,4-dithiane, 2,6-dimercapto-1-selena-4-thiane, 3,5-dimercapto-1-selena-4-thiane, 2,6-bis (mercaptomethyl) -1-selena-4-thian, 3,5-bis (mercaptomethyl) -1-selena-4-thian, 2,5-dimercapto-1,4-diselenane, 2, 6-dimercapto-1,4-diselenane, 2,5-bis (mercaptomethyl) -1,4-diselenane, 2,6-bis (mercaptomethyl) -1,4-diselenane, 2,5-dimercaptoselenan 3,4-dimercaptoselenane, 2,5-bis (mercaptomethyl) selenane, 3,4-bis (mercaptomethyl) selenane, 4,5-dimercapto-1,3-diselenolane, , 5-bis (mercaptomethyl) -1,3 Jiserenoran, 3,6-dimercapto tri seleno cyclooctane, 3,6-bis (mercaptomethyl) can be mentioned tri seleno cyclooctane. These may be used alone or in combination of two or more.

  Among the components (A) described above, bis (2-mercaptoethyl) sulfide, trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane trismercaptoglycolate, pentaerythritol tetrakis (3-mercaptopro) Pionate), pentaerythritol tetrakismercaptoglycolate, 2,5-bis (2-mercaptomethyl) -1,4-dithiane, more preferably bis (2-mercaptoethyl) sulfide, trimethylolpropane tris (3- Mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), 2,5-bis (2-mercaptomethyl) -1,4-dithiane. These may be used alone or in combination of two or more. Preferably, a compound having two or more mercapto groups is used in combination with a compound having two mercapto groups in one molecule.

  The component (B) is a polyurethane prepolymer having an NCO group terminal and is prepared from two kinds of raw materials. One of the raw materials is a polyol compound (raw material B1) having two or more OH groups in one molecule, and the other is a polyisocyanate compound (raw material B2) having two or more NCO groups per molecule.

  The polyol compound of the raw material B1 functions as a soft segment, and preferably is an aliphatic linear polyol compound having a number average molecular weight of 100 to 3000 or a linear polyol compound having an aliphatic group and an aromatic group. When the number average molecular weight is 100 or more, the ability as a soft segment is sufficient, and the resulting molded article has good impact resistance. Further, when the number average molecular weight is 3000 or less, the compatibility with the episulfide compound is good, the increase in viscosity can be avoided, and the handling is easy. Preferably, it is an aliphatic linear polyol compound having a number average molecular weight of 400 to 2000 or a linear polyol compound having an aliphatic group and an aromatic group, more preferably an aliphatic linear chain having a number average molecular weight of 400 to 2000. Diol or a linear diol having an aliphatic group and an aromatic group.

  Specific examples of the polyol compound (raw material B1) include polyoxyalkylene glycols such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, and polyoxypentamethylene glycol; polyvalerolactone diol, polycaprolactone diol, and the like. Polylactone polyol; one or more dibasic acids such as adipic acid, sebacic acid, maleic acid, terephthalic acid, isophthalic acid, ethylene glycol, propanediol (including isomers), butanediol (including isomers), Hexanediol (including isomers), methylpentanediol (including isomers), nonanediol (including isomers), methyloctanediol (including isomers), cyclohexanedimethanol (including isomers), glycerin Polyester polyols obtained from one or more polyols such as phloroglucinol, hexanetriol, trimethylolethane, trimethylolpropane, pentaerythritol; hexanediol (including isomers), methylpentanediol (including isomers) And polycarbonate diol obtained from one or more of nonanediol (including isomers) and methyloctanediol (including isomers) and a carbonate compound such as phosgene. These polyol compounds may be used alone or in combination of two or more.

  Preferably, polycaprolactone diol; adipic acid and 3-methyl-1,5-pentanediol, sebacic acid and 3-methyl-1,5-pentanediol, terephthalic acid and 3-methyl-1,5-pentanediol, isophthalic acid Obtained from a combination of acid and 3-methyl-1,5-pentanediol, adipic acid and terephthalic acid and 3-methyl-1,5-pentanediol, adipic acid, isophthalic acid and 3-methyl-1,5-pentanediol A polyester diol obtained from 1,6-hexanediol or 1,6-hexanediol and 3-methyl-1,5-pentanediol and a carbonate compound such as phosgene, more preferably Polycaprolactone diol; adipic acid and 3-methyl- , 5-pentanediol, terephthalic acid and 3-methyl-1,5-pentanediol, isophthalic acid and 3-methyl-1,5-pentanediol, adipic acid, terephthalic acid and 3-methyl-1,5-pentanediol A polyester diol obtained from a combination of adipic acid, isophthalic acid and 3-methyl-1,5-pentanediol; and 1,6-hexanediol or 1,6-hexanediol and 3-methyl-1,5- Polycarbonate diol obtained from pentanediol and a carbonate compound such as phosgene, more preferably polycaprolactone diol; adipic acid and 3-methyl-1,5-pentanediol, terephthalic acid and 3-methyl-1,5 -Pentanediol, isophthalic acid and 3-methyl-1,5-pe Tandiol, polyester diol obtained from a combination of adipic acid, terephthalic acid and 3-methyl-1,5-pentanediol, adipic acid, isophthalic acid and 3-methyl-1,5-pentanediol; and 1,6- Polycarbonate diol obtained from hexanediol or 1,6-hexanediol and 3-methyl-1,5-pentanediol and a carbonate compound such as phosgene and having a number average molecular weight of 400 to 1,000.

  The polyisocyanate compound of the raw material B2 is a compound having 2 or more NCO groups per molecule, and preferably a diisocyanate having 2 NCO groups per molecule and having a molecular weight of 500 or less. Specific examples thereof include diethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, isophorone. Diisocyanate, 2,6-bis (isocyanatomethyl) decahydronaphthalene, lysine triisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, o-tolidine diisocyanate, 4,4'-diphenylmethane diisocyanate, diphenyl ether Diisocyanate, 3- (2′-isocyanatocyclohexyl) propyl isocyanate, tris (phenylisocyanate) G) Thiophosphate, isopropylidenebis (cyclohexyl isocyanate), 2,2'-bis (4-isocyanatophenyl) propane, triphenylmethane triisocyanate, bis (diisocyanatotolyl) phenylmethane, 4,4 ', 4' '- Triisocyanate-2,5-dimethoxyphenylamine, 3,3′-dimethoxybenzidine-4,4′-diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diisocyanatobiphenyl, 4,4′-diisocyanato-3,3′-dimethylbiphenyl, dicyclohexylmethane-4,4′-diisocyanate, 1,1′-methylenebis (4-isocyanatobenzene), 1,1′-methylenebis (3-methyl- 4-isocyana Benzene), m-xylylene diisocyanate, p-xylylene diisocyanate, 1,3-bis (1-isocyanate-1-methylethyl) benzene, 1,4-bis (1-isocyanate-1-methylethyl) benzene, 1 , 3-bis (2-isocyanato-2-propyl) benzene, 2,6-bis (isocyanatomethyl) naphthalene, 1,5-naphthalene diisocyanate, bis (isocyanatomethyl) tetrahydrodicyclopentadiene, bis (isocyanatomethyl) di Cyclopentadiene, bis (isocyanatemethyl) tetrahydrothiophene, 2,5-diisocyanatemethylnorbornene, dimer acid diisocyanate, 1,3,5-tri (1-isocyanatohexyl) isocyanuric acid, bis (isocyanatemethyl) ada Mantan, thiodiethyl diisocyanate, thiodipropyl diisocyanate, thiodihexyl diisocyanate, bis [(4-isocyanatomethyl) phenyl] sulfide, 2,5-diisocyanato-1,4-dithiane, 2,5-diisocyanatomethyl-1 , 4-dithiane, 2,5-diisocyanatomethylthiophene, dithiodiethyl diisocyanate, dithiodipropyl diisocyanate and the like. These polyisocyanate compounds may be used alone or in combination of two or more.

  Of the polyisocyanate compounds (raw material B2) described above, preferably 1,3-bis (isocyanatomethyl) cyclohexane, 4,4′-diphenylmethane diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, m-xylylene diisocyanate 1,3-bis (2-isocyanato-2-propyl) benzene, more preferably dicyclohexylmethane-4,4′-diisocyanate.

The polyurethane prepolymer can be prepared by a heating reaction of the raw material B1 (polyol compound) and the raw material B2 (polyisocyanate compound). For example, it can be obtained by mixing the raw material B2 and the raw material B1 so that the molar ratio of NCO group / OH group is 1.1 to 4, and reacting at 90 to 140 ° C. for 1 to 5 hours. The number average molecular weight of the polyurethane prepolymer thus obtained is preferably 1,000 to 10,000.
Moreover, 90% or more of the terminal groups of this polyurethane prepolymer are NCO groups.

  (C) As a component, the 1 type, or 2 or more types of compound chosen from the polyisocyanate compound described as raw material B2 of the said (B) component is used.

  The component (D) has the following formula (1):

（式中、Ｒ^１は炭素数１〜１０の２価の炭化水素基又は単結合；Ｒ^２、Ｒ^３、及びＲ^４はそれぞれ炭素数１〜１０の炭化水素基又は水素；ＹはＯ又はＳ；ｍは１〜５の整数；および、ｎは０〜５の整数である）で表される構造を１分子中に１個以上有するエピスルフィド化合物である。
（１）式において、Ｒ^１は好ましくはメチレン基、エチレン基又は単結合、更に好ましくは、メチレン基を示す。Ｒ^２、Ｒ^３、及びＲ^４はそれぞれ、好ましくはメチル基又は水素、更に好ましくは水素を示す。Ｙは、好ましくはＳを示す。ｍは好ましくは1または２、更に好ましくは１を示す。ｎは好ましくは０又は１を示す。
好ましいエピスルフィド化合物は、（１）式で表される構造を１分子中に２個以上有し、（１）式のＹがＳを示し、分子量が５００以下の化合物である。より好ましいエピスルフィド化合物は、下記（２）式：

(Wherein R ¹ is a C 1-10 divalent hydrocarbon group or single bond; R ² , R ³ , and R ⁴ are each a C 1-10 hydrocarbon group or hydrogen; Y is O or S; m is an integer of 1 to 5; and n is an integer of 0 to 5), and is an episulfide compound having one or more structures in one molecule.
In the formula (1), R ¹ preferably represents a methylene group, an ethylene group or a single bond, more preferably a methylene group. R ² , R ³ and R ⁴ each preferably represents a methyl group or hydrogen, more preferably hydrogen. Y preferably represents S. m is preferably 1 or 2, more preferably 1. n preferably represents 0 or 1.
A preferred episulfide compound is a compound having two or more structures represented by the formula (1) in one molecule, Y in the formula (1) showing S, and a molecular weight of 500 or less. More preferred episulfide compounds are represented by the following formula (2):

（式中、Ｒ^５〜Ｒ^１０はそれぞれ、炭素数１〜５の炭化水素基又は水素を示し
ＸはＳ又はＯを示し、少なくとも一方のＸはＳであり、ｑは０〜６の整数、ｐは０〜４の整数を示す。）で表される化合物である。ここで、ｑは好ましくは０〜３の整数、更に好ましくは０又は１を示す。ｐは好ましくは０〜２の整数、更に好ましくは０又は１を示す。Ｒ^５〜Ｒ^１０はそれぞれ、好ましくはメチル基又は水素を示す。

(Wherein R ^{5 to} R ¹⁰ each represents a hydrocarbon group having 1 to 5 carbon atoms or hydrogen, X represents S or O, at least one X is S, and q is an integer of 0 to 6, p represents an integer of 0 to 4). Here, q preferably represents an integer of 0 to 3, more preferably 0 or 1. p is preferably an integer of 0 to 2, more preferably 0 or 1. R ^{5 to} R ¹⁰ each preferably represents a methyl group or hydrogen.

Specific examples of the episulfide compound include bis (β-epithiopropyl) sulfide, 1,1-bis (epithioethyl) methane, 1- (epithioethyl) -1- (β-epithiopropyl) methane, 1,1-bis. (Β-epithiopropyl) methane, 1- (epithioethyl) -1- (β-epithiopropyl) ethane, 1,2-bis (β-epithiopropyl) ethane, 1- (epithioethyl) -3- (β -Epithiopropyl) butane, 1,3-bis (β-epithiopropyl) propane, 1- (epithioethyl) -4- (β-epithiopropyl) pentane, 1,4-bis (β-epithiopropyl) Butane, 1- (epithioethyl) -5- (β-epithiopropyl) hexane, 1- (epithioethyl) -2- (γ-epithiobutylthio) ethane, 1- (epithio) Ethyl) -2- [2- (γ-epithiobutylthio) ethylthio] ethane, tetrakis (β-epithiopropyl) methane, 1,1,1-tris (β-epithiopropyl) propane, 1,3- Bis (β-epithiopropyl) -1- (β-epithiopropyl) -2-thiapropane, 1,5-bis (β-epithiopropyl) -2,4-bis (β-epithiopropyl) -3 -Thiapentane, (1,3 or 1,4) -bis (epithioethyl) cyclohexane, (1,3 or 1,4) -bis (β-epithiopropyl) cyclohexane, bis [4- (epithioethyl) cyclohexyl] methane, Bis [4- (β-epithiopropyl) cyclohexyl] methane, 2,2-bis [4- (epithioethyl) cyclohexyl] propane, 2,2-bis [4- (β-epithio) Propyl) cyclohexyl] propane, bis [4- (β-epithiopropyl) cyclohexyl] sulfide, bis [4- (epithioethyl) cyclohexyl] sulfide, 2,5-bis (epithioethyl) -1,4-dithiane, 2,5 -Bis (β-epithiopropyl) -1,4-dithiane, 4-epithioethyl-1,2-cyclohexene sulfide, (1,3 or 1,4) -bis (epithioethyl) benzene, (1,3 or 1, 4) -Bis (β-epithiopropyl) benzene, bis [4- (epithioethyl) phenyl] methane, bis [4- (β-epithiopropyl) phenyl] methane, 2,2-bis [4- (epithioethyl) Phenyl] propane, 2,2-bis [4- (β-epithiopropyl) phenyl] propane, bis [4- (epithio) Til) phenyl] sulfide, bis [4- (β-epithiopropyl) phenyl] sulfide, bis [4- (epithioethyl) phenyl] sulfone, bis [4- (β-epithiopropyl) phenyl] sulfone, 4,4 '-Bis (epithioethyl) biphenyl, 4,4'-bis (β-epithiopropyl) biphenyl, 1,5-bis (2,3-epithiopropyl) -1,2,4,5-tetrathiapentane, 1,6-bis (2,3-epithiopropyl) -1,2,5,6-tetrathiahexane, 1,2,3-tris (4,5-epithio-1,2-dithiapentyl) propane, bis (Β-epithiopropyl) disulfide, bis (epithioethyl) disulfide, bis (β-epithiopropyl) trisulfide, methylthioglycidyl ether, ethylthio Lysidyl ether, propylthioglycidyl ether, butylthioglycidyl ether, bis (β-epithiopropyl) ether, bis (β-epithiopropyloxy) methane, 1,2-bis (β-epithiopropyloxy) ethane, 1,3-bis (β-epithiopropyloxy) propane, 1,2-bis (β-epithiopropyloxy) propane, 1- (β-epithiopropyloxy) -2- (β-epithiopropyloxy) Methyl) propane, 1,4-bis (β-epithiopropyloxy) butane, 1,3-bis (β-epithiopropyloxy) butane, 1- (β-epithiopropyloxy) -3- (β- Epithiopropyloxymethyl) butane, 1,5-bis (β-epithiopropyloxy) pentane, 1- (β-epithiopropyloxy) -4 (Β-epithiopropyloxymethyl) pentane, 1,6-bis (β-epithiopropyloxy) hexane, 1- (β-epithiopropyloxy) -5- (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-epithiopropyloxymethyl) -3-thiapentane, 1,5-bis (β-epithiopropyloxy) -2,4- Bis (β-epithiopropyloxymethyl) -3-thiapentane, 1- (β-epithiopropyloxy) -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-epithiopropyloxy) Methyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropyloxy) -4,5bis (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- Lis (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-[(2-β-epithiopropyloxyethyl) ) Oxymethyl] -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropyloxy) -4,7-bis (β-epithiopropyloxymethyl) -3,6,9- Trithiaundecane, (1,3 or 1,4) -bis (β-epithiopropyloxy) cyclohexane, (1,3 or 1,4) -bis (β-epithiopropyloxymethyl) cyclohexane, bis [4 -(Β-epithiopropyloxy) cyclohexyl] methane, 2,2-bis [4- (β-epithiopropyloxy) cyclohexyl] propane, bis [4- (β-epithiopropyl) Xyl) cyclohexyl] sulfide, 2,5-bis (β-epithiopropyloxymethyl) -1,4-dithiane, 2,5-bis (β-epithiopropyloxyethyloxymethyl) -1,4-dithiane, (1,3 or 1,4) -bis (β-epithiopropyloxy) benzene, (1,3 or 1,4) -bis (β-epithiopropyloxymethyl) benzene, bis [4- (β- Epithiopropyl) phenyl] methane, 2,2-bis [4- (β-epithiopropylthio) phenyl] propane, bis [4- (β-epithiopropylthio) phenyl] sulfide, bis [4- (β -Epithiopropylthio) phenyl] sulfone, 4,4'-bis (β-epithiopropylthio) biphenyl, bis (epithioethyl) sulfide, bis (epithioethyl) Sulfide, bis (β-epithiopropyl) sulfide, bis (β-epithiopropyl) disulfide, bis (β-epithiopropyl) trisulfide, bis (β-epithiopropylthio) methane, 1,2-bis ( β-epithiopropylthio) ethane, 1,3-bis (β-epithiopropylthio) propane, 1,2-bis (β-epithiopropylthio) propane, 1- (β-epithiopropylthio)- 2- (β-epithiopropylthiomethyl) propane, 1,4-bis (β-epithiopropylthio) butane, 1,3-bis (β-epithiopropylthio) butane, 1- (β-epithio Propylthio) -3- (β-epithiopropylthiomethyl) butane, 1,5-bis (β-epithiopropylthio) pentane, 1- (β-epithiopropylthio) -4- (β Epithiopropylthiomethyl) pentane, 1,6-bis (β-epithiopropylthio) hexane, 1- (β-epithiopropylthio) -5- (β-epithiopropylthiomethyl) hexane, 1- ( β-epithiopropylthio) -2-[(2-β-epithiopropylthioethyl) thio] ethane, 1- (β-epithiopropylthio) -2-[[2- (2-β-epithio Propylthioethyl) thioethyl] thio] ethane, tetrakis (β-epithiopropylthiomethyl) methane, 1,1,1-tris (β-epithiopropylthiomethyl) propane, 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-epithiopropylthio) -4, 4-bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -2,4,5-tris (β-epithiopropylthiomethyl)- 3,6-dithiaoc 1,8-bis (β-epithiopropylthio) -2,5-bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,9-bis (β-epithiopropylthio) -5- (β-epithiopropylthiomethyl) -5-[(2-β-epithiopropylthioethyl) thiomethyl] -3,7-dithianonane, 1,10-bis (β-epithiopropylthio)- 5,6-bis [(2-β-epithiopropylthioethyl) thio] -3,6,9-trithiadecane, 1,11-bis (β-epithiopropylthio) -4,8-bis (β- Epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropylthio) -5,7-bis (β-epithiopropylthiomethyl) -3,6 9-trithiaundecane, 1,11-bi (Β-epithiopropylthio) -5,7-[(2-β-epithiopropylthioethyl) thiomethyl] -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropylthio) ) -4,7-bis (β-epithiopropylthiomethyl) -3,6,9-trithiaundecane, tetra [2- (β-epithiopropylthio) acetylmethyl] methane, 1,1,1- Tri [2- (β-epithiopropylthio) acetylmethyl] propane, tetra [2- (β-epithiopropylthiomethyl) acetylmethyl] methane, 1,1,1-tri [2- (β-epithio Propylthiomethyl) acetylmethyl] propane, (1,3 or 1,4) -bis (β-epithiopropylthio) cyclohexane, (1,3 or 1,4) -bis (β-epithiopropylthiomethyl) ) Cyclohexane, bis [4- (β-epithiopropylthio) cyclohexyl] methane, 2,2-bis [4- (β-epithiopropylthio)
Cyclohexyl] propane, bis [4- (β-epithiopropylthio) cyclohexyl] sulfide, 2,5-bis (β-epithiopropylthiomethyl) -1,4-dithiane, 2,5-bis (β-epi Thiopropylthioethylthiomethyl) -1,4-dithiane, (1,3 or 1,4) -bis (β-epithiopropylthio) benzene, (1,3 or 1,4) -bis (β-epi Thiopropylthiomethyl) 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, 4,4′-bis (β-epithiopropylthio) biphenyl, vinyl E two thioether glycidyl ether, vinylbenzyl thioglycidyl ether, thioglycidyl methacrylate, thioglycidyl acrylate, Ali thioether glycidyl ether. These episulfide compounds may be used alone or in combination of two or more.

  Preferred episulfide compounds are bis (β-epithiopropyl) sulfide and bis (β-epithiopropyl) disulfide, and more preferred episulfide compounds are bis (β-epithiopropyl) sulfide.

  An optical material can be produced by subjecting the (A) component, (B) component, (C) component and (D) component of the polymerization composition to heat polymerization in the presence of a curing catalyst. Curing catalysts include amines, phosphine, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, secondary iodonium salts, mineral acids, Lewis acids, organic acids, silicic acids, tetrafluoride. Boric acids, peroxides, azo compounds, condensates of aldehydes and amine compounds, guanidines, thioureas, thiazoles, sulfenamides, thiurams, dithiocarbamates, xanthates, acidic phosphorus Examples include acid esters. The typical examples of these are shown below.

(1) Amines Ethylamine, n-propylamine, sec-propylamine, n-butylamine, sec-butylamine, isobutylamine, tert-butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, laurylamine, miss Tyrylamine, 1,2-dimethylhexylamine, 3-pentylamine, 2-ethylhexylamine, allylamine, aminoethanol, 1-aminopropanol, 2-aminopropanol, aminobutanol, aminopentanol, aminohexanol, 3-ethoxypropyl Amine, 3-propoxypropylamine, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 3- (2-ethylhexyloxy) propyl Piruamin, amino cyclopentane, diaminocyclohexane, amino norbornene, aminomethyl cyclohexane, aminobenzene, benzylamine, phenethylamine, alpha-phenylethylamine, naphthylamine, primary amines such as furfuryl amine;
Ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane 1,7-diaminoheptane, 1,8-diaminooctane, dimethylaminopropylamine, diethylaminopropylamine, bis- (3-aminopropyl) ether, 1,2-bis- (3-aminopropoxy) ethane, 1, 3-bis- (3-aminopropoxy) -2,2′-dimethylpropane, aminoethylethanolamine, 1,2-, 1,3- or 1,4-bisaminocyclohexane, 1,3- or 1,4 -Bisaminomethylcyclohexane, 1,3- or 1,4-bisaminoethylcyclohexane, 1,3- Or 1,4-bisaminopropylcyclohexane, hydrogenated 4,4′-diaminodiphenylmethane, 2- or 4-aminopiperidine, 2- or 4-aminomethylpiperidine, 2- or 4-aminoethylpiperidine, N-aminoethyl Piperidine, N-aminopropylpiperidine, N-aminoethylmorpholine, N-aminopropylmorpholine, isophoronediamine, menthanediamine, 1,4-bisaminopropylpiperazine, o-, m-, or p-phenylenediamine, 2,4 -Or 2,6-tolylenediamine, 2,4-toluenediamine, m-aminobenzylamine, 4-chloro-o-phenylenediamine, tetrachloro-p-xylylenediamine, 4-methoxy-6-methyl-m -Phenylenediamine, m-, there is Or p-xylylenediamine, 1,5- or 2,6-naphthalenediamine, benzidine, 4,4′-bis (o-toluidine), dianisidine, 4,4′-diaminodiphenylmethane, 2,2- ( 4,4′-diaminodiphenyl) propane, 4,4′-diaminodiphenyl ether, 4,4′-thiodianiline, 4,4′-diaminodiphenylsulfone, 4,4′-diaminoditolylsulfone, methylenebis (o-chloroaniline) ), 3,9-bis (3-aminopropyl) 2,4,8,10-tetraoxaspiro [5,5] undecane, diethylenetriamine, iminobispropylamine, methyliminobispropylamine, bis (hexamethylene) triamine , Triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-aminoethylpiperazine, N-aminopropylpiperazine, 1,4-bis (aminoethylpiperazine), 1,4-bis (aminopropylpiperazine), 2,6-diaminopyridine, bis (3,4-diaminophenyl) Primary polyamines such as sulfones;
Diethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine, diisobutylamine, di-n-pentylamine, di-3-pentylamine, dihexylamine, octylamine, di (2-ethylhexyl) amine, methyl Hexylamine, diallylamine, pyrrolidine, piperidine, 2-, 3-, 4-picoline, 2,4-, 2,6-, 3,5-lupetidine, diphenylamine, N-methylaniline, N-ethylaniline, dibenzylamine , Secondary amines such as methylbenzylamine, dinaphthylamine, pyrrole, indoline, indole, 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-1,6-di Aminohexane, piperazine, 2-methylpiperazine, 2,5- or 2,6-dimethylpiperazine, homopiperazine, 1,1-di- (4-piperidyl) methane, 1,2-di- (4-piperidyl) ethane Secondary polyamines such as 1,3-di- (4-piperidyl) propane, 1,4-di- (4-piperidyl) butane;
Trimethylamine, triethylamine, tri-n-propylamine, tri-iso-propylamine, tri-1,2-dimethylpropylamine, tri-3-methoxypropylamine, tri-n-butylamine, tri-iso-butylamine, tri- sec-butylamine, tri-pentylamine, tri-3-pentylamine, tri-n-hexylamine, tri-n-octylamine, tri-2-ethylhexylamine, tri-dodecylamine, tri-laurylamine, dicyclohexylethylamine, Cyclohexyldiethylamine, tri-cyclohexylamine, N, N-dimethylhexylamine, N-methyldihexylamine, N, N-dimethylcyclohexylamine, N-methyldicyclohexylamine, N, N-diethylethanol Min, N, N-dimethylethanolamine, N-ethyldiethanolamine, triethanolamine, tribenzylamine, N, N-dimethylbenzylamine, diethylbenzylamine, triphenylamine, N, N-dimethylamino-p-cresol, N, N-dimethylaminomethylphenol, 2- (N, N-dimethylaminomethyl) phenol, N, N-dimethylaniline, N, N-diethylaniline, pyridine, quinoline, N-methylmorpholine, N-methylpiperidine, Tertiary amines such as 2- (2-dimethylaminoethoxy) -4-methyl-1,3,2-dioxabornane;
Tetramethylethylenediamine, pyrazine, N, N′-dimethylpiperazine, N, N′-bis ((2-hydroxy) propyl) piperazine, hexamethylenetetramine, N, N, N ′, N′-tetramethyl-1,3 -Butaneamine, 2-dimethylamino-2-hydroxypropane, diethylaminoethanol, N, N, N-tris (3-dimethylaminopropyl) amine, 2,4,6-tris (N, N-dimethylaminomethyl) phenol, Tertiary polyamines such as heptamethylisobiguanide;
Imidazole, N-methylimidazole, 2-methylimidazole, 4-methylimidazole, N-ethylimidazole, 2-ethylimidazole, 4-ethylimidazole, N-butylimidazole, 2-butylimidazole, N-undecylimidazole, 2 -Undecylimidazole, N-phenylimidazole, 2-phenylimidazole, N-benzylimidazole, 2-benzylimidazole, 2-mercaptoimidazole, 2-mercapto-N-methylimidazole, 2-mercaptobenzimidazole, 3-mercapto-4 -Methyl-4H-1,2,4-triazole, 5-mercapto-1-methyl-tetrazole, 2,5-dimercapto-1,3,4-thiadiazole 1-benzyl-2-methylimidazole, N- (2 ' -Cyanoethyl) -2-methylimidazole, N- (2'-cyanoethyl) -2-undecylimidazole, N- (2'-cyanoethyl) -2-phenylimidazole, 3,3-bis- (2-ethyl-4) -Methylimidazolyl) Various imidazoles such as methane, alkylimidazole and isocyanuric acid adducts;
1,8-diazabicyclo (5,4,0) undecene-7,1,5-diazabicyclo (4,3,0) nonene-5,6-dibutylamino-1,8-diazabicyclo (5,4,0) undecene Amidines such as -7.

(2) A complex of the amines of (1) with borane and boron trifluoride.

(3) Phosphine trimethylphosphine, triethylphosphine, tri-iso-propylphosphine, tri-n-butylphosphine, tri-n-hexylphosphine, tri-n-octylphosphine, tricyclohexylphosphine, tri Phenylphosphine, tribenzylphosphine, tris (2-methylphenyl) phosphine, tris (3-methylphenyl) phosphine, tris (4-methylphenyl) phosphine, tris (diethylamino) phosphine, tris (4-methylphenyl) phosphine, Dimethylphenylphosphine, diethylphenylphosphine, dicyclohexylphenylphosphine, ethyldiphenylphosphine, diphenylcyclohexylphosphine, chlorodiphenylphosphine, etc.

(4) Quaternary ammonium salt tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium acetate, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium acetate, tetra-n-butylammonium fluoride, tetra-n-butylammonium chloride Tetra-n-butylammonium bromide, tetra-n-butylammonium iodide, tetra-n-butylammonium acetate, tetra-n-butylammonium borohydride, tetra-n-butylammonium hexafluorophosphite, tetra-n- Butylammonium hydrogen sulfite, tetra-n-butylammonium tetrafluoroborate , Tetra-n-butylammonium tetraphenylborate, tetra-n-butylammonium paratoluenesulfonate, tetra-n-hexylammonium chloride, tetra-n-hexylammonium bromide, tetra-n-hexylammonium acetate, tetra-n -Octylammonium chloride, tetra-n-octylammonium bromide, tetra-n-octylammonium acetate, trimethyl-n-octylammonium chloride, trimethyldecylammonium chloride, trimethyldodecylammonium chloride, trimethylcetylammonium chloride, trimethyllaurylammonium chloride, trimethyl Benzylammonium chloride, trimethylbenzylammonium Romide, triethyl-n-octylammonium chloride, triethylbenzylammonium chloride, triethylbenzylammonium bromide, tri-n-butyl-n-octylammonium chloride, tri-n-butylbenzylammonium fluoride, tri-n-butylbenzylammonium chloride , Tri-n-butylbenzylammonium bromide, tri-n-butylbenzylammonium iodide, n-butyldimethylbenzylammonium chloride, n-octyldimethylbenzylammonium chloride, decyldimethylbenzylammonium chloride, dodecyldimethylbenzylammonium chloride, cetyldimethyl Benzyl ammonium chloride, lauryl dimethyl benzyl ammonium Muchloride, methyltriphenylammonium chloride, methyltribenzylammonium chloride, methyltriphenylammonium bromide, methyltribenzylammonium bromide, ethyltriphenylammonium chloride, ethyltribenzylammonium chloride, ethyltriphenylammonium bromide, ethyltribenzylammonium bromide, n-butyltriphenylammonium chloride, n-butyltribenzylammonium chloride, n-butyltriphenylammonium bromide, n-butyltribenzylammonium bromide, 1-methylpyridinium chloride, 1-methylpyridinium bromide, 1-ethylpyridinium chloride, 1-ethylpyridinium bromide 1-n-butylpyridinium chloride, 1-n-butylpyridinium bromide, 1-n-hexylpyridinium chloride, 1-n-hexylpyridinium bromide, 1-n-octylpyridinium bromide, 1-n-dodecylpyridinium chloride, 1 -N-dodecylpyridinium bromide, 1-n-cetylpyridinium chloride, 1-n-cetylpyridinium bromide, 1-phenylpyridinium chloride, 1-phenylpyridinium bromide, 1-benzylpyridinium chloride, 1-benzylpyridinium bromide, 1-methyl Picolinium chloride, 1-methylpicolinium bromide, 1-ethylpicolinium chloride, 1-ethylpicolinium bromide, 1-n-butylpicolinium chloride Id, 1-n-butylpicolinium bromide, 1-n-hexylpicolinium chloride, 1-n-hexylpicolinium bromide, 1-n-octylpicolinium chloride, 1-n-octylpicolinium bromide, 1-n -Dodecylpicolinium chloride, 1-n-dodecylpicolinium bromide, 1-n-cetylpicolinium chloride, 1-n-cetylpicolinium bromide, 1-phenylpicolinium chloride, 1-phenylpicolinium bromide 1-benzylpicoli Nium chloride, 1-benzylpicolinium bromide, and the like.

(5) Quaternary phosphonium salt tetramethylphosphonium chloride, tetramethylphosphonium bromide, tetraethylphosphonium chloride, tetraethylphosphonium bromide, tetra-n-butylphosphonium chloride, tetra-n-butylphosphonium bromide, tetra-n-butylphosphonium iodide Tetra-n-hexylphosphonium bromide, tetra-n-octylphosphonium bromide, methyltriphenylphosphonium bromide, methyltriphenylphosphonium iodide, ethyltriphenylphosphonium bromide, ethyltriphenylphosphonium iodide, n-butyltriphenylphosphonium bromide , N-butyltriphenylphosphonium iodide, n-hexyltriphenyl Phosphonium bromide, n- octyl triphenylphosphonium bromide, tetraphenylphosphonium bromide, tetrakis hydroxymethyl phosphonium chloride, tetrakis hydroxymethyl phosphonium bromide, tetrakis hydroxyethyl phosphonium chloride, tetrakis hydroxybutyl phosphonium chloride and the like.

(6) Tertiary sulfonium salt trimethylsulfonium bromide, triethylsulfonium bromide, tri-n-butylsulfonium chloride, tri-n-butylsulfonium bromide, tri-n-butylsulfonium iodide, tri-n-butylsulfonium tetrafluoroborate Tri-n-hexylsulfonium bromide, tri-n-octylsulfonium bromide, triphenylsulfonium chloride, triphenylsulfonium bromide, triphenylsulfonium iodide and the like.

(7) Secondary iodonium salt diphenyliodonium chloride, diphenyliodonium bromide, diphenyliodonium iodide and the like.

(8) Mineral acids Mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and carbonic acid, and half esters thereof.

(9) Lewis acid boron trifluoride, boron trifluoride etherate, aluminum fluoride, aluminum chloride, triphenylaluminum, potassium octoate, calcium acetate, tetraisopropoxytitanium, tetrabutoxytitanium, tetrachlorotitanium, titanic acid 2-ethylhexyl, dimethyltin oxide, dimethyltin dichloride, dibutyltin diacetate, dibutyltin acetate, dibutyltin dilaurate, dibutyltin laurate, dibutyltin octanoate, dibutyltin bis (dodecyl mercaptide), dibutyltin bis (isooctylthioglycolate), dibutyltin Oxide, butyltin trichloride, dibutyltin dichloride, tributyltin chloride, tetrabutyltin, dioctyltin diacetate, di Dioctyltin dilaurate, dioctyltin laurate, dioctyltin diricinolate, dioctyltin dioleate, dioctyltin di (6-hydroxy) caproate, dioctyltin bis (isooctylthioglycolate), dioctyltin oxide, Dioctyltin dichloride, dioctyltin maleate, dioctyltin bis (butyl maleate), didodecyltin diricinolate, tin stearate, zinc chloride, acetylacetone zinc, copper oleate, acetylacetone copper, acetylacetone iron, naphthenate iron, lactic acid Iron, iron citrate, iron gluconate, etc.

(10) Organic acids and their half esters.

(11) Silicic acid and tetrafluoroboric acid.

(12) Peroxide cumyl peroxyneodecanoate, diisopropyl peroxydicarbonate, diallyl peroxydicarbonate, di-n-propyl peroxydicarbonate, dimyristyl peroxydicarbonate, cumyl peroxyneohexanoate Tert-hexylperoxyneodecanoate, tert-butylperoxyneodecanoate, tert-hexylperoxyneohexanoate, tert-butylperoxyneohexanoate, 2,4-dichlorobenzoyl peroxide, Peroxides such as benzoyl peroxide, dicumyl peroxide, di-ter-butyl peroxide; cumene hydroperoxide, tert-butyl hydroperoxide and the like.

(13) Azo compound 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2-cyclopropylpropionitrile), 2,2′-azobis (2 , 4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 1-[(1-Cyano-1-methylethyl) azo] formamide, 2-phenylazo-4-methoxy-2,4-dimethyl-valeronitrile 2, 2′-azobis (2-methylpropane), 2, 2 ′ -Azobis (2,4,4-trimethylpentane) and the like.

(14) Condensate of aldehyde and amine compound Reaction product of acetaldehyde and ammonia, condensate of formaldehyde and paratoluidine, condensate of acetaldehyde and paratoluidine, reaction product of formaldehyde and aniline, reaction product of acetaldehyde and aniline, butyraldehyde Reaction product of aniline with formaldehyde, acetaldehyde and aniline, reaction product of acetaldehyde and butyraldehyde and aniline, condensate of butyraldehyde and monobutylamine, reaction product of butyraldehyde and butylideneaniline, reaction of heptaldehyde and aniline Reactants, reactants of tricrotonylidene-tetramine, condensates of α-ethyl-β-propylacrolein and aniline, condensates of formaldehyde and alkylimidazoles, and the like.

(15) Guanidines Diphenylguanidine, phenyltolylguanidine, phenylxylylguanidine, tolyloxysilylguanidine, diortolylguanidine, orthotolylguanide, diphenylguanidine phthalate, tetramethylguanidine, diorthotolylguanidine salt of dicatecholboric acid etc.

(16) Thioureas Thiocarboanilide, diortolylthiourea, ethylenethiourea, diethylthiourea, dibutylthiourea, dilaurylthiourea, trimethylthiourea, dimethylethylthiourea, tetramethylthiourea and the like.

(17) Thiazoles 2-mercaptobenzothiazole, dibenzothiazyl disulfide, cyclohexylamine salt of 2-mercaptobenzothiazole, 2- (2,4-dinitrophenylthio) benzothiazole, 2- (morpholinodithio) benzothiazole, 2 -(2,6-dimethyl-4-morpholinothio) benzothiazole, N, N-diethylthiocarbamoyl-2-benzothiazolyl sulfide, 1,3-bis (2-benzothiazolylmercaptomethyl) urea, benzo Thiadiazylthiobenzoate, 2-mercaptothiazoline, sodium salt of 2-mercaptobenzothiazole, zinc salt of 2-mercaptobenzothiazole, complex salt of dibenzothiazyl disulfide and zinc chloride, and the like.

(18) Sulfenamides N-cyclohexyl-2-benzothiazylsulfenamide, N-tert-butyl-2-benzothiazylsulfenamide, N-tert-octyl-2-benzothiazylsulfenamide, N-oxydiethylene-2-benzothiazylsulfenamide, N, N-diethyl-2-benzothiazylsulfenamide, N, N-diisopropyl-2-benzothiazylsulfenamide, N, N-dicyclohexyl- 2-benzothiazylsulfenamide and the like.

(19) Thiurams tetramethylthiuram monosulfide, tetraethylthiuram monosulfide, tetrabutylthiuram monosulfide, dipentamethylenethiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, N, N′-dimethyl- N, N′-diphenylthiuram disulfide, N, N′-diethyl-N, N′-diphenylthiuram disulfide, dipentamethylenethiuram disulfide, dipentamethylenethiuram tetrasulfide, cyclic thiuram and the like.

(20) Dithiocarbamates Sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate, sodium dibutyldithiocarbamate, sodium pentamethylenedithiocarbamate, sodium cyclohexylethyldithiocarbamate, potassium dimethyldithiocarbamate, lead dimethyldithiocarbamate, zinc dimethyldithiocarbamate, diethyldithiocarbamate Zinc oxide, zinc dibutyldithiocarbamate, zinc dibenzyldithiocarbamate, zinc pentamethylenedithiocarbamate, zinc dimethylpentamethylenedithiocarbamate, zinc ethylphenyldithiocarbamate, bismuth dimethyldithiocarbamate, cadmium diethyldithiocarbamate, cadmium pentamethylenedithiocarbamate Selenium dimethyldithiocarbamate, selenium diethyldithiocarbamate, tellurium dimethyldithiocarbamate, tellurium diethyldithiocarbamate, iron dimethyldithiocarbamate, copper dimethyldithiocarbamate, diethylammonium diethyldithiocarbamate, N, N-cyclohexylammonium dibutyldithiocarbamate, pentamethylene Piperidine dithiocarbamate, cyclohexylethylammonium sodium cyclohexylethyldithiocarbamate, pipecoline methylpentamethylenedithiocarbamate, complex compounds of zinc pentamethylenedithiocarbamate and piperidine.

(21) Xanthates: sodium isopropylxanthate, zinc isopropylxanthate, zinc butylxanthate, dibutylxanthate disulfide and the like.

(22) Acid phosphate esters mono- and / or dimethyl phosphate, mono- and / or diethyl phosphate, mono- and / or dipropyl phosphate, mono- and / or dibutyl phosphate, mono- and / or dihexyl phosphate Mono- and / or dioctyl phosphate, mono- and / or didecyl phosphate, mono- and / or didodecyl phosphate, mono- and / or diphenyl phosphate, mono- and / or dibenzyl phosphate, mono- and / or didecano- Luric acid etc.

  The curing catalyst used in the present invention is not limited to the above compound as long as it is a compound that catalyzes polymerization and curing. These may be used alone or in combination of two or more. The addition amount of the catalyst used in the present invention is preferably 0.0001 to 10.0 parts by weight, more preferably 0.0005 to 5.0 parts by weight with respect to 100 parts by weight of the polymerizable composition. .

  In addition, when the composition of the present invention is polymerized and cured to obtain an optical material, a stabilizer described in JP-A-2002-332350 may be used. Preferable examples include halides of silicon, germanium, tin, and antimony. Among the halides of silicon, germanium, tin and antimony, preferred are chlorides, more preferred are trichloro or dichloro compounds, and further preferred are germanium, tin and antimony trichloro or dichloro compounds having an alkyl group. is there. Specific examples of the most preferred are dibutyltin dichloride, butyltin trichloride, dioctyltin dichloride, octyltin trichloride, dibutyldichlorogermanium, butyltrichlorogermanium, diphenyldichlorogermanium, phenyltrichlorogermanium, triphenylantimony dichloride. These may be used alone or in combination of two or more. The addition amount of the stabilizer is preferably 0.0001 to 10.0 parts by weight and more preferably 0.0005 to 5.0 parts by weight with respect to 100 parts by weight of the polymerizable composition.

  Furthermore, when the composition is polymerized and cured to obtain an optical material, a compound having at least one epoxy group described in Japanese Patent Application No. 2004-119619 may be used as a polymerization rate adjusting agent. The addition amount of a polymerization rate modifier is 0.0001-10.0 weight part with respect to 100 weight part of polymeric compositions, Preferably it is 0.0005-5.0 weight part.

  In addition, when the composition of the present invention is polymerized and cured to obtain an optical material, additives such as known antioxidants, ultraviolet absorbers, yellowing inhibitors, bluing agents, and pigments are added, Of course, it is possible to further improve the practicality of the obtained material. When the polymerizable composition of the present invention is easily peeled off from the mold during polymerization, a known external and / or internal adhesion improver is used or added to control and improve the adhesion between the obtained cured product and the mold. You may squeeze it. Examples of the internal adhesion improving agent include 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and 3-mercaptopropyl. Examples thereof include silane compounds such as trimethoxysilane, and 0.00001 to 5 parts by weight may be used with respect to 100 parts by weight of the polymerizable composition of the present invention. Conversely, when the polymerizable composition of the present invention is difficult to peel off from the mold after polymerization, a known external and / or internal mold release agent may be used or added to improve the mold release of the resulting cured product. Good. As the internal mold release agent, fluorine-based nonionic surfactant, silicon-based nonionic surfactant, alkyl quaternary ammonium salt, phosphate ester, acidic phosphate ester, oxyalkylene-type acidic phosphate ester, alkali metal salt of acidic phosphate ester, Examples include alkali metal salts of oxyalkylene acid phosphates, metal salts of higher fatty acids, higher fatty acid esters, paraffins, waxes, higher aliphatic amides, higher aliphatic alcohols, polysiloxanes, aliphatic amine ethylene oxide adducts, and the like. You may use 0.00001-5 weight part with respect to 100 weight part of polymeric compositions of this invention.

  The method for producing an optical material of the present invention comprises (A) component, (B) component, (C) component, (D) component and a curing catalyst, and a stabilizer, polymerization rate adjusting agent, and adhesiveness used as necessary. Additives such as improvers or releasability improvers, antioxidants, UV absorbers, yellowing inhibitors, bluing agents, pigments, etc., are uniformly mixed, injected into a glass or metal mold, and polymerized by heating. After curing, it is removed from the mold and manufactured.

  (A) component, (B) component, (C) component, (D) component and catalyst, and a stabilizer, a polymerization rate adjusting agent, an adhesion improving agent or a mold release improving agent used as necessary, antioxidant Additives, UV absorbers, anti-yellowing agents, bluing agents, pigments, etc. can be added to the same container all at the same time under stirring or by adding each component in stages. The components may be mixed separately and then remixed in the same container. Each component, additive and the like may be mixed in any order. Basically, the mixing temperature, mixing time, etc. may be sufficient if each component is sufficiently mixed. However, excessive temperature and time cause an undesirable reaction between each component and additive, and further increase in viscosity. This is not suitable because it makes casting operation difficult. The mixing temperature is preferably in the range of about −50 to 100 ° C., more preferably −30 to 70 ° C., and further preferably −5 to 50 ° C. The mixing time is preferably 1 minute to 12 hours, more preferably 5 minutes to 10 hours, and even more preferably about 5 minutes to 6 hours. It is preferable to perform a degassing operation under reduced pressure before, during or after mixing each component and additive from the viewpoint of preventing generation of bubbles during polymerization and curing. The degree of vacuum in the degassing operation is preferably about 0.1 to 700 mmHg, more preferably 0.5 to 300 mmHg. Furthermore, it is preferable to further refine the quality of the optical material of the present invention by purifying the mixture or each component before mixing with a filter having a pore size of about 0.05 to 3 μm to purify impurities. After pouring into a glass or metal mold, polymerization and curing are performed with or without heating using an electric furnace, water bath, oil bath or the like. The curing time is preferably 0.1 to 100 hours, more preferably 1 to 72 hours, and the curing temperature is preferably −10 to 160 ° C., more preferably 0 to 140 ° C. The polymerization can be carried out by holding at a predetermined polymerization temperature for a predetermined time, raising the temperature by 0.1 to 100 ° C./h, lowering the temperature by 0.1 to 100 ° C./h, and a combination thereof. Moreover, it is preferable to anneal the cured product at a temperature of 50 to 150 ° C. for about 10 minutes to 5 hours in order to remove distortion of the optical material of the present invention. Furthermore, if necessary, surface treatment such as dyeing, hard coat formation, antireflection, antifogging and impact resistance treatment can be performed. Further, if necessary, an optical material is obtained by polymerizing and curing a polymerizable composition containing (A) a compound having two or more mercapto groups, (B) a polyurethane prepolymer having an NCO group terminal, and (D) an episulfide compound. It can also be manufactured.

EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. The physical properties of the lens were measured according to the following method.

(1) Refractive index (nD)
The measurement was performed at 25 ° C. using a precision refractometer KPR-200 manufactured by Carnew.
(2) Abbe number (νD)
The measurement was performed at 25 ° C. using a precision refractometer KPR-200 manufactured by Carnew.
(3) Average falling ball impact energy The lens was sequentially dropped from a height of 127 cm onto a lens from a light steel ball to a heavy steel ball. The impact energy given to the lens by the steel ball when the lens broke was measured. The falling ball test was performed 10 times, and the average value was obtained.

Synthesis example 1
Preparation of PR1 A mixture of 60.0 g of Kuraray polyol P-510 (polyester diol manufactured by Kuraray; number average molecular weight 483) and 120.0 g of Kuraray polyol P-520 (polyester diol manufactured by Kuraray; number average molecular weight 501) at 90 ° C. Heated and degassed with stirring for 1 hour under vacuum. After mixing 152.6 g (0.58 mol) of dicyclohexylmethane-4,4′-diisocyanate (HMDI), the mixture was reacted at 130 ° C. for 2 hours to obtain a polyurethane prepolymer (PR1).

Synthesis example 2
Preparation of PR2 A polyurethane prepolymer (PR2) was obtained in the same manner as in Synthesis Example 1 using 70.2 g of Kuraray polyol P-520 (number average molecular weight 501) and 58.8 g (0.22 mol) of HMDI.

Example 1
Trimethylolpropane tris (3-mercaptopropionate) 9.0 parts by weight, bis (2-mercaptoethyl sulfide) 7.9 parts by weight, PR1 obtained in Synthesis Example 1 34.2 parts by weight, dicyclohexylmethane-4 , 4'-diisocyanate 14.9 parts by weight and bis (β-epithiopropyl) sulfide 34.0 parts by weight, tetra-n-butylphosphonium bromide 0.05 parts by weight as a catalyst, dibutyltin as a stabilizer 0.05 part by weight of dichloride, 0.6 part by weight of 2,2-bis (4-glycidyloxyphenyl) propane as a polymerization rate adjusting agent, and 0.007 part by weight of NIKKOL TCP-5 manufactured by Nikko Chemicals as an internal mold release agent Mix to obtain a uniform solution. This was then filtered through a 0.5 μm PTFE filter. The filtrate was poured into a 2.5 mm thick flat lens mold, heated in an oven from 30 ° C. to 130 ° C. over 30 hours, and polymerized to produce a lens. The obtained lens had good transparency and surface condition. The measurement results of refractive index, Abbe number and average falling ball impact energy are shown in Table 2.

Examples 2-4
Example 1 was repeated except that the composition shown in Table 1 was used. The physical properties of the obtained lens are shown in Table 2.

Comparative Example 1
A lens was produced in the same manner as in Example 1 except that the OYAS material manufactured by HOYA was used. The measurement results of refractive index, Abbe number and average falling ball impact energy are shown in Table 2.

The polymerizable composition of the present invention can provide an optical material and a lens having a refractive index of around 1.60 and an Abbe number of around 40 and high strength (high impact resistance), and is industrially useful. .

Claims (8)

(A) a compound having two or more mercapto groups;
(B) a polyurethane prepolymer having NCO group ends;
(C) a polyisocyanate compound; and (D) the following formula (1):

(In the formula, R ¹ is a C 1-10 divalent hydrocarbon group or single bond; R ² , R ³ , and R ⁴ are each a C 1-10 hydrocarbon group or hydrogen; Y is O or S; m is an integer of 1 to 5; and n is an integer of 0 to 5), and a polymerizable composition comprising an episulfide compound having one or more structures in one molecule ,
The compound having two or more mercapto groups as the component (A) is a combination of a compound having two mercapto groups and a compound having three mercapto groups, or a compound having two mercapto groups and four mercapto groups. Or a compound having two mercapto groups, a compound having three mercapto groups, and a compound having four mercapto groups . The polymerizable composition according to claim 1, wherein the molecular weight of the component (A) is 600 or less.   The component (B) is a prepolymer obtained from an aliphatic linear diol having a number average molecular weight of 400 to 2000 or a linear diol having an aliphatic group and an aromatic group, and a diisocyanate having a molecular weight of 500 or less. The polymerizable composition according to claim 1 or 2.   The molecular weight of the said (C) component is 500 or less, The polymeric composition in any one of Claims 1-3.   The component (D) has two or more structures represented by the formula (1) in one molecule, Y in the formula (1) is S, and the molecular weight is 500 or less. Polymeric composition in any one of 1-4.   The composition comprises (A) 1 to 40% by weight, (B) 1 to 70% by weight, (C) 1 to 50% by weight, and (D) 1 to 70% by weight. The polymerizable composition according to any one of the above.   An optical material obtained by polymerizing and curing the polymerizable composition according to claim 1.   An optical lens made of the optical material according to claim 7.