JP5034163B2 - Polymerizable composition - Google Patents

Description

  The present invention relates to an optical material composition having excellent optical properties and high mechanical strength, and a resin for optical materials obtained by polymerizing this optical material composition.

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

  In addition to low specific gravity, the main performance required for eyeglass lenses is excellent optical performance (high refractive index, high Abbe number), chromaticity (high transparency, low yellowness), high strength (high impact resistance), etc. Is mentioned.

  Diethylene glycol diallyl carbonate resin called CR39, which has been widely used as a spectacle lens material until now, has a high Abbe number of 58 but a low refractive index of 1.50. For this reason, when used as a lens, there is a problem that a particularly strong lens has an increased outer thickness and a center thickness, resulting in poor appearance and heavy weight. Furthermore, it has a drawback that the falling ball impact strength is 100 g or less and is easily broken.

  For the purpose of improving the refractive index, synthetic resin optical materials containing sulfur atoms having a high atomic refractive index have been developed. For example, a thermosetting optical material having a thiourethane structure obtained by a reaction between a polythiol compound and a polyisocyanate compound has been proposed (see Patent Document 1 and Patent Document 2). Various novel polythiol compounds as raw materials for these thiourethanes have also been proposed. For example, a branched polythiol compound having four sulfur atoms in one molecule (see Patent Document 3), a branched polythiol compound having five sulfur atoms in one molecule (see Patent Document 4), and dithiane in the molecule. Examples include polythiol compounds having a ring structure (see Patent Document 5). These materials have excellent optical characteristics with a refractive index of about 1.66 at maximum and an Abbe number of 33-40. Furthermore, an episulfide resin having extremely excellent optical properties such as a refractive index of 1.70 and an Abbe number of 36 has been proposed (see Patent Documents 6 and 7).

  However, the impact resistance of these materials is not satisfactory, especially when a practical hard coat is applied, the impact resistance is greatly reduced, and as it is, the eyeglass lens safety standards set by the FDA (Food and Drug Administration) It is known that it cannot pass (16g or more). Therefore, in general, impact resistance is improved by applying a special hard coat such as addition of a cushion coat, but there is a big problem that productivity is remarkably lowered.

  As impact-resistant lenses, lenses using polycarbonate, which is a thermoplastic resin, are increasingly used mainly in the United States. Polycarbonate lenses have a very high drop ball impact strength of 1 kg or more, but due to the structure containing a large number of benzene rings, optical distortion occurs, and the Abbe number is as low as 30, resulting in a great disadvantage that optical unevenness occurs. There is also a problem that secondary workability such as cutting workability, hard coat workability and dyeability is poor.

  In addition, a polyurethane material containing an aliphatic linear oligomer has been proposed as a material having high impact resistance (see Patent Document 8 and Patent Document 9). The Abbe number is as high as 46, and the impact strength is 1 kg or more, and the impact resistance is as high as that of a polycarbonate lens. However, it has a very low refractive index of about 1.53.

Japanese Patent Publication No. 4-58489 JP-A-5-148340 JP-A-5-148340 Japanese Patent Laid-Open No. 2-270859 JP-A-6-192250 Japanese Patent Laid-Open No. 9-110979 Japanese Patent Laid-Open No. 9-255781 US Pat. No. 5,962,617 US Pat. No. 6,127,505

  The problem to be solved by the present invention is an optical material composition for an optical lens having a high refractive index and a high Abbe number, and also having high impact resistance even after hard coating, and polymerization of the composition for optical material. The resin for optical materials obtained by processing is provided.

That is, the present invention
(1) A polymerizable composition comprising the following components (A), (B) and (C) (2) A polymerizable composition comprising the following components (A) and (B1) The composition can be polymerized. The present invention relates to an optical material to be manufactured and a manufacturing method thereof.
(1)
(A) Compound having two or more mercapto groups (excluding compounds having amino group or organosilyl group )
(B) Aliphatic linear oligomer (C) isocyanate compound and / or thioisocyanate compound which is a polyol compound and / or a polythiol compound having two or more OH groups or SH groups having a number average molecular weight of 200 or more and less than 5000 per molecule. (2)
(A) Compound having two or more mercapto groups (excluding compounds having amino group or organosilyl group )
(B1) Polyurethane prepolymer and / or polythiourethane prepolymer obtained by reacting component (B) and component (C) in advance

The material obtained by polymerizing and curing the composition of the present invention has a high refractive index and Abbe number, has high impact resistance even after hard coating, and has excellent hue and heat resistance, which is not found in the prior art. It becomes an optical lens.

  Hereinafter, the present invention will be described in detail. The present invention relates to an optical material composition for an optical lens having a high refractive index, a high Abbe number, and high impact resistance even after hard coating, and an optical material obtained by polymerizing this optical material composition. It relates to resin for materials.

  In the polymerizable composition of the present invention, the proportions of the components (A), (B), and (C) are not generally determined by the refractive index and viscosity of each component, various physical properties of the obtained optical material, (A) Component 1 to 70% by weight, (B) Component 1 to 70% by weight, and (C) Component 1 to 70% by weight. If these ranges are exceeded, the high impact resistance, high refractive index and high Abbe number, which are the objects of the present invention, cannot be obtained, the heat resistance necessary for practical use is insufficient, or the color tone of the cured product is not obtained. Inconveniences such as deterioration. More preferably, it is in the range of 5 to 60% by weight of component (A), 5 to 50% by weight of component (B), 5 to 60% by weight of component (C), more preferably 20 to 60% by weight of component (A), Component (B) is in the range of 5 to 40% by weight and component (C) in the range of 20 to 60% by weight. More preferably, it is the range of (A) component 30 to 60% by weight, (B) component 10 to 30% by weight, and (C) component 30 to 60% by weight.

  The component (A) of the present invention includes mercaptans having one or more mercapto groups per molecule, thiophenols, and mercaptans having unsaturated groups such as vinyl, aromatic vinyl, methacryl, acryl, allyl, thio Examples include phenols.

Specific examples include methyl mercaptan, ethyl mercaptan, n-propyl mercaptan, n-butyl mercaptan, allyl mercaptan, n-hexyl mercaptan, n-octyl mercaptan, n-decyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, n-hexadecyl mercaptan, n-octadecyl mercaptan, cyclohexyl mercaptan, i-propyl mercaptan, t-butyl mercaptan, t-nonyl mercaptan, t-dodecyl mercaptan, phenyl mercaptan, benzyl mercaptan, 3-methylphenyl mercaptan, 4-methylphenyl Mercaptan, 4-chlorobenzyl mercaptan, 4-vinylbenzyl mercaptan, 3-vinylbenzyl mercaptan, methyl mercapto Lopionate, ethyl thioglycolate, n-butyl butyl glycolate, n-octyl thioglycolate, methyl (3-mercaptopropionate), ethyl (3-mercaptopropionate), 3-methoxybutyl (3- Mercaptopropionate), n-butyl (3-mercaptopropionate), 2-ethylhexyl (3-ercaptopropionate), n-octyl (3-mercaptopropionate), 2-mercaptoethanol, 3- Mercapto-1,2-propanediol, 2-mercapto-1,3-propanediol, mercaptoacetic acid, mercaptoglycolic acid, mercaptopropionic acid, methanedithiol, methanetrithiol, 3-mercaptopropanol, 2-mercaptopropanol, 2- Phenyl-2-me Captoethanol, 1,2-dimercaptoethane, 1,2-dimercaptopropane, 1,3-dimercaptopropane, 2,2-dimercaptopropane, 1,4-dimercaptobutane, 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-di Mercaptobutane, 2- (2-mercaptoethylthio) -1,3-dimercaptopropane, 1,2-bis [ (2-mercaptoethyl) thio] -3-mercaptopropane, 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-mercaptopropionate), diethylene glycol bis (2 Mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), 1,4-butanediol bis (2-mercaptoacetate), 1,4-butanediol bis (3-mercaptopropionate), trimethylolpropane tris ( 2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 1,2-dimercaptocyclohexane, 1 , 3-dimercaptocyclohexane, 1,4-dimercaptocyclohexane, 1,3-bis (mercaptomethyl) cyclohexane, 1,4-bis (mercaptomethyl) cyclohexane, 2,5-bis (mer) Puttomethyl) -1,4-dithiane, 2,5-bis (2-mercaptoethyl) -1,4-dithiane, 2,5-bis (2-mercaptoethylthiomethyl) -1,4-dithiane, 2,5 -Bis (mercaptomethyl) -1-thian, 2,5-bis (2-mercaptoethyl) -1-thian, 2,5-bis (mercaptomethyl) thiophene, thiophenol, 4-tert-butylthiophenol, 2 -Methylthiophenol, 3-methylthiophenol, 4-methylthiophenol, 2-vinylthiophenol, 3-vinylthiophenol, 4-vinylthiophenol, 2-hydroxythiophenol, 3-hydroxythiophenol, 4-hydroxythiophenol, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimer Captobenzene, 1,3-bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl) 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, mercaptobenzoic acid, 2-mercaptoimidazole, 2-mercapto-1 -Methylimidazole, 2,5-dimethyl Capto-1,3,4-thiadiazole, 3,4-thiophenedithiol, glyceryl dithioglycolate, 2-selenoethanol, bis (2-mercaptoethyl) selenide, bis (1,3-dimercapto-2-propyl) selenide, 2,3-bis (mercaptoethylseleno) -1-propanethiol, 2-mercaptomethyl-1,5-dimercapto-3-selenapentane, 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 (mercaptoethylselenomethyl) benzene, 2,5-diseleno-1,4-dithiane, 2,5-bis (selenomethyl) -1,4-dithiane, 2,5-bis (mercaptoethylselenomethyl) -1,4-dithiane, 2,6-dimercapto-1-selena-4-thiane, 3,5 Dimercapto-1-selena-4-thian, 2,6-bis (mercaptomethyl) -1-selena-4-thian, 3,5-bis (mercapto Til) -1-selena-4-thiane, 2,5-dimercapto-1,4-diselenan, 2,6-dimercapto-1,4-diselenan, 2,5-bis (mercaptomethyl) -1,4-diselenan 2,6-bis (mercaptomethyl) -1,4-diselenan, 2,5-dimercaptoselenane, 3,4-dimercaptoselenane, 2,5-bis (mercaptomethyl) selenane, 3,4- Bis (mercaptomethyl) selenane, 2,5-bis (selenomethyl) selenane, 3,4-bis (selenomethyl) selenane, 4,5-dimercapto-1,3-diselenolane, 4,5-bis (mercaptomethyl) -1 , 3-diselenolan, 3,6-dimercaptotriselenocyclooctane-dimercaptotriselenocyclooctane, 3,6-bis (mercaptomethyl) tri Mercaptans such as renocyclooctane, 3,6-diselenotriselenocyclooctane, 3,6-bis (selenomethyl) triselenocyclooctane, and among these polymercaptans, dimer to 20-mer Although an oligomer can be mentioned, it is not limited to these.

  These may be used alone or in combination of two or more. Among the components (A) described above, a compound having two or more mercapto groups in one molecule is preferable. More preferably, a compound having two or more mercapto groups is used in combination with a compound having two mercapto groups in one molecule.

  As the component (B) of the present composition, an aliphatic linear oligomer having a number average molecular weight of 200 or more that serves as a soft segment is used. As a suitable aliphatic linear oligomer, a polyol compound or a polythiol compound having at least one OH group or SH group, preferably two or more per molecule is desirable. When the number average molecular weight is less than 200, the ability as a soft segment is not sufficient, and the impact resistance of the obtained molded article is lowered. On the other hand, if the number average molecular weight exceeds 5000, the viscosity becomes high and handling becomes difficult. Therefore, a polyol compound or polythiol compound having a number average molecular weight of 200 to 5000 or a mixture thereof is desirable. More preferred are polyol compounds or polythiol compounds having a number average molecular weight of 300 to 3000, and even more preferred are polyol compounds or polythiol compounds having a number average molecular weight of 500 to 2000.

  Specific examples include polyether polyols, polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyether polyols such as polyoxypentamethylene glycol and polyether polyols having side chains, adipic acid, sebacic acid, One or more of dibasic acids such as maleic acid, glycols such as ethylene glycol, propylene glycol, butanediol, hexamethylene glycol, cyclohexane methanol, or glycerin, phloroglucinol, hexanetriol, trimethylolethane, trimethylolpropane Polyester polyols, polycaprolactones, polyvalerolactones, etc. obtained from one or more polyols such as Polycarbonate polyols such as lactone polyol, polyhexamethylene carbonate polyol, neopentylene carbonate polyol, polyester thiol, polythioester thiol, polyethylene sulfide thiol, polyethylene disulfide thiol, polyethylene polysulfide thiol and other polysulfide thiols, polyethylene sulfide diol, polyethylene disulfide diol, polyethylene Polysulfide diols such as polysulfide diol, oligo (2,5-dithiane) disulfide obtained by oxidizing 2,5-dimercaptodithiane, polythiocarbonate thiol and the like are preferably used. Furthermore, polyol compounds such as polydimethylsiloxane diol are also included. Moreover, a block copolymer of a plurality of polyol compounds, a random copolymer, a mixture of a plurality of polyol compounds, and the like can be given, but the invention is not limited thereto.

  One or more of these polyols may be used in combination with a polyol such as glycerin, phloroglicinol, hexanetriol, trimethylolethane, trimethylolpropane, pentaerythritol, 3-methylpentane-1,3,5-triol. it can.

  The component (C) of the present invention includes all compounds having at least one isocyanate group and / or isothiocyanate group per molecule. Although the specific example is given to the following, it is not limited to them. A compound having two (thio) isocyanate groups in one molecule is preferred.

  Methyl isocyanate, ethyl isocyanate, propyl isocyanate, iso-propyl isocyanate, n-butyl isocyanate, sec-butyl isocyanate, tert-butyl isocyanate, pentyl isocyanate, hexyl isocyanate, octyl isocyanate, dodecyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, toluyl isocyanate, Diethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,2-bis (isocyanato) ethoxyethane, cyclohexane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanato) Methyl) cyclohex , 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) thiophosphate, isopropylidenebis (cyclohexylisocyanate), 2,2′-bis (4-isocyanatophenyl) propane, triphenylmethane Triisocyanate, bis (diisocyanatetolyl) phenylmethane, 4,4 ′, 4 ″ -triisocyanate-2,5-dimethoxyphenyl 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-isocyanatobenzene), m-xylylene diisocyanate, p-xylylene diisocyanate, temethethylyl xylylene diisocyanate, 1,3-bis (1-isocyanate-1-methylethyl) benzene, 1,4-bis (1-isocyanate-1-methylethyl) Benzene, 1,3-bis (2-isocyanato-2-pro Pyr) benzene, 2,6-bis (isocyanatomethyl) naphthalene, 1,5-naphthalene diisocyanate, bis (isocyanatomethyl) tetrahydrodicyclopentadiene, bis (isocyanatomethyl) dicyclopentadiene, bis (isocyanatomethyl) tetrahydrothiophene, 2,5-diisocyanate methylnorbornene, bis (isocyanatemethyl) adamantane, dimer acid diisocyanate, 1,3,5-tri (1-isocyanatohexyl) isocyanuric acid, thiodiethyl diisocyanate, thiodipropyl diisocyanate, thiodihexyl diisocyanate, bis [(4-Isocyanatomethyl) phenyl] sulfide, 2,5-diisocyanato-1,4-dithiane, 2,5-diisocyanatomethyl-1,4-di Isocyanates such as An, 2,5-diisocyanatomethylthiophene, dithiodiethyl diisocyanate, dithiodipropyl diisocyanate, and compounds in which all or part of the isocyanate groups of the above isocyanates are changed to thioisocyanate groups Among them, compounds having two (thio) isocyanate groups in one molecule are preferable. Examples of polyisocyanates include dimers, cyclized trimers and adducts of alcohols or thiols by a burette-type reaction. These may be used alone or in combination of two or more.

  Moreover, (B) component and (C) component can be made to react beforehand, and it can also be used as a polyurethane prepolymer or polythiourethane. This poly (thio) urethane prepolymer is referred to as (B1).

  The poly (thio) urethane prepolymer (B1) can be prepared by a commonly used method. For example, (C) component (thio) isocyanate and (B) component aliphatic linear oligomer having SH group or OH group are mixed and reacted at 80 to 110 ° C. for 1 to 5 hours. A prepolymer can also be prepared by adding trifunctional or higher thiols or alcohols to an aliphatic linear oligomer. Further, after the reaction of poly (thio) isocyanate with an aliphatic linear oligomer having an SH group or OH group is completed, other non-reacting components such as poly (thio) isocyanate can be mixed to form a prepolymer. This technique is effective particularly when the viscosity of the reaction mixture is high.

  The resin of the present invention can be produced by heat polymerization of the component (A), the component (B) and the component (C) in the presence or absence of a curing catalyst. A preferable method is a method using a curing catalyst, and examples of the curing catalyst include amines, phosphine, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, secondary iodonium salts, mineral acids, Lewis acids, organic acids, silicic acids, tetrafluoroboric acids, peroxides, azotized compounds, condensates of aldehydes and ammonia compounds, guanidines, thioureas, thiazoles, sulfenamides, thiuram , Dithiocarbamates, xanthates, acidic phosphates and the like. The typical examples of these are shown below.

(A) Ethylamine, n-propylamine, sec-propylamine, n-butylamine, sec-butylamine, i-butylamine, tert-butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, laurylamine, mistyri Ruamine, 1,2-dimethylhexylamine, 3-pentylamine, 2-ethylhexylamine, allylamine, aminoethanol, 1-aminopropanol, 2-aminopropanol, aminobutanol, aminopentanol, aminohexanol, 3-ethoxypropylamine 3-propoxypropylamine, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 3- (2-ethylhexyloxy) propylamine Primary amines such as ethylene, aminocyclopentane, aminocyclohexane, aminonorbornene, aminomethylcyclohexane, aminobenzene, benzylamine, phenethylamine, α-phenylethylamine, naphthylamine, furfurylamine; 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'-dimethyl Propane, aminoethylethanolamine, 1,2-, 1,3- or 1,4-bisaminocyclohexane, 1,3- or 1,4-bisaminomethylcyclohexane, 1,3- or 1,4-bisamino Ethylcyclohexane, 1,3- or 1,4-bisaminopropylcyclohexane, hydrogenated 4,4′-diaminodiphenylmethane, 2- or 4-aminopiperidine, 2- or 4-aminomethylpiperidine, 2- or 4-amino Ethylpiperidine, N-aminoethylpiperidine, 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-, 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-tetrao Saspiro [5,5] undecane, diethylenetriamine, iminobispropylamine, methyliminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-aminoethylpiperazine, N-amino Primary polyamines such as propylpiperazine, 1,4-bis (aminoethylpiperazine), 1,4-bis (aminopropylpiperazine), 2,6-diaminopyridine, bis (3,4-diaminophenyl) sulfone; Dipropylamine, di-n-butylamine, di-sec-butylamine, diisobutylamine, di-n-pentylamine, di-3-pentylamine, dihexylamine, octylamine, di (2-ethylhexyl) amine, methyl Ruhexylamine, diallylamine, pyrrolidine, piperidine, 2-, 3-, 4-picoline, 2,4-, 2,6-, 3,5-lupetidine, diphenylamine, N-methylaniline, N-ethylaniline, dibenzylamine , Methylbenzylamine, dinaphthylamine, pyrrole, indoline, indole, morpholine and other secondary amines; 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-diaminohexane, piperazine, 2-methyl Piperazine, 2,5- or 2,6-dimethylpiperazine, homopiperazine, 1,1-di- (4-piperidyl) methane, 1,2-di- (4-piperidyl) ethane, 1,3-di- ( Secondary polyamines such as 4-piperidyl) propane, 1,4-di- (4-piperidyl) butane; trimethylamine, triethylamine, tri-n-propylamine, tri-iso-propyl Min, 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-diethylethanolamine, N, N-dimethylethanolamine, N-ethyldiethanolamine, triethanol Amine, tribenzylamine, N, N-dimethylbenzylamine, diethylbenzylamine, triphenylamine, N, N-dimethylamino-p-cresol, N, N-dimethylaminomethylphenol, 2- (N, N-dimethyl) Aminomethyl) phenol, N, N-dimethylaniline, N, N-diethylaniline, pyridine, quinoline, N-methylmorpholine, N-methylpiperidine, 2- (2-dimethylaminoethoxy) -4-methyl-1,3 , 2-dioxabornane and the like; tetramethylethylenediamine, pyrazine, N, N′-dimethylpiperazine, N, N′-bis ((2-hydroxy) propyl) piperazine, hexamethylenetetramine, N, N, N ′ , N′-tetramethyl-1,3-butanamine, 2-dimethylamino-2 Tertiary polyamines such as hydroxypropane, diethylaminoethanol, N, N, N-tris (3-dimethylaminopropyl) amine, 2,4,6-tris (N, N-dimethylaminomethyl) phenol, 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-mercaptobenzo Imidazole, 3-mercapto-4-methyl-4H-1,2,4-triazole, 5-mercapto-1-methyl-tetrazole, 2,5-dimercapto-1,3,4-thiadiazole 1-benzyl-2-methyl Imidazole, N- (2′-cyanoethyl) -2-methylimidazole, N- (2′-cyanoethyl) -2-undecylimidazole, N- (2′-cyanoethyl) -2-phenylimidazole, 3,3-bis Various imidazoles such as-(2-ethyl-4-methylimidazolyl) methane, an adduct of alkyl imidazole and isocyanuric acid; 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-7 Oxazines; amine compounds represented by above.
(B) A complex of the amines of (a) with borane and boron trifluoride.
(C) Trimethylphosphine, triethylphosphine, tri-iso-propylphosphine, tri-n-butylphosphine, tri-n-hexylphosphine, tri-n-octylphosphine, tricyclohexylphosphine, triphenylphosphine Fins, tribenzylphosphine, tris (2-methylphenyl) phosphine, tris (3-methylphenyl) phosphine, tris (4-methylphenyl) phosphine, tris (diethylamino) phosphine, tris (4-methylphenyl) phosphine, dimethylphenyl Phosphine such as phosphine, diethylphenylphosphine, dicyclohexylphenylphosphine, ethyldiphenylphosphine, diphenylcyclohexylphosphine, chlorodiphenylphosphine .
(D) 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 hydrogensal Fight, tetra-n-butylammonium tetrafluoroborate, tetra-n-butyl Ruammonium 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, trimethylbenzylammonium chloride, trimethyl Benzyl ammonium bromide, trie Ru-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, cetyldimethylbenzylammonium Chloride, lauryldimethylbenzylammonium chloride, methyl Rutriphenylammonium chloride, methyltribenzylammonium chloride, methyltriphenylammonium bromide, methyltribenzylammonium bromide, ethyltriphenylammonium chloride, ethyltribenzylammonium chloride, ethyltriphenylammonium bromide, ethyltribenzylammonium bromide, n-butyl Triphenylammonium chloride, n-butyltribenzylammonium chloride, n-butyltriphenylammonium bromide, n-butyltribenzylammonium bromide, 1-methylpyridinium chloride, 1-methylpyridinium bromide, 1-ethylpyridinium chloride, 1-ethyl Pyridinium bromide, 1-n-butyl Lidinium 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-methylpicolinium chloride, 1 -Methylpicolinium bromide, 1-ethylpicolinium chloride, 1-ethylpicolinium bromide, 1-n-butylpicolinium chloride, 1-n-butyl Rupicolinium 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-benzylpicolinium chloride, 1-benzyl Quaternary ammonium salts such as picolinium bromide.
(E) 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-butyltri Phenylphosphonium iodide, n-hexyltriphenylphosphonium bromide De, n- octyl triphenylphosphonium bromide, tetraphenylphosphonium bromide, tetrakis hydroxymethyl phosphonium chloride, tetrakis hydroxymethyl phosphonium bromide, tetrakis hydroxyethyl phosphonium chloride, phosphonium salts such as tetrakis hydroxybutyl phosphonium chloride.
(F) Trimethylsulfonium bromide, triethylsulfonium bromide, tri-n-butylsulfonium chloride, tri-n-butylsulfonium bromide, tri-n-butylsulfonium iodide, tri-n-butylsulfonium tetrafluoroborate, tri-n- Sulfonium salts such as hexylsulfonium bromide, tri-n-octylsulfonium bromide, triphenylsulfonium chloride, triphenylsulfonium bromide, triphenylsulfonium iodide.
(G) Iodonium salts such as diphenyliodonium chloride, diphenyliodonium bromide, and diphenyliodonium iodide.
(H) Mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and carbonic acid, and half esters thereof.
(I) Boron trifluoride, boron trifluoride etherate, aluminum fluoride, aluminum chloride, triphenylaluminum, potassium octoate, calcium acetate, tetraisopropoxy titanium, tetrabutoxy titanium, tetrachloro titanium, 2-titanate 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, dioctyl Acetate, dioctyltin dilaurate, dioctyltin laurate, dioctyltin diricinolate, dioctyltin dioleate, dioctyltin di (6-hydroxy) caproate, dioctyltin bis (isooctylthioglycolate), dioctyltin oxide, dioctyl Tin dichloride, dioctyltin maleate, dioctyltin bis (butyl maleate), didodecyltin diricinolate, tin stearate, zinc chloride, acetylacetone zinc, oleic acid copper, acetylacetone copper, acetylacetone iron, naphthenic acid iron, iron lactate Lewis acids represented by iron citrate, iron gluconate and the like.
(J) Organic acids and their half esters.
(K) Silicic acid, tetrafluoroboric acid.
(L) Cumyl peroxyneodecanoate, diisopropyl peroxydicarbonate, diallyl peroxydicarbonate, di-n-propyl peroxydicarbonate, dimyristyl peroxydicarbonate, cumyl peroxyneohexanoate, tert- Hexyl peroxyneodecanoate, tert-butylperoxyneodecanoate, tert-hexylperoxyneohexanoate, tert-butylperoxyneohexanoate, 2,4-dichlorobenzoyl peroxide, benzoyl peroxide Peroxides such as dicumyl peroxide and di-ter-butyl peroxide; peroxides such as cumene hydroperoxide and tert-butyl hydroperoxide.
(M) 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.
(N) Acetaldehyde and ammonia reactant, formaldehyde and paraylidine condensate, acetaldehyde and paraylidine condensate, formaldehyde and aniline reactant, acetaldehyde and aniline reactant, butyraldehyde and aniline reactant, formaldehyde and acetaldehyde Reaction product of aniline, reaction product of acetaldehyde, butyraldehyde and aniline, condensation product of butyraldehyde and monobutylamine, reaction product of butyraldehyde and butylideneaniline, reaction product of heptaldehyde and aniline, reaction of tricrotonylidene-tetramine , Condensates of aldehydes and amine compounds, such as condensates of α-ethyl-β-propylacrolein and aniline, condensates of formaldehyde and alkylimidazoles.
(O) diphenylguanidine, phenyltolylguanidine, phenylxylylguanidine, tolyloxysilylguanidine, diortolylguanidine, orthotolylguanide, diphenylguanidine phthalate, tetramethylguanidine, diorthotolylguanidine salt of dicatecholboric acid, etc. Guanidines.
(P) Thioureas such as thiocarboanilide, diortolylthiourea, ethylenethiourea, diethylthiourea, dibutylthiourea, dilaurylthiourea, trimethylthiourea, dimethylethylthiourea, tetramethylthiourea, and the like.
(Q) 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, benzothiadiadi Thiazoles such as ruthiobenzoate, 2-mercaptothiazoline, sodium salt of 2-mercaptobenzothiazole, zinc salt of 2-mercaptobenzothiazole, complex salt of dibenzothiazyl disulfide and zinc chloride.
(R) 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-benzothia Sulfenamides such as dirusulfenamide.
(S) Tetramethylthiuram monosulfide, tetraethylthiuram monosulfide, tetrabutylthiuram monosulfide, dipentamethylenethiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, N, N′-dimethyl-N, Thiurams such as N′-diphenylthiuram disulfide, N, N′-diethyl-N, N′-diphenylthiuram disulfide, dipentamethylenethiuram disulfide, dipentamethylenethiuram tetrasulfide, and cyclic thiuram.
(T) sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate, sodium dibutyldithiocarbamate, sodium pentamethylenedithiocarbamate, sodium cyclohexylethyldithiocarbamate, potassium dimethyldithiocarbamate, lead dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, Zinc dibutyldithiocarbamate, zinc dibenzyldithiocarbamate, zinc pentamethylenedithiocarbamate, zinc dimethylpentamethylenedithiocarbamate, zinc ethylphenyldithiocarbamate, bismuth dimethyldithiocarbamate, cadmium diethyldithiocarbamate, cadmium pentamethylenedithiocarbamate, dimethyldithioca Selenium bamates, selenium diethyldithiocarbamate, tellurium dimethyldithiocarbamate, tellurium diethyldithiocarbamate, iron dimethyldithiocarbamate, copper dimethyldithiocarbamate, diethylammonium diethyldithiocarbamate, dibutyldithiocarbamate N, N-cyclohexylammonium, pentamethylenedithiocarbamate piperidine Dithiocarbamates such as sodium cyclohexylethylammonium cyclohexylethyldithiocarbamate, pipecoline methylpentamethylenedithiocarbamate, and a complex compound of zinc pentamethylenedithiocarbamate and piperidine.
(U) Xanthates such as sodium isopropylxanthate, zinc isopropylxanthate, zinc butylxanthate, and dibutylxanthate disulfide. (V) 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 acid such as 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 didecanol phosphate Phosphate esters.

  As mentioned above, although the polymerization catalyst at the time of carrying out the polymerization hardening of the composition of this invention was illustrated, if the effect of polymerization hardening is expressed, it will not be limited to these listed compounds. These may be used alone or in combination of two or more. The addition amount of the catalyst used in the present invention is 0.0001 to 10.0 parts by weight, preferably 0.0005 to 5.0 parts per 100 parts by weight of the composition (1) or (2). Parts by weight. When the amount of the curing catalyst is more than 10.0 parts by weight, the refractive index of the cured product is lowered and colored. On the other hand, if it is less than 0.0001 part by weight, it will not be cured sufficiently and the heat resistance will be insufficient.

  In the composition for optical materials of the present invention, in addition to the composition of (1) or (2), a part of the composition components or the like for the purpose of improving various performances such as oxidation resistance, weather resistance, dyeability, strength, etc. It is also possible to carry out curing polymerization by adding a compound capable of reacting with all of them. In this case, a known polymerization curing catalyst can be added separately as necessary for the reaction.

  Compounds that can react with some or all of the composition components include epoxy compounds, carboxylic acids, carboxylic anhydrides, phenols, amines, vinyl compounds, allyl compounds, acrylic compounds, methacrylic compounds, etc. Can be mentioned. The typical examples of these are shown below.

(A) Monoepoxy compounds such as ethylene oxide and propylene oxide, produced by condensation of polyhalogen compounds such as hydroquinone, catechol, resorcin, bisphenol A, bisphenol F, bisphenol ether, halogenated bisphenol A, novolac resin and epihalohydrin Phenolic epoxy compounds, methanol, ethanol, propanol, butanol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-propanediol, 1,4-butanediol 1,6-hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythrito 1,3- and 1,4-cyclohexanediol, 1,3- and 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, bisphenol A / ethylene oxide adduct, bisphenol A / propylene oxide adduct, etc. Alcohol-based epoxy compound produced by condensation of a compound and epihalohydrin, urethane-based epoxy compound produced from the above alcohol and phenol compound and diisocyanate, acetic acid, propionic acid, benzoic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, Dimer acid, phthalic acid, iso, terephthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, het acid, nadic acid, maleic acid, succinic acid, fumaric acid, trimellitic acid, benze Glycidyl ester epoxy compounds produced by condensation of carboxylic acid compounds such as tetracarboxylic acid, benzophenone tetracarboxylic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid and epihalohydrin, 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, bis- (3-aminopropyl) ether, 1,2-bis- (3-aminopropoxy) ethane, 1,3-bis- (3-aminopropoxy) -2 , 2'-dimethylpropane, 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, isophoronediamine, 1,4-bisaminopropylpiperazine, m-, or p-phenylenediamine, 2,4- or 2,6-tolylenediamine, m-, or p-xylylenediamine Amine, 1,5- or 2,6-naphthalenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 2,2- (4,4'-diaminodiphenyl) propane, 2-aminobenzene Thiol, 3-aminobenzenethiol, 4-aminobenzenethiol, 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-dia Nohexane, piperazine, 2-methylpiperazine, 2,5- or 2,6-dimethylpiperazine, homopiperazine, 1,1-di- (4-piperidyl) -methane, 1,2-di- (4-piperidyl)- Ethane, 1,3-di- (4-piperidyl) -propane, amine epoxy compound produced by condensation of 1,4-di- (4-piperidyl) -butane and epihalohydrin, bis (β-epoxypropyl) sulfide Bis (β-epoxypropylthio) methane, 1,2-bis (β-epoxypropylthio) ethane, 1,3-bis (β-epoxypropylthio) propane, 1,2-bis (β-epoxypropylthio) ) Propane, 1- (β-epoxypropylthio) -2- (β-epoxypropylthiomethyl) propane, 1,4-bis (β-epoxypro) Ruthio) butane, 1,3-bis (β-epoxypropylthio) butane, 1- (β-epoxypropylthio) -3- (β-epoxypropylthiomethyl) butane, 1,5-bis (β-epoxypropyl) Thio) pentane, 1- (β-epoxypropylthio) -4- (β-epoxypropylthiomethyl) pentane, 1,6-bis (β-epoxypropylthio) hexane, 1- (β-epoxypropylthio)- 5- (β-epoxypropylthiomethyl) hexane, 1- (β-epoxypropylthio) -2-[(2-β-epoxypropylthioethyl) thio] ethane, 1- (β-epoxypropylthio) -2 -[[2- (2-β-epoxypropylthioethyl) thioethyl] thio] ethane, tetrakis (β-epoxypropylthiomethyl) methane, 1,1,1- Lis (β-epoxypropylthiomethyl) propane, 1,5-bis (β-epoxypropylthio) -2- (β-epoxypropylthiomethyl) -3-thiapentane, 1,5-bis (β-epoxypropylthio) ) -2,4-bis (β-epoxypropylthiomethyl) -3-thiapentane, 1- (β-epoxypropylthio) -2,2-bis (β-epoxypropylthiomethyl) -4-thiahexane, 5,6-Tris (β-epoxypropylthio) -4- (β-epoxypropylthiomethyl) -3-thiahexane, 1,8-bis (β-epoxypropylthio) -4- (β-epoxypropylthiomethyl) ) -3,6-dithiaoctane, 1,8-bis (β-epoxypropylthio) -4,5bis (β-epoxypropylthiomethyl) -3,6-dithiaoct 1,8-bis (β-epoxypropylthio) -4,4-bis (β-epoxypropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epoxypropylthio) -2, 4,5-tris (β-epoxypropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epoxypropylthio) -2,5-bis (β-epoxypropylthiomethyl) -3,6 -Dithiaoctane, 1,9-bis (β-epoxypropylthio) -5- (β-epoxypropylthiomethyl) -5-[(2-β-epoxypropylthioethyl) thiomethyl] -3,7-dithianonane, 1 , 10-bis (β-epoxypropylthio) -5,6-bis [(2-β-epoxypropylthioethyl) thio] -3,6,9-trithiadecane, 1,11-bis (β-epoxy Propylthio) -4,8-bis (β-epoxypropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epoxypropylthio) -5,7-bis (β-epoxypropyl) Thiomethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epoxypropylthio) -5,7-[(2-β-epoxypropylthioethyl) thiomethyl] -3,6,9 -Trithiaundecane, 1,11-bis (β-epoxypropylthio) -4,7-bis (β-epoxypropylthiomethyl) -3,6,9-trithiaundecane, 1,3 and 1,4- Bis (β-epoxypropylthio) cyclohexane, 1,3 and 1,4-bis (β-epoxypropylthiomethyl) cyclohexane, bis [4- (β-epoxypropylthio) cyclohexane Sil] methane, 2,2-bis [4- (β-epoxypropylthio) cyclohexyl] propane, bis [4- (β-epoxypropylthio) cyclohexyl] sulfide, 2,5-bis (β-epoxypropylthiomethyl) ) -1,4-dithiane, 2,5-bis (β-epoxypropylthioethylthiomethyl) -1,4-dithiane, 1,3 and 1,4-bis (β-epoxypropylthio) benzene, 1, 3, and 1,4-bis (β-epoxypropylthiomethyl) benzene, bis [4- (β-epoxypropylthio) phenyl] methane, 2,2-bis [4- (β-epoxypropylthio) phenyl] propane Bis [4- (β-epoxypropylthio) phenyl] sulfide, bis [4- (β-epoxypropylthio) phenyl] sulfone, 4,4 ′ Sulfur-containing epoxy compounds such as bis (β-epoxypropylthio) biphenyl, 3,4-epoxycyclohexyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexanedioxide, 2- (3,4-epoxycyclohexyl) -5 , 5-spiro-3,4-epoxycyclohexane-meta-dioxane, alicyclic epoxy compounds such as bis (3,4-epoxycyclohexyl) adipate, cyclopentadiene epoxide, epoxidized soybean oil, epoxidized polybutadiene, vinylcyclohexene epoxide Epoxy compounds produced by epoxidation of unsaturated compounds such as vinyl phenyl glycidyl ether, vinyl benzyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether Epoxy compounds having an unsaturated group such as epoxy compounds.
(B) Carboxylic acids exemplified as the starting material of the partner to be reacted with the epihalohydrin described in the epoxy compound of (a).
(C) Carboxylic anhydrides exemplified as the raw material of the partner to be reacted with the epihalohydrin described in the epoxy compound of (a).
(D) Phenols exemplified as the starting material of the partner to be reacted with the epihalohydrin described in the epoxy compound of (a).
(E) Amines exemplified as the starting material of the partner to be reacted with the epihalohydrin described in the epoxy compound of (a).
(F) Vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, phenyl vinyl ether, benzyl vinyl ether, 2-chloroethyl vinyl ether, cyclohexyl vinyl ether, vinyl glycidyl ether, vinyl alcohol, methyl vinyl carbinol, ethylene glycol monovinyl ether, ethylene glycol Divinyl ether, diethylene glycol monovinyl ether, diethylene glycol divinyl ether, tetramethylene glycol monovinyl ether, divinyl sulfide, vinyl ethyl sulfide, vinyl phenyl sulfide, methyl vinyl ketone, divinyl dicarbonate, vinyl diglycol carbonate, vinylene carbonate, vinyl acetate, chloro Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, vinyl 2-ethylhexanoate, divinyl adipate, vinyl benzoate, vinyl salicylate, vinyl acrylate, vinyl methacrylate, vinyl bromide, vinyl iodide, vinyl phosphate, Vinylurea, styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4,6-trimethylstyrene, 4-t-butylstyrene, stilbene, vinylphenol, 3-vinylbenzyl Alcohol, 4-vinylbenzyl alcohol, 2- (4-vinylphenylthio) ethanol, 2- (3-vinylphenylthio) ethanol, 2- (4-vinylbenzylthio) ethanol, 2- (3-vinylbenzylthio) Ethanol, 1,3-bis (4- Vinylbenzylthio) -2-propanol, 1,3-bis (3-vinylbenzylthio) -2-propanol, 2,3-bis (4-vinylbenzylthio) -1-propanol, 2,3-bis (3 -Vinylbenzylthio) -1-propanol, cinnamyl alcohol, cinnamaldehyde, 1,3-divinylbenzene, 1,4-divinylbenzene, trivinylbenzene, divinylphthalate, 2-chlorostyrene, 3-chlorostyrene, 4- Chlorostyrene, 3-chloromethylstyrene, 4-chloromethylstyrene, 4-aminostyrene, 3-cyanomethylstyrene, 4-cyanomethylstyrene, 4-vinylbiphenyl, 2,2'-divinylbiphenyl, 4,4'- Divinylbiphenyl, 2,2'-distyryl ether, 4,4'-distyryl ether 2,2′-distyryl sulfide, 4,4′-distyryl sulfide, 2,2-bis (4-vinylphenyl) propane, bis (4-vinylphenyl) ether, 2,2-bis (4-vinyl) Vinyl compounds such as (roxyphenyl) propane;

(G) Allyl compounds in which some or all of the vinyl groups of the compounds exemplified as the vinyl compounds in (f) are replaced with allyl groups.
(H) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 3-phenoxy-2-hydroxypropyl acrylate, trimethylolpropane mono Acrylate, 2-hydroxyethyl isocyanurate monoacrylate, 2-hydroxyethyl isocyanurate diacrylate, 2-hydroxyethyl cyanurate monoacrylate, 2-hydroxyethyl cyanurate diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, 1,3 -Butylene glycol diacrylate, triethylene glycol diacrylate Polyethylene glycol diacrylate, propylene glycol diacrylate, 1,3-propanediol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate Acrylate, polypropylene glycol diacrylate, 2-hydroxy-1,3-diacryloxypropane, 2,2-bis [4- (acryloxyethoxy) phenyl] propane, 2,2-bis [4- (acryloxyethoxy) Cyclohexyl] propane, 2,2-bis [4- (2-hydroxy-3-acryloxypropoxy) phenyl] propane, 2,2-bis [4- (acryloxy-diethoxy) phenyl] propane, 2,2-bis [ 4- (Acryl Polyethoxy) phenyl] propane, trimethylolpropane triacrylate, pentaerythritol monoacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaacrylate of bis (2,2,2-trimethylolethyl) ether , Acrylic compounds such as hexaacrylate of bis (2,2,2-trimethylolethyl) ether, bis (4-acryloylthiophenyl) sulfide.
(I) Methacrylic compounds in which part or all of the acrylic groups of the compounds exemplified as the acrylic compounds of (h) are replaced with methacrylic groups.

  It is also possible to use an inorganic compound containing a sulfur atom and / or selenium atom for the purpose of improving the refractive index. Specific examples of the refractive index improving component include sulfur, hydrogen sulfide, carbon disulfide, carbon selenosulfide, ammonium sulfide, sulfur dioxide, sulfur trioxide, and other sulfur oxides, thiocarbonate, sulfuric acid and its salts, hydrogen sulfate. Salts, sulfites, hyposulfites, persulfates, thiocyanates, thiosulfates, sulfur dichloride, thionyl chloride, thiophosgene and other halides, boron sulfide, nitrogen sulfide, silicon sulfide, phosphorus sulfide, arsenic sulfide, metal Excluding inorganic compounds having sulfur atoms such as sulfides and metal hydrosulfides, and selenium sulfide, all inorganic compounds satisfying this condition are included. Specific examples include selenium oxides such as selenium, hydrogen selenide, selenium dioxide, carbon diselenide, ammonium selenide, selenium dioxide, selenic acid and salts thereof, selenite and salts thereof, hydrogen selenate salts, seleno Sulfuric acid and salts thereof, selenopyrosulfuric acid and salts thereof, halides such as selenium tetrabromide and selenium oxychloride, selenium atoms such as selenocyanate, boron selenide, phosphorus selenide, arsenic selenide and metal selenides Examples include inorganic compounds. These inorganic compounds having a sulfur atom and a selenium atom may be used alone or in combination of two or more.

  In addition, when an optical material is obtained by polymerizing and curing the composition of the present invention, a material obtained by adding an additive such as a known antioxidant, ultraviolet absorber, yellowing inhibitor, bluing agent, pigment, etc. It is also possible to improve the performance.

  Further, when the 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 material and the mold. Is also necessary. Examples of the internal adhesion improving agent mentioned here include 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3 Examples include silane compounds such as mercaptopropyltrimethoxysilane, and 0.00001 to 5 parts by weight can be used with respect to 100 parts by weight of the composition of the present invention. Conversely, when the composition of the present invention is difficult to peel off from the mold after polymerization, a known external and / or internal mold release agent is used or added to improve the mold releasability from the mold of the resulting cured material. Is also possible. The internal mold release agent mentioned here is a fluorine-based nonionic surfactant, a silicon-based nonionic surfactant, an alkyl quaternary ammonium salt, a phosphate ester, an acidic phosphate ester, an oxyalkylene-type acidic phosphate ester, an alkali of an acidic phosphate ester. Metal salts, 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, etc. For example, and can be used in an amount of 0.00001 to 5 parts by weight based on 100 parts by weight of the composition of the present invention.

  In the invention, a method for producing an optical material, and a composition comprising a performance improver, a catalyst, an adhesion improver or a release improver, an antioxidant, an ultraviolet absorber, a yellowing inhibitor, a bluing agent, a pigment, and the like After the additives are mixed and uniformed, the mixture is poured into a glass or metal mold, the polymerization curing reaction is advanced by heating, and then the mold is removed from the mold.

  In the method for producing a cured resin optical material of the present invention, a part or all of the composition comprising the composition of (1) or (2) above and a performance improving agent is present in the presence or absence of a catalyst before casting. After preliminarily polymerizing at −100 to 160 ° C. for 0.1 to 480 hours with stirring or without stirring, a composition for optical material can be prepared and cast. In particular, when the compound in the composition for optical materials contains a solid component and handling is not easy, this preliminary polymerization is effective. The preliminary polymerization conditions are preferably −10 to 120 ° C. for 0.1 to 240 hours, more preferably 0 to 100 ° C. for 0.1 to 120 hours. Additives such as property improvers, antioxidants, ultraviolet absorbers, yellowing inhibitors, bluing agents and pigments may be added simultaneously.

  The manufacturing method of the cured resin optical material of the present invention is as follows in more detail. As described above, the main raw material and auxiliary raw material are mixed and then injected and cured into a mold. The composition of (1) or (2) and a part or all of the composition components used as a performance improver are prepared. Additives such as compounds, catalysts, adhesion improvers or releasability improvers, antioxidants, UV absorbers, yellowing inhibitors, bluing agents, pigments, etc., all of which can be simultaneously stirred in the same container It may be mixed below, each raw material may be added and mixed in stages, or several components may be mixed separately and then remixed in the same container. Each raw material, additive and the like may be mixed in any order. In mixing, the set temperature, the time required for this, etc., basically need only be the conditions that each component is sufficiently mixed, but the excessive temperature, time is an undesirable reaction between each raw material and additive, Furthermore, the viscosity is increased, making the casting operation difficult, and so on. The mixing temperature should be about −50 ° C. to 100 ° C., preferably −30 ° C. to 70 ° C., more preferably −5 ° C. to 50 ° C. The mixing time is 1 minute to 12 hours, preferably 5 minutes to 10 hours, and most preferably about 5 minutes to 6 hours. Performing the degassing operation under reduced pressure before, during or after mixing the raw materials and additives is a preferable method from the viewpoint of preventing the generation of bubbles during the subsequent cast polymerization curing. The degree of decompression at this time is about 0.1 mmHg to 700 mmHg, and preferably 0.5 mmHg 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 the main and sub raw materials before mixing with a filter having a pore size of about 0.05 to 3 μm to purify impurities and the like. . After pouring into a glass or metal mold, polymerization and curing is performed with an electric furnace, water or an oil bath, etc., but the curing time is 0.1 to 100 hours, usually 1 to 72 hours, and the curing temperature is −10 to 160. ° C, usually 0 to 140 ° C. The polymerization can be carried out by holding at a predetermined polymerization temperature for a predetermined time, raising the temperature from 0.1 ° C to 100 ° C / h, lowering the temperature from 0.1 ° C to 100 ° C / h, and a combination thereof. In addition, after the curing is completed, annealing the material at a temperature of 50 to 150 ° C. for about 10 minutes to 5 hours is a preferable treatment for removing the distortion of the optical material of the present invention. Furthermore, surface treatment such as dyeing, hard coating, antireflection, antifogging and impact resistance can be performed as necessary.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to these examples at all. In addition, the physical property of the molded object obtained in the Example, the application example, and the physical property of the polymer obtained by the comparative application example were measured according to the method shown below.

(A) Refractive index (nd ), Abbe number (νd ): Measured at 25 ° C. using a precision refractometer KPR-200 manufactured by Kalnew.
(B) YI value: A 2.5 mm thick flat plate was measured using a color analyzer SE2000 manufactured by Nippon Denshoku.
(C) Heat resistance: Using TMA (Thermomechanical analyzer manufactured by SEIKO), a load of 10 g was applied to a 1 mm pin, and the temperature was raised at 10 ° C./min, and the softening point was measured.
(D) Impact resistance: A falling ball test was performed in which a hard steel coated 2.5 mm thick flat plate was dropped from a light steel ball to a heavy steel ball in order from a height of 127 cm. (Evaluate the weight at the time of destruction)

Synthesis example 1
Preparation of Prepolymer (1) A mixture of 19.5 g of Plaxel 205 (number average molecular weight 530) and 78.0 g of Plaxel 212 (number average molecular weight 1234), a polycaprolactone diol manufactured by Daicel Chemical Industries, was heated to 90 ° C. and stirred. The mixture was degassed under vacuum for 1 hour. After mixing 37.6 g (0.20 mol) of xylylene diisocyanate (XDI), the mixture was reacted at 135 ° C. for 1 hour. The prepolymer after the reaction had an NCO value of 1.48 mmol / g and a number average molecular weight of 4500.

Example 1
PLACCEL 205 (number average molecular weight 530) 10.1 g, 1,2,6,7-tetramercapto-4-thiaheptane (TMTH) 23.7 g, pentaerythritol tetrakis (3-mercaptopropionate) (4TP) 17.0 g 1,3-Xylylene diisocyanate (XDI) 49.3 g and 0.01 parts by weight of dibutyltin chloride as a catalyst were mixed to obtain a uniform solution. Subsequently, this was filtered with a filter having a pore size of 0.5 μm. The filtrate was poured into a 2.5 mm thick flat lens mold, and heated and polymerized and cured in an oven from 30 ° C. to 130 ° C. over 26 hours to produce a lens. The lens obtained by demolding had good transparency and surface condition.

Example 2
Prepolymer (1) 4.7 g, 1,2,6,7-tetramercapto-4-thiaheptane (TMTH) 16.5 g, pentaerythritol tetrakis (3-mercaptopropionate) (4TP) 28.0 g, 1, After mixing 40.9 g of 3-xylylene diisocyanate (XDI) and 0.01 part by weight of dibutyltin chloride as a catalyst, a uniform solution was obtained. Subsequently, this was filtered with a filter having a pore size of 0.5 μm. The filtrate was poured into a 2.5 mm thick flat lens mold, and heated and polymerized and cured in an oven from 30 ° C. to 130 ° C. over 26 hours to produce a lens. The lens obtained by demolding had good transparency and surface condition.

  The obtained lens was heated at 120 ° C. for 30 minutes and then allowed to cool at room temperature. The lens was ultrasonically washed in a 10% NaOH aqueous solution at 50 ° C. and then ultrasonically washed twice in ion-exchanged water. The washed lens was vacuum dried at room temperature for 24 hours.

  A coating solution for forming a hard coat film was prepared by the method described in JP-A No. 11-172152, page 6, column 9, line 42 to page 6, column 10, line 34. Prepare a matrix-forming component obtained by hydrolyzing iron oxide, titanium oxide composite oxide sol and γ-glycidoxypropyltrimethoxysilane, and mix these two liquids with aluminum acetylacetonate for hard coat film formation A coating solution was obtained.

  The cleaned and dried lens was immersed in the coating solution, then pulled up at a pulling rate of 80 mm / min, dried at 90 ° C. for 18 minutes, and heated and cured at 104 ° C. for 120 minutes to form a hard coat film.

  The refractive index, Abbe number, impact resistance, color tone and heat resistance of the lens thus obtained were measured. The results are shown in Table 1.

Examples 2-5, Comparative Examples 1-2
A lens was prepared and evaluated in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 1. The evaluation results are shown in Table 1.

ＴＭＴＨ：１，２，６，７−テトラメルカプト−４−チアヘプタン
４ＴＰ：ペンタエリスリトールテトラキスチオグリコレート
ＰＣＬ：ポリカプトラクトンジオール（ダイセル化学工業社製 商品名プラクセル）
ＸＤＩ：１，３−キシリレンジイソシアネート
ＢＩＣ：１，３−ビスイソシアナートメチルシクロヘキサン

TMTH: 1,2,6,7-tetramercapto-4-thiaheptane 4TP: pentaerythritol tetrakisthioglycolate PCL: polycaptolactone diol (trade name Plaxel manufactured by Daicel Chemical Industries)
XDI: 1,3-xylylene diisocyanate BIC: 1,3-bisisocyanatomethylcyclohexane

Claims (9)

A polymerizable composition comprising the following components (A), (B), and (C).
(A) Compound having two or more mercapto groups (excluding compounds having amino group or organosilyl group)
(B) Aliphatic linear oligomer (C) isocyanate compound and / or thioisocyanate compound which is a polyol compound and / or a polythiol compound having two or more OH groups or SH groups having a number average molecular weight of 200 or more and less than 5000 per molecule. A polymerizable composition comprising the following components (A) and (B1).
(A) Compound having two or more mercapto groups (excluding compounds having amino group or organosilyl group)
(B1) below the component (B) and (C) a polyurethane obtained a pre-reacted component prepolymers and / or polythiourethane prepolymer
(B) An aliphatic linear oligomer which is a polyol compound and / or a polythiol compound having two or more OH groups or SH groups having a number average molecular weight of 200 or more and less than 5000 per molecule.
(C) Isocyanate compound and / or thioisocyanate compound   The polymerizable composition according to claim 1 or 2, further comprising a thermosetting catalyst.   The component (B) is at least one polyol compound selected from the group consisting of a polyol compound composed of polyether polyol, polyester polyol, polylactone polyol, polycarbonate polyol, and a block copolymer or random copolymer of the polyol compound. The polymerizable composition according to claim 1 or 2. The polymerizable composition according to claim 1, comprising 5% to 50% by weight of the component (B).   A resin obtained by polymerizing and curing the composition according to claim 1.   A method for obtaining a resin by polymerizing and curing the composition according to claim 1.   An optical material obtained by polymerizing and curing the composition according to claim 1.   An optical lens made of the optical material according to claim 8.