JP2019156952A - Optical material composition and use thereof - Google Patents

Abstract

To provide an optical material composition that can yield a formed body having a high Abbe number and a high refractive index and further having an excellent transparency and dimensional stability.SOLUTION: The composition for optical material of the present invention comprises (A) an epoxy group-containing compound and (B) a thiol compound, and in which the thiol compound (B) is at least one of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis (mercaptomethylthio)ethyl)-1,3-dithietane, and 2,5-bis(mercaptomethyl)-1,4-dithiane.SELECTED DRAWING: None

Description

  The present invention relates to a composition for optical materials and use thereof.

  Plastic lenses are rapidly spreading as optical materials such as eyeglass lenses and camera lenses because they are lighter and harder to break than inorganic lenses and can be dyed. Various resins for optical materials have been developed and used so far. An epoxy resin is mentioned as such a resin for optical materials.

  Patent Document 1 describes a cured epoxy resin obtained by curing a bisphenol type epoxy resin and / or an alicyclic epoxy resin with an acid anhydride. And it is described that the refractive index of the obtained lens can be adjusted in the range of 1.50 to 1.60.

  Patent Document 2 describes a lens obtained by curing a liquid epoxy resin composition in which a curing agent, a curing accelerator, and a stabilizer are blended with a bisphenol A type epoxy resin. The document describes that the obtained lens is excellent in refractive index, dimensional stability, and the like.

  Patent Document 3 describes a method for producing an epoxy resin-based lens, wherein an internal mold release agent is added to a mixture of an epoxide compound containing an unsaturated bond and a hydroxy compound, and cast polymerization is performed. Yes. This document describes that according to this method, a lens having excellent surface accuracy can be obtained.

  Patent Document 4 casts a mixture of an epoxy resin and a compound having two or more functional groups capable of reacting with the epoxy resin (excluding compounds having only a mercapto group as a functional group) and an internal mold release agent. A lens obtained by polymerization is described. This document describes that according to this method, a lens having excellent surface accuracy can be obtained.

  Patent Document 5 describes an epoxy resin composition for sealing an optical semiconductor element containing an epoxy compound, an acid anhydride, polyorganosiloxane, and thiol. Examples of thiols include tetraethylene glycol-bis-3-mercaptopropionate and the like, which are added to improve adhesion to metals.

JP 59-199713 A JP 59-22001 JP-A-1-213602 JP-A-3-81320 JP 2009-91438 A

  However, the techniques described in these documents have room for improvement in the following points.

  A resin molded body made of an epoxy compound has properties suitable for lenses with high transparency and high dimensional stability, but has a problem that it is difficult to achieve both a high Abbe number and a high refractive index. It has not been widely used as a resin.

  For example, when an epoxy compound having an aromatic ring is used, a resin having a high refractive index can be obtained, but there is a problem that the Abbe number of the resin is lowered. On the other hand, when an aliphatic epoxy compound is used, the high Abbe number is Although it can be realized, there is a problem that the refractive index of the resin is lowered.

In view of the above problems, the present inventors have studied and found that these characteristics can be improved by using a predetermined thiol compound as a curing agent. That is, when an epoxy compound having an aromatic ring and a predetermined thiol compound are used in combination, a resin having a high refractive index can be obtained while suppressing a decrease in the Abbe number, and an aliphatic or alicyclic epoxy compound is obtained. And a predetermined thiol compound in combination, it was found that a high refractive index of the resin can be realized while minimizing the decrease in the Abbe number.
Furthermore, it discovered that the heat resistance of an epoxy resin improved by using an acid anhydride together.

The present invention can be described below.
[1] (A) an epoxy group-containing compound;
(B) a thiol compound,
The thiol compound (B) is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 1,1, 3,3-tetrakis (mercaptomethylthio) propane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-dithietane, and 2 , 5-bis (mercaptomethyl) -1,4-dithiane, a composition for optical materials.
[2] The composition for optical materials according to [1], further comprising (C) an acid anhydride.
[3] The composition for optical materials according to [1] or [2], wherein the epoxy group-containing compound (A) has a viscosity at 25 ° C. of 1 to 30,000 mPa · s.
[4] The composition for optical materials according to any one of [1] to [3], wherein the epoxy group-containing compound (A) has two or more of either a glycidyl group or an epoxycyclohexyl group.
[5] The epoxy group-containing compound (A) is (hydrogenated) bisphenol A type epoxy resin, (hydrogenated) bisphenol F type epoxy resin, 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate The composition for optical materials according to any one of [1] to [4], which is at least one selected from the group consisting of:
[6] Acid anhydride (C) is methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride, bicyclo [2.2.1] heptane-2, The composition for optical materials according to [2], which is at least one selected from 3-dicarboxylic acid anhydride and phthalic anhydride.
[7] A molded product obtained by curing the composition for optical materials according to any one of [1] to [6].
[8] An optical material comprising the molded article according to [7].
[9] A lens made of the optical material according to [8].

According to the composition for optical materials of the present invention, it is possible to obtain an epoxy resin molded body having a high Abbe number and a high refractive index, and further excellent in transparency and dimensional stability.
According to the present invention, a composition for an optical material useful as a high refractive index eyeglass lens material can be provided.

Embodiments of the present invention will be described below.
The composition for an optical material of the present embodiment includes (A) an epoxy group-containing compound,
(B) a thiol compound.

[Epoxy group-containing compound (A)]
In this embodiment, various compounds can be used as the epoxy group-containing compound (A). From the viewpoint of the effect of the present invention, the viscosity at 25 ° C. is 1 to 30,000 mPa · s, preferably 5 to 15 It is preferable to use a compound having a viscosity of 1,000 mPa · s.

  Specifically, as the epoxy group-containing compound (A), a compound having two or more of either a glycidyl group represented by the following formula (1) or an epoxycyclohexyl group represented by the following formula (2) is used. Can do.

In the formula, * indicates a bond.
The epoxy group-containing compound (A) has two or more of any substituents, and when used in combination with a predetermined thiol compound (B) described later, has a high Abbe number and a high refractive index, and further has transparency and An epoxy resin molded article having excellent dimensional stability can be obtained.

  Examples of the epoxy group-containing compound (A) include aliphatic glycidyl ether type epoxy compounds, hydrogenated epoxy compounds, alicyclic epoxy compounds, aromatic epoxy compounds, glycidyl ester compounds, glycidyl amine compounds, and heterocyclic epoxies. A compound etc. can be mentioned, These 1 type (s) or 2 or more types can be used in combination.

  Specific examples of the aliphatic glycidyl ether type epoxy resin include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (PEG), propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and polypropylene. Condensation of epihalohydrin with glycol (PPG), glycerol, diglycerol, tetraglycerol, polyglycerol, trimethylolpropane and its multimers, pentaerythritol and its multimers, mono / polysaccharides such as glucose, fructose, lactose, maltose, etc. Examples thereof include those obtained by the reaction, glycidyl ethers having an oxyalkylene skeleton, and the like.

  As the hydrogenated epoxy compound, a polyfunctional glycidyl ether compound having a glycidyl ether group directly or indirectly bonded to a saturated aliphatic cyclic hydrocarbon skeleton (hereinafter also simply referred to as “polyfunctional glycidyl ether compound”) is preferable. It is. Specifically, a hydrogenated product of an aromatic polyfunctional glycidyl ether compound such as a bisphenol-type epoxy resin is suitable, and one or more of these can be used in combination. More preferred are hydrogenated bisphenol A type epoxy resins, hydrogenated bisphenol S type epoxy resins, hydrogenated bisphenol F type epoxy resins, and the like. More preferred are hydrogenated bisphenol A type epoxy resins and hydrogenated bisphenol F type epoxy resins.

  Examples of the alicyclic epoxy compound include a polyfunctional alicyclic epoxy compound having an alicyclic epoxy group (hereinafter also simply referred to as “polyfunctional alicyclic epoxy compound”). Specifically, an epoxy resin having an epoxycyclohexane skeleton (epoxycyclohexyl group), an epoxy resin in which an epoxy group is added directly or via a hydrocarbon group to a cyclic aliphatic hydrocarbon, and the like are suitable. Two or more kinds can be used in combination. More preferably, it is an epoxy resin having an epoxycyclohexane skeleton. Examples of the epoxy resin having an epoxycyclohexane skeleton include 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Celoxide 2021P, manufactured by Daicel), ε-caprolactone-modified 3 ′, 4′-epoxycyclohexyl. Examples include methyl 3,4-epoxycyclohexanecarboxylate (Celoxide 2081, manufactured by Daicel Corporation), bis- (3,4-epoxycyclohexyl) adipate, and the like.

  As an alicyclic epoxy compound other than the epoxy resin having the epoxycyclohexane skeleton, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol (EHPE) -3150 (manufactured by Daicel Corporation).

  Examples of the aromatic epoxy compound include glycidyl compounds having an aromatic ring conjugated system such as a bisphenol skeleton, a fluorene skeleton, a biphenyl skeleton, a naphthalene ring, and an anthracene ring, and one or more of these can be used in combination. . An epoxy and / or glycidyl compound (fluorene compound) having a bisphenol skeleton is preferable.

  Specific examples of the aromatic epoxy compound include those obtained by condensation reaction of bisphenols such as bisphenol A, bisphenol F, bisphenol S, and fluorene bisphenol with epihalohydrin, fluorene epoxy (manufactured by Osaka Gas Chemical Co., Ltd.) oncoat EX -1020 or ogsol EG210, fluorene epoxy (Osaka Gas Chemical Co., Ltd.) on-coat EX-1010 or ogsol PG, epibis type glycidyl ether type epoxy resin, high molecular weight epibis type glycidyl ether type epoxy resin, novolak aralkyl type glycidyl ether Type epoxy resin, phenyl glycidyl ether and the like. As the high molecular weight epibis type glycidyl ether type epoxy resin, those obtained by further reacting the above epibis type glycidyl ether type epoxy resin with bisphenols such as the above bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, etc. 1 type or 2 types or more can be used in combination. Bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenyl glycidyl ether are preferable.

  As the above-mentioned novolak aralkyl type glycidyl ether type epoxy resin, phenol, cresol, xylenol, naphthol, resorcin, catechol, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol and other phenols and formaldehyde, acetoaldehyde, propionaldehyde, Polyhydric phenols obtained by condensation reaction of benzaldehyde, hydroxybenzaldehyde, salicylaldehyde, dicyclopentadiene, terpene, coumarin, paraxylylene glycol dimethyl ether, dichloroparaxylylene, bishydroxymethylbiphenyl, etc. are further condensed with epihalohydrin. What is obtained by this is suitable.

  As the aromatic epoxy compound, tetramethylbiphenol, tetramethylbisphenol F, hydroquinone, naphthalene diol and the like, and an aromatic crystalline epoxy resin obtained by a condensation reaction of epihalohydrin, and the above bisphenols and tetramethylbiphenol, A high molecular weight polymer of an aromatic crystalline epoxy resin obtained by addition reaction of tetramethylbisphenol F, hydroquinone, naphthalene diol, or the like can also be used.

  Examples of glycidyl ester compounds include diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, diglycidyl methyl hexahydrophthalate, dichroic acid glycidyl ester, modified glycidyl ester dichroic acid, allocotic diglycidyl ester, cycloaliphatic Examples thereof include glycidyl ester type epoxy resins such as fattic diglycidyl ester.

  Examples of glycidylamine compounds include tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, diglycidylaniline, diglycidyltoluidine, tetraglycidylmetaxylenediamine, diglycidyltribromoaniline, tetraglycidylbis. Examples thereof include glycidylamine type epoxy resins such as aminomethylcyclohexane.

  Examples of the heterocyclic epoxy resin include isocyanurate type epoxy resins such as triglycidyl isocyanurate, and hydantoin type epoxy resins such as diglycidyl hydantoin and glycidyl glycidoxyalkylhydantoin.

  In the present embodiment, from the viewpoint of the effect of the present invention, the epoxy group-containing compound (A) is a (hydrogenated) bisphenol A type epoxy resin, a (hydrogenated) bisphenol F type epoxy resin, or a 3 ′, 4′-epoxy. It is preferably at least one selected from cyclohexylmethyl-3,4-epoxycyclohexanecarboxylate.

[Thiol Compound (B)]
The thiol compound (B) is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 1,1, 3,3-tetrakis (mercaptomethylthio) propane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-dithietane, and 2 , 5-bis (mercaptomethyl) -1,4-dithiane.

  In the present embodiment, from the viewpoint of the effect of the present invention, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9 -Trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-tri It is preferably at least one selected from thiaundecane.

  By using these thiol compounds, it is possible to obtain an epoxy resin molded body having a high Abbe number and a high refractive index, and further excellent in transparency and dimensional stability.

  From the viewpoint of the effect of the present invention, the thiol compound (B) is 5 to 75% by weight, preferably 15 to 70% by weight, and more preferably 30 to 65% by weight with respect to 100% by weight of the epoxy group-containing compound (A). % Can be included.

[Acid anhydride (C)]
The composition for optical materials of this embodiment can further contain an acid anhydride (C). By including the acid anhydride (C), an epoxy resin molded body having a high Abbe number and a high refractive index, excellent in transparency and dimensional stability, and excellent in heat resistance can be obtained.

  Examples of the acid anhydride (C) include succinic anhydride, phthalic anhydride, maleic anhydride, tetrabromophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, alkyl Methyltetrahydrophthalic anhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride, bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride, trimellitic anhydride , Succinic anhydride, pyromellitic anhydride, methyl nadic anhydride, anhydrous nadic acid, glutaric anhydride, dimethyl glutaric anhydride, diethyl glutaric anhydride, methyl hymic anhydride, and the like. These may be used alone or in combination of two or more. The acid anhydride preferably has a molecular weight of about 140 to 200, and is preferably a colorless or light yellow acid anhydride.

  In the present embodiment, from the viewpoint of the effect of the present invention, the acid anhydride (C) is methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid. It is preferably at least one selected from an acid anhydride, bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride, and phthalic anhydride.

  The acid anhydride (C) can be contained in an amount of 5 to 40% by weight, preferably 10 to 30% by weight, based on 100% by weight of the total of (A) and (B).

[Other ingredients]
The composition for optical materials of the present embodiment can contain other reactive compounds as long as the effects of the present invention are not impaired, and further includes a curing accelerator, an ultraviolet absorber, a photochromic dye, a photochromic dye, and a resin modification. It may contain quality agents, internal mold release agents, antioxidants, non-light-controlling pigments and dyes, nanometer-sized organic or inorganic particles, and the like.

  Examples of other reactive compounds include (thio) carboxylic acid compounds, iso (thio) cyanate compounds, alcohol compounds, amine compounds, and thioepoxy compounds.

(Thio) carboxylic acid compounds include succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, orthophthalic acid, phthalic anhydride, tetrahydrophthalic acid, hexahydrophthalic acid, naphthalenedicarboxylic acid , Biphenyl dicarboxylic acid, dimer acid, trimellitic acid, pyromellitic acid, ε-caprolactone, thiobenzoic acid, dithiobenzoic acid, glycolic acid, thioglycolic acid and the like.
The polymerization reactive compounds may be used alone or in combination of two or more.

Iso (thio) cyanate compounds include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate. Aliphatic polyisocyanate compounds such as lysine diisocyanatomethyl ester, lysine triisocyanate, xylylene diisocyanate;
Isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, dicyclohexyldimethylmethane isocyanate, 2,5-bis (isocyanatomethyl) bicyclo- [2.2.1] -heptane, 2,6-bis (isocyanato) Methyl) bicyclo- [2.2.1] -heptane, 3,8-bis (isocyanatomethyl) tricyclodecane, 3,9-bis (isocyanatomethyl) tricyclodecane, 4,8-bis (isocyanato) Alicyclic polyisocyanate compounds such as methyl) tricyclodecane and 4,9-bis (isocyanatomethyl) tricyclodecane;
Aromatic polyisocyanate compounds such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, diphenyl sulfide-4,4-diisocyanate, phenylene diisocyanate;
2,5-diisocyanatothiophene, 2,5-bis (isocyanatomethyl) thiophene, 2,5-diisocyanatotetrahydrothiophene, 2,5-bis (isocyanatomethyl) tetrahydrothiophene, 3,4-bis ( Isocyanatomethyl) tetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, 2,5-bis (isocyanatomethyl) -1,4-dithiane, 4,5-diisocyanato-1,3-dithiolane, 4, Heterocyclic polyisocyanate compounds such as 5-bis (isocyanatomethyl) -1,3-dithiolane;
Hexamethylene diisothiocyanate, lysine diisothiocyanate methyl ester, lysine triisothiocyanate, m-xylylene diisothiocyanate, bis (isothiocyanatomethyl) sulfide, bis (isothiocyanatoethyl) sulfide, bis (isothiocyanatoethyl) Aliphatic polyisothiocyanate compounds such as disulfides;
Isophorone diisothiocyanate, bis (isothiocyanatomethyl) cyclohexane, dicyclohexylmethane diisothiocyanate, cyclohexane diisothiocyanate, methylcyclohexane diisothiocyanate, 2,5-bis (isothiocyanatomethyl) bicyclo- [2.2.1 ] -Heptane, 2,6-bis (isothiocyanatomethyl) bicyclo- [2.2.1] -heptane, 3,8-bis (isothiocyanatomethyl) tricyclodecane, 3,9-bis (isothiocyana) Alicyclic polyisothiocyanate compounds such as tomethyl) tricyclodecane, 4,8-bis (isothiocyanatomethyl) tricyclodecane, 4,9-bis (isothiocyanatomethyl) tricyclodecane;
Aromatic polyisothiocyanate compounds such as tolylene diisothiocyanate, 4,4-diphenylmethane diisothiocyanate, diphenyl disulfide-4,4-diisothiocyanate;
2,5-diisothiocyanatothiophene, 2,5-bis (isothiocyanatomethyl) thiophene, 2,5-isothiocyanatotetrahydrothiophene, 2,5-bis (isothiocyanatomethyl) tetrahydrothiophene, 3,4 -Bis (isothiocyanatomethyl) tetrahydrothiophene, 2,5-diisothiocyanato-1,4-dithiane, 2,5-bis (isothiocyanatomethyl) -1,4-dithiane, 4,5-diisothiene Examples thereof include sulfur-containing heterocyclic polyisothiocyanate compounds such as oocyanato-1,3-dithiolane and 4,5-bis (isothiocyanatomethyl) -1,3-dithiolane.

Examples of the alcohol compound include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, neopentyl glycol, glycerin, trimethylol ethane, trimethylol propane, ditrimethylol propane, butane triol, 1,2- Methyl glucoside, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, erythritol, threitol, ribitol, arabinitol, xylitol, allitol, mannitol, dolitol, iditol, glycol, inositol, hexanetriol, triglycerose, diglycerol, triethylene Glycol, polyethylene glycol, polyp Propylene glycol, tris (2-hydroxyethyl) isocyanurate, cyclobutanediol, cyclopentane diol, cyclohexane diol, cycloheptane diol, cyclooctane diol, cyclohexane dimethanol, hydroxypropyl cyclohexanol, tricyclo [5.2.1.0 ^{2 , 6} ] decane-dimethanol, bicyclo [4.3.0] -nonanediol, dicyclohexanediol, tricyclo [5,3,1,1] dodecanediol, bicyclo [4.3.0] nonanedimethanol, tricyclo [5.3.1.1] dodecanediethanol, hydroxypropyltricyclo [5.3.1.1] dodecanol, spiro [3.4] octanediol, butylcyclohexanediol, 1,1'-bicyclohexylidene di Lumpur, cyclohexane triol, maltitol, aliphatic polyols such as lactose;
Dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol, biphenyltetraol, pyrogallol, (hydroxynaphthyl) pyrogallol, trihydroxyphenanthrene, bisphenol A, bisphenol F, xylylene glycol, di (2-hydroxyethoxy) Aromatic polyols such as benzene, bisphenol A-bis- (2-hydroxyethyl ether), tetrabromobisphenol A, tetrabromobisphenol A-bis- (2-hydroxyethyl ether);
Halogenated polyols such as dibromoneopentyl glycol;
High molecular polyols such as epoxy resins can be mentioned. In the present embodiment, at least one selected from these can be used in combination.

Other alcohol compounds include oxalic acid, glutamic acid, adipic acid, acetic acid, propionic acid, cyclohexanecarboxylic acid, β-oxocyclohexanepropionic acid, dimer acid, phthalic acid, isophthalic acid, salicylic acid, 3-bromopropionic acid, 2 A condensation reaction product of an organic acid such as bromoglycol, dicarboxycyclohexane, pyromellitic acid, butanetetracarboxylic acid, bromophthalic acid and the above polyol;
An addition reaction product of the alcohol compound with an alkylene oxide such as ethylene oxide or propylene oxide;
An addition reaction product of an alkylene polyamine and an alkylene oxide such as ethylene oxide or propylene oxide;
Bis- [4- (hydroxyethoxy) phenyl] sulfide, bis- [4- (2-hydroxypropoxy) phenyl] sulfide, bis- [4- (2,3-dihydroxypropoxy) phenyl] sulfide, bis- [4- (4-Hydroxycyclohexyloxy) phenyl] sulfide, bis- [2-methyl-4- (hydroxyethoxy) -6-butylphenyl] sulfide and these compounds have an average of 3 or less molecules of ethylene oxide and / or propylene oxide per hydroxyl group. Added compounds;
Di- (2-hydroxyethyl) sulfide, 1,2-bis- (2-hydroxyethylmercapto) ethane, bis (2-hydroxyethyl) disulfide, 1,4-dithian-2,5-diol, bis (2, 3-dihydroxypropyl) sulfide, tetrakis (4-hydroxy-2-thiabutyl) methane, bis (4-hydroxyphenyl) sulfone (bisphenol S), tetrabromobisphenol S, tetramethylbisphenol S, 4,4′-thiobis (6 And polyols containing sulfur atoms such as -tert-butyl-3-methylphenol) and 1,3-bis (2-hydroxyethylthioethyl) -cyclohexane. In the present embodiment, at least one selected from these can be used in combination.

Examples of amine compounds include ethylenediamine, 1,2-, or 1,3-diaminopropane, 1,2-, 1,3-, or 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diamino. Hexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,10-diaminodecane, 1,2-, 1,3- or 1,4-diaminocyclohexane, o-, m- or p-diamino Benzene, 3,4- or 4,4'-diaminobenzophenone, 3,4- or 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'- Or 4,4′-diaminodiphenylsulfone, 2,7-diaminofluorene, 1,5-, 1,8-, or 2,3-dia Nonaphthalene, 2,3-, 2,6-, or 3,4-diaminopyridine, 2,4-, or 2,6-diaminotoluene, m-, or p-xylylenediamine, isophoronediamine, diaminomethylbicyclo Heptane, 1,3-, or 1,4-diaminomethylcyclohexane, 2-, or 4-aminopiperidine, 2-, or 4-aminomethylpiperidine, 2-, or 4-aminoethylpiperidine, N-aminoethylmorpholine Primary polyamine compounds such as N-aminopropylmorpholine;
Diethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine, diisobutylamine, di-n-pentylamine, di-3-pentylamine, dihexylamine, dioctylamine, di (2-ethylhexyl) amine, methyl Hexylamine, diallylamine, N-methylallylamine, piperidine, pyrrolidine, diphenylamine, N-methylamine, N-ethylamine, dibenzylamine, N-methylbenzylamine, N-ethylbenzylamine, dicyclohexylamine, N-methylaniline, N -Monofunctional secondary amine compounds such as ethylaniline, dinaphthylamine, 1-methylpiperazine, morpholine;
N, N′-dimethylethylenediamine, N, N′-dimethyl-1,2-diaminopropane, N, N′-dimethyl-1,3-diaminopropane, N, N′-dimethyl-1,2-diaminobutane, N, N′-dimethyl-1,3-diaminobutane, N, N′-dimethyl-1,4-diaminobutane, N, N′-dimethyl-1,5-diaminopentane, N, N′-dimethyl-1 , 6-Diaminohexane, N, N′-dimethyl-1,7-diaminoheptane, N, N′-diethylethylenediamine, N, N′-diethyl-1,2-diaminopropane, N, N′-diethyl-1 , 3-diaminopropane, N, N′-diethyl-1,2-diaminobutane, N, N′-diethyl-1,3-diaminobutane, N, N′-diethyl-1,4-diaminobutane, N, N'-diethyl-1,5-di Aminopentane, N, N′-diethyl-1,6-diaminohexane, N, N′-diethyl-1,7-diaminoheptane, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 2,6-dimethyl Piperazine, homopiperazine, 1,1-di- (4-piperidyl) methane, 1,2-di- (4-piperidyl) ethane, 1,3-di- (4-piperidyl) propane, 1,4-di- Secondary polyamine compounds such as (4-piperidyl) butane and tetramethylguanidine;

As a thioepoxy compound,
Bis (2,3-epoxypropyl) sulfide, bis (2,3-epoxypropyl) disulfide, bis (2,3-epoxypropylthio) methane, 1,2-bis (2,3-epoxypropylthio) ethane, 1,2-bis (2,3-epoxypropylthio) propane, 1,3-bis (2,3-epoxypropylthio) propane, 1,3-bis (2,3-epoxypropylthio) -2-methyl Propane, 1,4-bis (2,3-epoxypropylthio) butane, 1,4-bis (2,3-epoxypropylthio) -2-methylbutane, 1,3-bis (2,3-epoxypropylthio) ) Butane, 1,5-bis (2,3-epoxypropylthio) pentane, 1,5-bis (2,3-epoxypropylthio) -2-methylpentane, 1,5-bis (2, -Epoxypropylthio) -3-thiapentane, 1,6-bis (2,3-epoxypropylthio) hexane, 1,6-bis (2,3-epoxypropylthio) -2-methylhexane, 3,8- Bis (2,3-epoxypropylthio) -3,6-dithiaoctane, 1,2,3-tris (2,3-epoxypropylthio) propane, 2,2-bis (2,3-epoxypropylthio)- 1,3-bis (2,3-epoxypropylthiomethyl) propane, 2,2-bis (2,3-epoxypropylthiomethyl) -1- (2,3-epoxypropylthio) butane, 1,5- Bis (2,3-epoxypropylthio) -2- (2,3-epoxypropylthiomethyl) -3-thiapentane, 1,5-bis (2,3-epoxypropylthio) -2,4-bis ( , 3-epoxypropylthiomethyl) -3-thiapentane, 1- (2,3-epoxypropylthio) -2,2-bis (2,3-epoxypropylthiomethyl) -4-thiahexane, 1,5,6 -Tris (2,3-epoxypropylthio) -4- (2,3-epoxypropylthiomethyl) -3-thiahexane, 1,8-bis (2,3-epoxypropylthio) -4- (2,3 -Epoxypropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epoxypropylthio) -4,5-bis (2,3-epoxypropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epoxypropylthio) -4,4-bis (2,3-epoxypropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epoxypropyl) (Lopylthio) -2,5-bis (2,3-epoxypropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epoxypropylthio) -2,4,5-tris (2, 3-epoxypropylthiomethyl) -3,6-dithiaoctane, 1,1,1-tris [[2- (2,3-epoxypropylthio) ethyl] thiomethyl] -2- (2,3-epoxypropylthio) Ethane, 1,1,2,2-tetrakis [[2- (2,3-epoxypropylthio) ethyl] thiomethyl] ethane, 1,11-bis (2,3-epoxypropylthio) -4,8-bis (2,3-epoxypropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epoxypropylthio) -4,7-bis (2,3-epoxypropylthiomethyl) ) 3,6,9-trithiaundecane, 1,11-bis (2,3-epoxypropylthio) -5,7-bis (2,3-epoxypropylthiomethyl) -3,6,9-trithiaundecane Chain aliphatic 2,3-epoxypropylthio compounds such as
1,3-bis (2,3-epoxypropylthio) cyclohexane, 1,4-bis (2,3-epoxypropylthio) cyclohexane, 1,3-bis (2,3-epoxypropylthiomethyl) cyclohexane, 1 , 4-bis (2,3-epoxypropylthiomethyl) cyclohexane, 2,5-bis (2,3-epoxypropylthiomethyl) -1,4-dithiane, 2,5-bis [[2- (2, Cyclic epoxy such as 3-epoxypropylthio) ethyl] thiomethyl] -1,4-dithiane, 2,5-bis (2,3-epoxypropylthiomethyl) -2,5-dimethyl-1,4-dithiane 2,3-epoxypropylthio compound;
1,2-bis (2,3-epoxypropylthio) benzene, 1,3-bis (2,3-epoxypropylthio) benzene, 1,4-bis (2,3-epoxypropylthio) benzene, 1, 2-bis (2,3-epoxypropylthiomethyl) benzene, 1,3-bis (2,3-epoxypropylthiomethyl) benzene, 1,4-bis (2,3-epoxypropylthiomethyl) benzene, bis [4- (2,3-epoxypropylthio) phenyl] methane, 2,2-bis [4- (2,3-epoxypropylthio) phenyl] propane, bis [4- (2,3-epoxypropylthio) Aromatic] such as phenyl] sulfide, bis [4- (2,3-epoxypropylthio) phenyl] sulfone, 4,4′-bis (2,3-epoxypropylthio) biphenyl Examples include 2,3-epoxypropylthio compounds.

  Curing accelerators include tertiary amines and salts thereof, quaternary ammonium salts, heterocyclic amines such as imidazoles and diazabicyclo compounds and salts thereof, organic carboxylates thereof, organic carboxylate metal salts, metal- Organic chelate compounds, aromatic sulfonium salts, organic phosphine compounds, phosphonium compounds, cationic curing catalysts, and the like can be used.

Specific examples of the curing accelerator other than the cationic curing catalyst include 2-heptadecylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 4-methylimidazole, 4 -Ethylimidazole, 2-phenyl-4-hydroxymethylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl- 4,5-dihydroxymethylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4 -Mechi Imidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-Ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2 '-Ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2 -Imidazoles such as phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenylimidazoline;
1,8-diazabicyclo [5,4,0] undecene-7 (DBU), 1,5-diazabicyclo [4,3,0] nonene, 5,6-dibutylamino-1,8-diazabicyclo [5,4 0] diazabicyclo compounds such as undecene-7 and salts thereof;
Triethylamine, triethylenediamine, benzyldimethylamine, α-methylbenzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, N, N-dimethylcyclohexylamine, N, N-dicyclohexylmethylamine, etc. Secondary amines;
Tetrabutylammonium chloride, tetrabutylammonium bromide, tetraethylammonium bromide, benzyltriethylammonium chloride, benzalkonium chloride, benzyldimethylphenylammonium chloride, benzyltrimethylammonium chloride, benzyltributylammonium chloride, dodecyltrimethylammonium chloride, decyltrimethylammonium chloride, Di-n-alkyldimethylammonium chloride, didodecyldimethylammonium chloride, hexadecyltrimethylammonium chloride, (2-methoxyethoxymethyl) triethylammonium chloride, triethylmethylammonium chloride, n-octyltrimethylammonium chloride, trimethylstearylammonium Chloride, tetraethylammonium chloride, trimethyltetradecylammonium chloride, methyltri-n-octylammonium chloride, tetraamylammonium chloride, tetrapropylammonium chloride, benzyltriethylammonium bromide, benzyltributylammonium bromide, benzyltrimethylammonium bromide, benzyldodecyldimethylammonium bromide Ethyl hexadecyl dimethyl ammonium bromide, decyl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide, dilauryl dimethyl ammonium bromide, dimethyl dioctadecyl ammonium bromide, dimethyl dipalmityl ammonium bromide, dimethyl dimyristyl ammonium bromide, dide Dimethylammonium bromide, dimethyldioctylammonium bromide, hexadecyltrimethylammonium bromide, hexyltrimethylammonium bromide, hexyldimethyloctylammonium bromide, heptadecyltrimethylammonium bromide, n-octyltrimethylammonium bromide, trimethylstearylammonium bromide, tetraethylammonium bromide, tetra Propyl ammonium bromide, tetradecyltrimethylammonium bromide, tetra (decyl) ammonium bromide, tetraamylammonium bromide, tetrahexylammonium bromide, tetraheptylammonium bromide, tetra-n-octylammonium bromide, trimethylnonylammonium bromide, tri Ammonium salts such as chill propyl ammonium bromide;
Trimethylphosphine, triethylphosphine, tributylphosphine, triphenylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, methyldiphenylphosphine, dibutylphenylphosphine, tricyclohexylphosphine, bis (diphenylphosphino) methane, 1 , 2-bis (diphenylphosphino) ethane, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium dicyanamide, n-butyltriphenylphosphonium dicyanamide, tetraphenyl Phosphonium bromide, n-butyltriphenylphosphonium bromide, tetrabutylphosphonium bromide Mido, tetrabutylphosphonium chloride, tetrabutylphosphonium decanoate, tetra-n-butylphosphonium-tetraphenylborate, tetra-n-butylphosphonium-o, o-diethylphosphorodithioate, tetra-n-butylphosphonium-tetra Examples thereof include organic phosphine compounds such as fluoroborate, tetraethylphosphonium bromide, phenylphosphine triphenylborane, tributyldodecylphosphonium bromide, tributylhexadecylphosphonium bromide, and tributyl-n-octylphosphonium bromide. These may be used individually by 1 type, and may mix and use 2 or more types.

  The content of the curing accelerator other than the cationic curing catalyst is 0.01 to 100% in terms of solid content (in terms of the amount of the active ingredient not including the solvent) with respect to 100% by mass of the resin composition combined with the organic resin component. 15 mass% is preferable. More preferably, it is 0.05-10.0 mass%, More preferably, it is 0.1-5.0 mass%. If the amount of the catalyst is reduced too much to be less than 0.01% by mass, curing is slow, and if it exceeds 10% by mass, there is a risk of coloring during curing or heating of the molded body.

  The cationic curing catalyst is preferably a thermal acid generator (thermal latent curing catalyst) or a photoacid generator. There is no particular limitation as long as a cationic species that initiates polymerization is generated by heat or light. By using a thermal acid generator, a compound containing a cationic species is excited by heating, a thermal decomposition reaction occurs, and thermal curing proceeds. Further, by using a photoacid generator, a compound containing a cation species is excited by light, a photolysis reaction occurs, and photocuring proceeds.

  The catalyst amount (usage amount) of the cation curing catalyst is 0.01 to 10 in terms of solid content (without solvent and the like, in the amount of active ingredient) with respect to 100% by mass of the resin composition combined with the organic resin component. Mass% is preferred. More preferably, it is 0.05-5.0 mass%, More preferably, it is 0.1-3.0 mass%. If the amount of the catalyst is reduced too much to be less than 0.01% by mass, curing is slow, and if it exceeds 10% by mass, there is a risk of coloring during curing or heating of the molded body.

  When the above heat latent curing catalyst is used, the moisture resistance of the cured product of the resulting resin composition is dramatically improved, and the excellent optical properties of the resin composition are maintained even in harsh usage environments. Therefore, it can be suitably used for the following applications. Usually, if water having a low refractive index is contained in the resin composition or its cured product, it causes turbidity.However, if a heat-latent curing catalyst is used, excellent moisture resistance can be exhibited. It is suppressed and can be suitably used for optical applications such as lenses. Especially in applications such as in-vehicle cameras and bar code readers for home delivery companies, there are concerns over yellowing and deterioration of strength due to prolonged ultraviolet irradiation and high temperature exposure in summer. It is thought that the generation of oxygen radicals is caused by the synergistic effect of exposure to heat rays. By improving moisture resistance, moisture absorption into the resin composition is suppressed, and generation of oxygen radicals due to the synergistic effect of ultraviolet irradiation or heat ray exposure is also suppressed. Excellent heat resistance over time.

The heat latent cation generator is preferably one represented by the following general formula (1).
_{^{(R 1 a R 2 b R}} 3 c R 4 d Z) (AX n) (1)
In formula (1), Z represents at least one element selected from the group consisting of S, Se, Te, P, As, Sb, Bi, O, N, and a halogen element. R ¹ , R ² , R ³ and R ⁴ are the same or different and represent an organic group. a, b, c and d are 0 or a positive number, and the sum of a, b, c and d is equal to the valence of Z. The cation (R ¹ _a R ² _b R ³ _c R ⁴ _d Z) represents an onium salt. A represents a metal element or metalloid (metalloid) which is a central atom of a halide complex, and is composed of B, P, As, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, and Co. It is at least one selected from the group. X represents a halogen element. m is the net charge of the halide complex ion. n is the number of halogen elements in the halide complex ion.

Specific examples of the anion (AX _n ) of the general formula (1) include tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), hexafluoroantimonate (SbF ₆ ⁻ ), hexafluoroarce. Nate (AsF ₆ ⁻ ), hexachloroantimonate (SbCl ₆ ⁻ ) and the like.
Further general formula _AX n (OH) ^- can also be used anion represented by. Other anions include perchlorate ion (ClO ₄ ⁻ ), trifluoromethyl sulfite ion (CF ₃ SO ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ), toluenesulfonate ion, and trinitrobenzenesulfone. An acid ion etc. are mentioned.

  Specific products of the above-described heat-latent cation generator include diazonium salt types: AMERICURE series (manufactured by American Can), ULTRASET series (manufactured by Adeka), WPAG series (manufactured by Wako Pure Chemical Industries), iodonium salt type: UVE series (manufactured by General Electric), FC series (manufactured by 3M), UV9310C (manufactured by GE Toshiba Silicone), Photoinitiator 2074 (manufactured by Rhone-Poulenc), WPI series (manufactured by Wako Pure Chemical Industries), sulfonium salt type: CYRACURE Series (manufactured by Union Carbide), UVI series (manufactured by General Electric), FC series (manufactured by 3M), CD series (manufactured by Satomer), optomer SP series, optomer CP series (manufactured by Adeka) , San-Aid SI series (Sanshin Chemical Industry Co., Ltd.), CI series (manufactured by Nippon Soda Co., Ltd.), WPAG series (manufactured by Wako Pure Chemical Industries, Ltd.), CPI series (manufactured by San-Apro Ltd.), and the like.

  In order to prevent the molded body made of the cured resin in the present embodiment from being deteriorated even when exposed to the outside for a long period of time, an ultraviolet absorber and a hindered amine light stabilizer are further added to the composition in the present embodiment, and the weather resistance is increased. It is desirable that the composition is imparted with properties.

  The ultraviolet absorber is not particularly limited. For example, a benzotriazole ultraviolet absorber, a triazine ultraviolet absorber, a benzophenone ultraviolet absorber, a benzoate ultraviolet absorber, a propanedioic acid ester ultraviolet absorber, or an oxanilide type. Various ultraviolet absorbers such as an ultraviolet absorber can be used.

  Specifically, for example, 2- (2H-benzotriazol-2-yl) -4-methyl-6- (3,4,5,6-tetrahydrophthalibidylmethyl) phenol, 2- (2H-benzotriazole -2-yl) -p-cresol, 2- (2H-benzotriazol-2-yl) -4-tert-butylphenol, 2- (2H-benzotriazol-2-yl) -4,6-di-tert- Butylphenol, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -4- (1, 1,3,3-tetramethylbutyl) -6- (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -4- (3-one-4 Oxa-dodecyl) -6-tert-butyl-phenol, 2- {5-chloro (2H) -benzotriazol-2-yl} -4- (3-one-4-oxa-dodecyl) -6-tert-butyl -Phenol, 2- {5-chloro (2H) -benzotriazol-2-yl} -4-methyl-6-tert-butyl-phenol, 2- (2H-benzotriazol-2-yl) -4,6- Di-tert-pentylphenol, 2- {5-chloro (2H) -benzotriazol-2-yl} -4,6-di-tert-butylphenol, 2- (2H-benzotriazol-2-yl) -4- tert-octylphenol, 2- (2H-benzotriazol-2-yl) -4-methyl-6-n-dodecylphenol, 3- [3-tert-butyl-5 (5-Chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] octyl propionate, 3- [3-tert-butyl-5- (5-chloro-2H-benzotriazol-2-yl)- 4-hydroxyphenyl] propionate 2-ethylhexyl, methyl-3- {3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl} propionate / polyethylene glycol 300 reaction product, Trade name Biosorb 583 (manufactured by Kyodo Yakuhin Co., Ltd.), trade name Tinuvin 326 (manufactured by BASF), trade name Tinuvin 384-2 (manufactured by BASF), trade name Tinuvin PS (manufactured by BASF), trade name Seasorb 706 (Sipro Kasei Co., Ltd.) Company name), product name EVERSORB109 (Everlight company) Benzotriazole ultraviolet absorbers; 2- (4-phenoxy-2-hydroxy-phenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-oxa-hexadecyloxy) ) -4,6-di (2,4-dimethyl-phenyl) -1,3,5-triazine, 2- (2-hydroxy-4-oxa-heptadecyloxy) -4,6-di (2,4-dimethyl) -Phenyl) -1,3,5-triazine, 2- (2-hydroxy-4-iso-octyloxy-phenyl) -4,6-di (2,4-dimethyl-phenyl) -1,3,5-triazine , Brand name Tinuvin 400 (BASF), brand name Tinuvin 405 (BASF), brand name Tinuvin 460 (BASF), brand name Line absorbers; benzophenone ultraviolet absorbers such as 2-hydroxy-4-n-methoxybenzophenone and 2-hydroxy-4-n-octoxybenzophenone; 2,4-di-tert-butylphenyl-3,5-di -Benzoate ultraviolet absorbers such as tert-butyl-4-hydroxybenzoate; Propandioic acid-{(4-methoxyphenyl) -methylene} -dimethyl ester, trade name Hostabin PR-25 (manufactured by Clariant Japan KK) Propanedioc acid-based ultraviolet absorbers such as trade name hostabin B-CAP (manufactured by Clariant Japan); 2-ethyl-2′-ethoxy-oxanilide, trade name Sanduvor VSU (manufactured by Clariant Japan) And oxanilide-based UV absorbersAmong these ultraviolet absorbers, benzotriazole and triazine ultraviolet absorbers tend to be preferable.

  Furthermore, for the purpose of imparting light control properties, a light control dye or a light control pigment may be added. As typical photochromic dyes or photochromic dyes, for example, one or two or more of spiropyran compounds, spirooxazine compounds, fulgide compounds, naphthopyran compounds, and bisimidazole compounds may be used depending on the desired coloration. Can be used.

Olefin compounds including episulfide compounds, alcohol compounds, amine compounds, epoxy compounds, organic acids and anhydrides thereof, (meth) acrylate compounds, etc., as resin modifiers, as long as the effects of the present invention are not impaired. Etc. can be used.
Examples of the internal mold release agent include acidic phosphate esters such as phosphate monoesters and phosphate diesters, (modified) silicone compounds such as dimethyl silicone and polyether-modified silicone, fluorine compounds, poly (oxyalkylene) alkyl ethers, and the like. Examples thereof include surface active compounds such as higher fatty acids and salts thereof, wax compounds such as carnauba wax and polyolefin.

<Optical material composition and method for producing molded article>
The composition for optical materials of the present embodiment includes an epoxy group-containing compound (A), a thiol compound (B), and, if necessary, an acid anhydride (C), and further contains the other components described above. Can be included. The composition can be prepared by mixing these components at once or by mixing them and then finally mixing them together.

  The mixing temperature is usually 25 ° C. or lower. From the viewpoint of the pot life of the composition for optical materials, it may be preferable to lower the temperature further. However, if the solubility of the catalyst and additive in the monomer is not good, it is possible to preheat and dissolve in the monomer and resin modifier.

  In this embodiment, the manufacturing method of a molded object is not specifically limited, However, Cast polymerization is mentioned as a preferable manufacturing method. First, a polymerizable composition is injected between molding molds held by a gasket or a tape. At this time, depending on the physical properties required for the obtained plastic lens, it may be preferable to subject the polymerizable composition to defoaming treatment under reduced pressure, filtration treatment such as pressurization, reduced pressure, or the like, if necessary. Many.

  The polymerization conditions are not limited because the conditions vary greatly depending on the composition of the polymerizable composition, the type and amount of catalyst used, the shape of the mold, etc., but are approximately 1 to 50 at a temperature of −50 to 150 ° C. Done over time. Depending on the case, it is preferable to hold or gradually raise the temperature in a temperature range of 10 to 150 ° C. and cure in 1 to 48 hours.

  The molded body may be subjected to a treatment such as annealing as necessary. The treatment temperature is usually 50 to 150 ° C, preferably 90 to 140 ° C, and more preferably 100 to 130 ° C.

  In the present embodiment, when producing a molded product, in addition to the above-mentioned “other components”, a chain extender, a crosslinking agent, a light stabilizer, an antioxidant, as in the known molding method, depending on the purpose. Various additives such as bluing agents, oil-soluble dyes, fillers, and adhesion improvers may be added.

<Application>
The resin molded body of the present embodiment can be formed into various shapes by changing the type of mold at the time of casting polymerization.

The molded body obtained from the optical material composition of the present embodiment has a high Abbe number and a high refractive index, is excellent in transparency and dimensional stability, and further contains an acid anhydride (C). Since it has excellent heat resistance, it can be used for various optical materials such as plastic lenses, plastic polarizing lenses, and photochromic lenses. The plastic polarizing lens includes a polarizing film and a base material layer formed on at least one surface of the polarizing film and made of a molded body obtained by curing the composition of the present embodiment.
These lenses are composed of a lens substrate made of the above-described composition, and a coating layer can be formed on the lens substrate.

  Specific examples of the coating layer include a primer layer, a hard coat layer, an antireflection layer, an antifogging coat layer, a stainproof layer, and a water repellent layer. Each of these coating layers can be used alone, or a plurality of coating layers can be used in multiple layers. When a coating layer is applied to both sides, a similar coating layer or a different coating layer may be applied to each surface.

Each of these coating layers is an infrared absorber for the purpose of protecting the eyes from infrared rays, a light stabilizer and an antioxidant for the purpose of improving the weather resistance of the lens, and a dye, a pigment and an antistatic agent for the purpose of improving the fashionability of the lens. In addition, a known additive for enhancing the performance of the lens may be used in combination.
For the layer to be coated by coating, various leveling agents for the purpose of improving coating properties may be used.
As mentioned above, although embodiment of this invention was described, these are the illustrations of this invention, In the range which does not impair the effect of this invention, various structures other than the above are employable.

  EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In this embodiment, the part is based on weight.

<Evaluation method>
-Refractive index, Abbe number: It measured at 20 degreeC using the refractometer KPR-20 (made by a Calnew optical industry company).
Heat resistance (glass transition temperature: Tg): Measured with a thermomechanical analyzer TMA-60 manufactured by Shimadzu Corporation by TMA penetration method (50 g load, pin tip 0.5 mmφ, heating rate 10 ° C./min).
Viscosity: Measured at 25 ° C. using a B-type rotational viscometer (manufactured by Brookfield, USA). The rotor and rotation conditions were appropriately selected and measured.

[Example 1]
1.5 parts of tetrabutylphosphonium bromide (manufactured by Wako Pure Chemical Industries, Ltd.) as a curing catalyst, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane as a polymerization reactive compound, A mixture of 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane In addition to 35.8 parts of a glass sample bottle, the mixture was stirred and mixed at 20 ° C. to obtain a uniform solution. For this homogeneous solution, 0.5 parts of Prisurf A212C (Daiichi Kogyo Seiyaku Co., Ltd.) as an internal mold release agent and Epomic R139S (bisphenol A epoxy resin, Mitsui Chemicals Co., Ltd.) 62. 2 parts was added and stirred and mixed at 20 ° C. to obtain a uniform polymerizable composition. This polymerizable composition was degassed for 30 minutes under a reduced pressure of 1 kPa or less, then filtered through a PTFE filter, and a cavity formed of a glass mold and a tape (curve shape: 4 curves for both concave and convex surfaces, center thickness) : 2 mm) and sealed with tape. These were placed in a polymerization oven, gradually heated from 25 ° C. to 120 ° C. over 19 hours, and then held at 120 ° C. for 2 hours for polymerization. After cooling, the glass mold and the tape were peeled off, and a molded body (plastic lens) made of a cured resin formed inside was taken out. The obtained molded body (plastic lens) was colorless and transparent. The results of measuring optical properties and heat resistance are shown in Table-1.
In addition, the viscosity at 25 degrees C of Epomic R139S was 9,000-11,000 mPa * s.

[Example 2]
0.5 part of tetrabutylphosphonium bromide (manufactured by Wako Pure Chemical Industries, Ltd.) as a curing catalyst, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane as a polymerization reactive compound, A mixture of 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane 21.4 parts, 18.1 parts of acid anhydride epoxy resin curing agent HN-5500 (Methylhexahydrophthalic anhydride, manufactured by Hitachi Chemical Co., Ltd.) is added to a glass sample bottle and stirred and mixed at 20 ° C. to obtain a uniform solution. Obtained. To this homogeneous solution, 60.6 parts of Epomic R139S (bisphenol A type epoxy resin, manufactured by Mitsui Chemicals) was added as a polymerization reactive compound, and the mixture was stirred and mixed at 20 ° C. to obtain a uniform polymerizable composition. The polymerizable composition was degassed for 5 minutes under a reduced pressure of 1 kPa or less, then filtered through a PTFE filter, and a cavity (curve shape: uneven surface) formed of an external mold release agent-treated glass mold and tape. Both were injected into 4 curves, center thickness: 2 mm) and sealed with tape. These were placed in a polymerization oven, gradually heated from 25 ° C. to 120 ° C. over 19 hours, and then held at 120 ° C. for 2 hours for polymerization. After cooling, the glass mold and the tape were peeled off, and a molded body (plastic lens) made of a cured resin formed inside was taken out. The obtained molded body (plastic lens) was colorless and transparent. The results of measuring optical properties and heat resistance are shown in Table-1.

[Example 3]
0.5 parts of tetraphenylphosphonium tetra-p-tolylborate (manufactured by Tokyo Chemical Industry Co., Ltd.) as a curing catalyst and 21.7 parts of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane as a polymerization reactive compound 16.2 parts of Ricacid MH-700 (4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30, manufactured by Shin Nippon Rika Co., Ltd.) to a glass sample bottle, and stirred and mixed at 20 ° C. A solution was obtained. To this homogeneous solution, 62.1 parts of Epomic R139S (bisphenol A type epoxy resin, manufactured by Mitsui Chemicals) was added as a polymerization reactive compound, and the mixture was stirred and mixed at 20 ° C. to obtain a uniform polymerizable composition. The polymerizable composition was degassed for 5 minutes under a reduced pressure of 1 kPa or less, then filtered through a PTFE filter, and a cavity (curve shape: uneven surface) formed of an external mold release agent-treated glass mold and tape. Both were injected into 4 curves, center thickness: 2 mm) and sealed with tape. These were placed in a polymerization oven, gradually heated from 25 ° C. to 120 ° C. over 19 hours, and then held at 120 ° C. for 2 hours for polymerization. After cooling, the glass mold and the tape were peeled off, and a molded body (plastic lens) made of a cured resin formed inside was taken out. The obtained molded body (plastic lens) was transparent. The results of measuring optical properties and heat resistance are shown in Table-1.

[Example 4]
0.1 part of tetrabutylphosphonium bromide (manufactured by Wako Pure Chemical Industries, Ltd.) as a curing catalyst, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane as a polymerization reactive compound, A mixture of 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane and 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane 25.6 parts, 21.6 parts of acid anhydride epoxy resin curing agent HN-5500 (Methylhexahydrophthalic anhydride, manufactured by Hitachi Chemical Co., Ltd.) are added to a glass sample bottle and stirred and mixed at 20 ° C. to obtain a uniform solution. Obtained. To this homogeneous solution, 52.9 parts of Celoxide 2021P (3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, manufactured by Daicel) was added as a polymerization reactive compound, and the mixture was stirred and mixed at 20 ° C. A uniform polymerizable composition was obtained. The polymerizable composition was degassed for 5 minutes under a reduced pressure of 1 kPa or less, then filtered through a PTFE filter, and a cavity (curve shape: uneven surface) formed of an external mold release agent-treated glass mold and tape. Both were injected into 4 curves, center thickness: 2 mm) and sealed with tape. These were placed in a polymerization oven, gradually heated from 25 ° C. to 120 ° C. over 19 hours, and then held at 120 ° C. for 2 hours for polymerization. After cooling, the glass mold and the tape were peeled off, and a molded body (plastic lens) made of a cured resin formed inside was taken out. The obtained molded body (plastic lens) was transparent. The results of measuring optical properties and heat resistance are shown in Table-1.
The viscosity of Celoxide 2021P at 25 ° C. was 100 to 600 mPa · s.

[Comparative Example 1]
Add 5 parts of N, N-dimethylcyclohexylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) as a curing catalyst, 100 parts of Epomic R139S (bisphenol A type epoxy resin, Mitsui Chemicals) as a polymerization reactive compound, add a glass sample bottle, 20 The mixture was stirred and mixed at 0 ° C. to obtain a uniform solution. The polymerizable composition was degassed for 5 minutes under a reduced pressure of 1 kPa or less, then filtered through a PTFE filter, and a cavity (curve shape: uneven surface) formed of an external mold release agent-treated glass mold and tape. Both were injected into 4 curves, center thickness: 2 mm) and sealed with tape. These were placed in a polymerization oven, gradually heated from 25 ° C. to 120 ° C. over 19 hours, and then held at 120 ° C. for 2 hours for polymerization. After cooling, the glass mold and the tape were peeled off, and a molded body (plastic lens) made of a cured resin formed inside was taken out. The obtained molded body (plastic lens) was transparent. The results of measuring optical properties and heat resistance are shown in Table 2.

Claims (9)

(A) an epoxy group-containing compound;
(B) a thiol compound,
The thiol compound (B) is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 1,1, 3,3-tetrakis (mercaptomethylthio) propane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-dithietane, and 2 , 5-bis (mercaptomethyl) -1,4-dithiane, a composition for optical materials.   Furthermore, the composition for optical materials of Claim 1 containing (C) acid anhydride.   The composition for optical materials according to claim 1 or 2, wherein the viscosity at 25 ° C of the epoxy group-containing compound (A) is 1 to 30,000 mPa · s.   The composition for optical materials according to any one of claims 1 to 3, wherein the epoxy group-containing compound (A) has two or more of either a glycidyl group or an epoxycyclohexyl group.   The epoxy group-containing compound (A) is selected from (hydrogenated) bisphenol A type epoxy resin, (hydrogenated) bisphenol F type epoxy resin, 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate The composition for optical materials according to any one of claims 1 to 4, which is at least one kind.   Acid anhydride (C) is methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride, bicyclo [2.2.1] heptane-2 The composition for optical materials according to claim 2, which is at least one selected from 1,3-dicarboxylic acid anhydride and phthalic anhydride.   The molded object which hardened | cured the composition for optical materials in any one of Claims 1-6.   An optical material comprising the molded article according to claim 7.   A lens made of the optical material according to claim 8.