JP2011212850A - Optical lens, and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an optical lens reduced in striae generation even when a lens of large volume, a strength lens, or a semi-finished lens is produced.SOLUTION: The optical lens manufacturing method in which an optical resin composition 3 composed of a compound whose structure is represented by formula (1) (wherein, Ris a 1-10C hydrocarbon group; R, Rand Rare each independently a 1-10C hydrocarbon group or hydrogen; Y is O, S, Se or Te; I is 0-5; m is 0 or 1; and n is 1-5), an inorganic compound having a sulfur atom and/or a selenium atom, and a compound having a mercapto group, is injected into a mold 5 having a pair of glass molds 2 and 4, and then the composition 3 is polymerized and cured, includes a process in which the side face part 5c and the peripheral parts 5a and 5b of the mold 5 are heat-insulated with a heat insulating material 1 having a thermal resistance of at least 0.010 mK/W.

Description

  The present invention relates to an optical lens and a manufacturing method thereof.

  In recent years, plastic materials have been widely used for various optical elements, particularly spectacle lenses, because they are light and tough and relatively easy to dye.

The spectacle lens is required to have low specific gravity, high transparency, low yellowness, high refractive index, high Abbe number, toughness, and the like. A high refractive index makes it possible to reduce the thickness of the lens, and a high Abbe number makes it possible to reduce the chromatic aberration of the lens.
Therefore, in recent years, for the purpose of thinning, an optical material composition that provides an optical material having a refractive index of 1.7 or more and an Abbe number of 30 or more has been proposed.
Recently, a composition for an optical material using an episulfide compound capable of further increasing the refractive index has been proposed.

However, these compositions have a problem that striae are likely to occur in lens production.
As a method of reducing striae, after injecting a plastic raw material into a lens mold for molding a semi-finished lens, the convex side of the lens mold is fixed at an angle of 0 ° to less than 45 ° with respect to the horizontal plane. A manufacturing method of a lens for performing polymerization (see, for example, Patent Document 1), or after injecting a plastic lens material into a molding lens mold, sin θ = d / (2R) (d: diameter of upper mold, R: upper mold) When the angle at which the relationship of the curvature radius of the mold is established is θ °, a lens manufacturing method (for example, patent) in which the lens mold is tilted with respect to the horizontal plane by an angle of θ ° or more and less than θ ° + 15 °. Document 2) is known.
Further, it has been common practice to reduce striae due to the polymerization pattern during polymerization and curing.

JP 2003-145555 A JP 2005-103915 A

  However, the striae reduction method as described above has a small degree of improvement and has not reached a level where it can be commercialized.

  The present invention has been made in view of the above circumstances, and a method of manufacturing an optical lens with little striae even when a lens, a strength lens, or a semi-finished lens having a large volume per sheet is manufactured. The purpose is to provide.

［式中、Ｒ^１は炭素数１〜１０の炭化水素基を表し、Ｒ^２、Ｒ^３およびＲ^４はそれぞれ独立して炭素数１〜１０の炭化水素基または水素を表し、ＹはＯ、Ｓ、ＳｅまたはＴｅを表し、ｌ＝０〜５、ｍ＝０または１、ｎ＝１〜５である。］
（２）本発明の光学レンズの製造方法は、前記断熱材の耐熱温度が１００℃以上であることが好ましい。
（３）本発明の光学レンズの製造方法は、前記成形用モールドの側面部から５〜ｄ／４［ｍｍ］（ｄはガラスモールドの直径である。）が断熱処理されることが好ましい。
（４）本発明の光学レンズの製造方法は、前記化合物（Ａ）を２５〜９６重量％、前記化合物（Ｂ）を０．１〜３０重量％、前記化合物（Ｃ）を０〜４０重量％の範囲で含有することが好ましい。
（５）本発明の光学レンズの製造方法は、染料および／または顔料をさらに含有することが好ましい。
（６）本発明の光学レンズの製造方法は、前記光学レンズの片面または両面に、光照射により青色に着色するフォトクロミック性能を有するコーティング層を少なくとも１層有することが好ましい。
（７）本発明の光学レンズの製造方法は、前記光学レンズの片面または両面に、衝撃強度を付与するためのプライマー層を少なくとも１層有することが好ましい。
（８）本発明の光学レンズの製造方法は、前記光学レンズの表面に、ハードコート層および反射防止層を有することが好ましい。
（９）本発明の光学レンズの製造方法は、前記ハードコート層が、酸化チタンを主成分とする複合酸化物粒子と、有機ケイ素化合物とを主成分として含有することが好ましい。
（１０）本発明の光学レンズの製造方法は、前記反射防止層が、多層無機酸化物層からなることが好ましい。
（１１）本発明の光学レンズは、前記製造方法で得られることを特徴とする。 (1) The method for producing an optical lens of the present invention comprises a compound (A) having at least one structure represented by the following general formula (1) in one molecule, an inorganic compound having a sulfur atom and / or a selenium atom ( B) and an optical resin composition composed of a compound (C) having one or more mercapto groups in one molecule are injected into a molding mold having a pair of glass molds, and the optical resin composition is polymerized. A method for producing an optical lens to be cured, comprising a step of heat-insulating a side surface portion and a peripheral portion of the molding mold before or after injection with a heat insulating material, and the heat resistance of the heat insulating material is 0.010 m ² K. / W or more.

[Wherein, R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms, R ² , R ³ and R ⁴ each independently represents a hydrocarbon group having 1 to 10 carbon atoms or hydrogen, and Y represents O, S, Se or Te is represented, and l = 0 to 5, m = 0 or 1, and n = 1 to 5. ]
(2) In the method for producing an optical lens of the present invention, it is preferable that the heat-resistant temperature of the heat insulating material is 100 ° C. or higher.
(3) In the method for producing an optical lens of the present invention, it is preferable that 5 to d / 4 [mm] (d is the diameter of the glass mold) is heat-insulated from the side surface portion of the molding mold.
(4) In the method for producing an optical lens of the present invention, the compound (A) is 25 to 96% by weight, the compound (B) is 0.1 to 30% by weight, and the compound (C) is 0 to 40% by weight. It is preferable to contain in the range.
(5) It is preferable that the manufacturing method of the optical lens of this invention further contains dye and / or a pigment.
(6) It is preferable that the manufacturing method of the optical lens of this invention has at least one coating layer which has the photochromic performance colored in blue by light irradiation on the one or both surfaces of the said optical lens.
(7) The method for producing an optical lens of the present invention preferably has at least one primer layer for imparting impact strength on one or both surfaces of the optical lens.
(8) The method for producing an optical lens of the present invention preferably has a hard coat layer and an antireflection layer on the surface of the optical lens.
(9) In the method for producing an optical lens of the present invention, the hard coat layer preferably contains composite oxide particles containing titanium oxide as main components and an organosilicon compound as main components.
(10) In the method for producing an optical lens of the present invention, the antireflection layer is preferably composed of a multilayer inorganic oxide layer.
(11) The optical lens of the present invention is obtained by the manufacturing method.

  According to the present invention, it is possible to provide an optical lens with little striae even when a lens, a strength lens, or a semi-finished lens having a large volume per sheet is produced, and a method for producing the same.

It is a schematic sectional drawing of the one aspect | mode of the molding mold used for the manufacturing method of the optical lens of this invention, and a heat insulating material. It is a sample figure which showed the evaluation criteria of a striae level.

［式中、Ｒ^１は炭素数１〜１０の炭化水素基を表し、Ｒ^２、Ｒ^３およびＲ^４はそれぞれ独立して炭素数１〜１０の炭化水素基または水素を表し、ＹはＯ、Ｓ、ＳｅまたはＴｅを表し、ｌ＝０〜５、ｍ＝０または１、ｎ＝１〜５である。］ Hereinafter, the optical lens of the present invention and the manufacturing method thereof will be described in detail.
The method for producing an optical lens of the present invention includes a compound (A) having at least one structure represented by the following general formula (1) in one molecule, an inorganic compound (B) having a sulfur atom and / or a selenium atom, And an optical resin composition comprising a compound (C) having one or more mercapto groups in one molecule is poured into a molding mold having a pair of glass molds, and after injection, the side surface and the periphery of the molding mold It is a manufacturing method of the optical lens which heat-treats a part with a heat insulating material, and polymerizes and cures the optical resin composition, wherein the heat resistance of the heat insulating material is 0.010 m ² K / W or more. .

[Wherein, R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms, R ² , R ³ and R ⁴ each independently represents a hydrocarbon group having 1 to 10 carbon atoms or hydrogen, and Y represents O, S, Se or Te is represented, and l = 0 to 5, m = 0 or 1, and n = 1 to 5. ]

First, the optical resin composition (hereinafter referred to as “the optical resin composition of the present invention”) used in the method for producing an optical lens of the present invention will be described.
The optical resin composition of the present invention comprises a compound (A) having at least one structure represented by the general formula (1) in one molecule, an inorganic compound (B) having a sulfur atom and / or a selenium atom, and It consists of a compound (C) having one or more mercapto groups in one molecule.

“Compound (A) having at least one structure represented by the general formula (1) in one molecule”
As the compound (A), a compound having at least one structure represented by the general formula (1) in one molecule is essential, and a compound having at least two structures is preferable. Specifically, a compound having two or more episulfide groups in the molecule is preferable. Examples of such a compound include all known bifunctional or higher functional episulfide compounds.

In General Formula (1), R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms, R ² , R ^3, and R ⁴ each independently represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, Y represents O, S, Se or Te, and 1 = 0 to 5, m = 0 or 1, and n = 1 to 5.

Specific examples of the divalent hydrocarbon group having 1 to 10 carbon atoms as R ¹ include linear, branched or cyclic alkylene having 1 to 10 carbon atoms, phenylene, alkyl-substituted phenylene, naphthalene, and the like. And an arylene group having 6 to 10 carbon atoms, or an aralkylene group having 7 to 10 carbon atoms composed of a combination of alkylene and arylene. Among these, a C1-C10 alkylene group is preferable, a methylene group or ethylene group is more preferable, and a methylene group is still more preferable.
m is preferably 1.
The hydrocarbon group having 1 to 10 carbon atoms which is R ² , R ³ and R ⁴ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, carbon The aralkyl group of several 7-10 is mentioned. R ² , R ³ and R ⁴ are preferably a hydrogen atom or an alkylene group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a methyl group, and still more preferably a hydrogen atom.
Y is preferably S, Se or Te, and more preferably S from the viewpoint of producing an optical lens having a high refractive index.
l is preferably 0 to 4, more preferably 0 or 1, and particularly preferably 1.
n is preferably 1 or 2, and more preferably 1.

Examples of the compound having at least one structure represented by the general formula (1) of the present invention in one molecule include the following.
(A) an organic compound having an epithio group, (b) an organic compound having an epithioalkyloxy group, (c) an organic compound having an epithioalkylthio group, (d) an organic compound having an epithioalkylseleno group, (e ) An organic compound having an epithioalkyltelluro group.
The above (a), (b), (c), (d), and (e) may be used alone or in admixture of two or more.
In addition, the above (a), (b), (c), (d), (e) are a chain compound, a branched compound, an aliphatic cyclic compound, an aromatic compound, or nitrogen, oxygen, sulfur, selenium, It has a heterocyclic compound containing a tellurium atom as its main skeleton, and has an epithio group, an epithioalkyloxy group, an epithioalkylthio group, an epithioalkylseleno group, and an epithioalkyltelluro group simultaneously in one molecule. Also good.
Furthermore, these compounds may contain bonds such as sulfide, selenide, telluride, ether, sulfone, ketone, ester, amide, urethane, etc. in the molecule.

  (A) As an organic compound having one or more epithio groups, a compound obtained by substituting one or more epoxy groups of an epoxy group (not a glycidyl group) with an epithio group can be cited as a representative example. Organic compounds having an aliphatic skeleton, compounds having an aliphatic cyclic skeleton, and compounds having an aromatic skeleton.

  Examples of the organic compound having a chain aliphatic skeleton include 1,1-bis (epithioethyl) methane, 1- (epithioethyl) -1- (β-epithiopropyl) methane, and 1,1-bis (β-epithiopropyl). ) Methane, 1- (epithioethyl) -1- (β-epithiopropyl) ethane, 1,2-bis (β-epithiopropyl) ethane, 1- (epithioethyl) -3- (β-epithiopropyl) butane 1,3-bis (β-epithiopropyl) propane, 1- (epithioethyl) -4- (β-epithiopropyl) pentane, 1,4-bis (β-epithiopropyl) butane, 1- (epithioethyl) ) -5- (β-epithiopropyl) hexane, 1- (epithioethyl) -2- (γ-epithiobutylthio) ethane, 1- (epithioethyl) -2- [2- (γ-epithiobu) Tilthio) ethylthio] ethane, tetrakis (β-epithiopropyl) methane, 1,1,1-tris (β-epithiopropyl) propane, 1,3-bis (β-epithiopropyl) -1- (β- Epithiopropyl) -2-thiapropane, 1,5-bis (β-epithiopropyl) -2,4-bis (β-epithiopropyl) -3-thiapentane, and the like.

  Examples of the compound having an aliphatic cyclic skeleton include 1,3 or 1,4-bis (epithioethyl) cyclohexane, 1,3 or 1,4-bis (β-epithiopropyl) cyclohexane, 2,5-bis (epithioethyl). -1,4-dithiane, 2,5-bis (β-epithiopropyl) -1,4-dithiane, 4-epithioethyl-1,2-cyclohexene sulfide, 4-epoxy-1,2-cyclohexene sulfide, etc. Compounds having one aliphatic cyclic structure, 2,2-bis [4- (epithioethyl) cyclohexyl] propane, 2,2-bis [4- (β-epithiopropyl) cyclohexyl] propane, bis [4- ( Epithioethyl) cyclohexyl] methane, bis [4- (β-epithiopropyl) cyclohexyl] methane, bis [4- (β-epithio) Examples thereof include compounds having two aliphatic cyclic structures such as (propyl) cyclohexyl] sulfide and bis [4- (epithioethyl) cyclohexyl] sulfide.

  The compound having an aromatic skeleton has one aromatic skeleton such as 1,3 or 1,4-bis (epithioethyl) benzene, 1,3 or 1,4-bis (β-epithiopropyl) benzene. Compounds, bis [4- (epithioethyl) phenyl] methane, bis [4- (β-epithiopropyl) phenyl] methane, 2,2-bis [4- (epithioethyl) phenyl] propane, 2,2-bis [ 4- (β-epithiopropyl) phenyl] propane, bis [4- (epithioethyl) phenyl] sulfide, bis [4- (β-epithiopropyl) phenyl] sulfide, bis [4- (epithioethyl) phenyl] sulfone, Bis [4- (β-epithiopropyl) phenyl] sulfone, 4,4′-bis (epithioethyl) biphenyl, 4,4′-bis (β Epithiopropyl) biphenyl, a compound having two aromatic backbone of the like. Furthermore, compounds in which at least one hydrogen of the epithio group of these compounds is substituted with a methyl group are also included.

  (B) Examples of the organic compound having one or more epithioalkyloxy groups include compounds in which one or more glycidyl groups of an epoxy compound derived from epihalohydrin are substituted with epithioalkyloxy groups (thioglycidyl groups). .

Specific examples of the epoxy compound are produced by condensation of a polyhydric phenol compound such as hydroquinone, catechol, resorcin, bisphenol A, bisphenol F, bisphenol sulfone, bisphenol ether, bisphenol sulfide, halogenated bisphenol A, novolac resin, and epihalohydrin. Phenolic epoxy compounds; ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neo Pentyl glycol, glycerin, trimethylolpropane trimethacrylate, pentaerythritol, 1,3- Or polyhydric alcohol compounds such as 1,4-cyclohexanediol, 1,3- or 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, bisphenol A / ethylene oxide adduct, bisphenol A / propylene oxide adduct and epihalohydrin Alcohol-based epoxy compounds produced by condensation of adipic acid, sebacic acid, dodecanedicarboxylic acid, dimer acid, phthalic acid, iso, terephthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, hexahydroisophthalic acid , Hexahydroterephthalic acid, het acid, nadic acid, maleic acid, succinic acid, fumaric acid, trimellitic acid, benzenetetracarboxylic acid, benzophenonetetracarboxylic acid, naphthalene dicarboxylic acid, diphenyldi Glycidyl ester epoxy compounds produced by condensation of polycarboxylic acid compounds such as rubonic acid and epihalohydrins; 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, 1,5- or 2,6-naphthalenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 2,2- Primary diamine such as (4,4′-diaminodiphenyl) propane, 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-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)- Produced from amine-based epoxy compounds produced by condensation of secondary diamines such as lopan, 1,4-di- (4-piperidyl) -butane and epihalohydrins, the above-mentioned polyhydric alcohols, phenol compounds and diisocyanates and glycidol. Examples include urethane-based epoxy compounds.
More specifically, an organic compound having a chain aliphatic skeleton, a compound having an aliphatic cyclic skeleton, and a compound having an aromatic skeleton can be given.

  Examples of the organic compound having a chain aliphatic skeleton include bis (β-epithiopropyl) ether, bis (β-epithiopropyloxy) methane, 1,2-bis (β-epithiopropyloxy) ethane, 1, 3-bis (β-epithiopropyloxy) propane, 1,2-bis (β-epithiopropyloxy) propane, 1- (β-epithiopropyloxy) -2- (β-epithiopropyloxymethyl) Propane, 1,4-bis (β-epithiopropyloxy) butane, 1,3-bis (β-epithiopropyloxy) butane, 1- (β-epithiopropyloxy) -3- (β-epithio Propyloxymethyl) butane, 1,5-bis (β-epithiopropyloxy) pentane, 1- (β-epithiopropyloxy) -4- (β-epithiopropyloxymethyl) pe Lanthanum, 1,6-bis (β-epithiopropyloxy) hexane, 1- (β-epithiopropyloxy) -5- (β-epithiopropyloxymethyl) hexane, 1- (β-epithiopropyloxy) ) -2-[(2-β-epithiopropyloxyethyl) oxy] ethane, 1- (β-epithiopropyloxy) -2-[[2- (2-β-epithiopropyloxyethyl) oxyethyl] Oxy] ethane, tetrakis (β-epithiopropyloxymethyl) methane, 1,1,1-tris (β-epithiopropyloxymethyl) propane, 1,5-bis (β-epithiopropyloxy) -2- (Β-epithiopropyloxymethyl) -3-thiapentane, 1,5-bis (β-epithiopropyloxy) -2,4-bis (β-epithiopropyloxymethyl) -3-thiapentane, 1- (β-epithiopropyloxy) -2,2-bis (β-epithiopropyloxymethyl) -4-thiahexane, 1,5,6-tris (β-epithiopropyloxy) -4- (β-epithiopropyloxymethyl) -3-thiahexane, 1,8-bis (β-epithiopropyloxy) -4- (β-epithiopropyloxymethyl) -3,6-dithiaoctane, , 8-bis (β-epithiopropyloxy) -4,5bis (β-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropyloxy) -4,4 -Bis (β-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropyloxy) -2,4,5-tris (β-epithiopropyloxymethyl) ) -3,6-dithiaoctane, 1,8-bis (β-epithiopropyloxy) -2,5-bis (β-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,9-bis (β -Epithiopropyloxy) -5- (β-epithiopropyloxymethyl) -5-[(2-β-epithiopropyloxyethyl) oxymethyl] -3,7-dithianonane, 1,10-bis (β -Epithiopropyloxy) -5,6-bis [(2-β-epithiopropyloxyethyl) oxy] -3,6,9-trithiadecane, 1,11-bis (β-epithiopropyloxy) -4 , 8-bis (β-epithiopropyloxymethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropyloxy) -5,7-bis (β-epithiopropyloxy) Methyl ) -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropyloxy) -5,7-[(2-β-epithiopropyloxyethyl) oxymethyl] -3,6 Examples include 9-trithiaundecane and 1,11-bis (β-epithiopropyloxy) -4,7-bis (β-epithiopropyloxymethyl) -3,6,9-trithiaundecane.

  Examples of the compound having an aliphatic cyclic skeleton include 1,3 or 1,4-bis (β-epithiopropyloxy) cyclohexane, 1,3 or 1,4-bis (β-epithiopropyloxymethyl) cyclohexane, bis [4- (β-epithiopropyloxy) cyclohexyl] methane, 2,2-bis [4- (β-epithiopropyloxy) cyclohexyl] propane, bis [4- (β-epithiopropyloxy) cyclohexyl] sulfide 2,5-bis (β-epithiopropyloxymethyl) -1,4-dithiane, 2,5-bis (β-epithiopropyloxyethyloxymethyl) -1,4-dithiane, and the like.

  Examples of the compound having an aromatic skeleton include 1,3 or 1,4-bis (β-epithiopropyloxy) benzene, 1,3 or 1,4-bis (β-epithiopropyloxymethyl) benzene, and the like. Compounds having one aromatic skeleton, bis [4- (β-epithiopropyl) phenyl] methane, 2,2-bis [4- (β-epithiopropylthio) phenyl] propane, bis [4- ( Two aromatic skeletons such as β-epithiopropylthio) phenyl] sulfide, bis [4- (β-epithiopropylthio) phenyl] sulfone, 4,4′-bis (β-epithiopropylthio) biphenyl The compound which has is mentioned. Furthermore, compounds in which at least one hydrogen of the epithio group of these compounds is substituted with a methyl group are also included.

(C) As an organic compound having one or more epithioalkylthio groups, one epoxyalkylthio group (specifically, β-epoxypropylthio group) of an epoxy compound derived from a compound having a mercapto group and an epihalohydrin The compound which substituted the above by the epithioalkylthio group is mentioned.
More specifically, an organic compound having a chain aliphatic skeleton, a compound having an aliphatic cyclic skeleton, and a compound having an aromatic skeleton can be given.

  Examples of organic compounds having a chain aliphatic skeleton include bis (β-epithiopropyl) sulfide, bis (β-epithiopropyl) disulfide, bis (β-epithiopropyl) trisulfide, and bis (β-epithiopropyl). Thio) methane, bis (β-epithiopropyldithio) methane, bis (β-epithiopropyldithio) ethane, bis (β-epithiopropyldithioethyl) sulfide, bis (β-epithiopropyldithioethyl) disulfide, 1,2-bis (β-epithiopropylthio) ethane, 1,3-bis (β-epithiopropylthio) propane, 1,2-bis (β-epithiopropylthio) propane, 1- (β- Epithiopropylthio) -2- (β-epithiopropylthiomethyl) propane, 1,4-bis (β-epithiopropylthio) butane, 1,3-bis (β-epithiopropylthio) butane, 1- (β-epithiopropylthio) -3- (β-epithiopropylthiomethyl) butane, 1,5-bis (β-epithiopropyl) Thio) pentane, 1- (β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) pentane, 1,6-bis (β-epithiopropylthio) hexane, 1- (β-epithio) Propylthio) -5- (β-epithiopropylthiomethyl) hexane, 1- (β-epithiopropylthio) -2-[(2-β-epithiopropylthioethyl) thio] ethane, 1- (β -Epithiopropylthio) -2-[[2- (2-β-epithiopropylthioethyl) thioethyl] thio] ethanetetrakis (β-epithiopropylthiomethyl) methane, tetrakis (β-epithiopropyl) Thiomethyl) methane, 1,1,1-tris (β-epithiopropylthiomethyl) propane, 1,2,3-tris (β-epithiopropyldithio) propane, 1,5-bis (β-epithiopropyl) Thio) -2- (β-epithiopropylthiomethyl) -3-thiapentane, 1,5-bis (β-epithiopropylthio) -2,4-bis (β-epithiopropylthiomethyl) -3- Thiapentane, 1,6-bis (β-epithiopropyldithiomethyl) -2- (β-epithiopropyldithioethylthio) -4-thiahexane, 1- (β-epithiopropylthio) -2,2-bis (Β-epithiopropylthiomethyl) -4-thiahexane, 1,5,6-tris (β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) -3-thiahexane, 1, -Bis (β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -4,5bis (β- Epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -4,4-bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1, 8-bis (β-epithiopropylthio) -2,4,5-tris (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -2 , 5-bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,9-bis (β-epithiopropylthio) -5- (β-epithiopropylthiomethyl) -5-[( 2-β-epithiopropyl Oethyl) thiomethyl] -3,7-dithianonane, 1,10-bis (β-epithiopropylthio) -5,6-bis [(2-β-epithiopropylthioethyl) thio] -3,6,9 -Trithiadecane, 1,11-bis (β-epithiopropylthio) -4,8-bis (β-epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (β- Epithiopropylthio) -5,7-bis (β-epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropylthio) -5,7- [ (2-β-epithiopropylthioethyl) thiomethyl] -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropylthio) -4,7-bis (β-epithiopropylthio) Methyl) -3,6,9-tri Thiaundecane and the like can be mentioned.

  Examples of the chain compound having an ester group and an epithioalkylthio group include tetra [2- (β-epithiopropylthio) acetylmethyl] methane, 1,1,1-tri [2- (β-epithiopropylthio). Acetylmethyl] propane, tetra [2- (β-epithiopropylthiomethyl) acetylmethyl] methane, 1,1,1-tri [2- (β-epithiopropylthiomethyl) acetylmethyl] propane and the like. .

  Examples of the compound having an aliphatic cyclic skeleton include 1,3 or 1,4-bis (β-epithiopropylthio) cyclohexane, 1,3 or 1,4-bis (β-epithiopropylthiomethyl) cyclohexane 2, 5-bis (β-epithiopropylthiomethyl) -1,4-dithiane, 2,5-bis (β-epithiopropyldithiomethyl) -1,4-dithiane, 2,5-bis (β-epithiol) A compound having one aliphatic cyclic skeleton such as propylthioethylthiomethyl) -1,4-dithiane, bis [4- (β-epithiopropylthio) cyclohexyl] methane, 2,2-bis [4- ( β-epithiopropylthio) cyclohexyl] propane, bis [4- (β-epithiopropylthio) cyclohexyl] sulfide, 2,2-bis [4- (β-epithiopropylthio) Kurohekishiru] propane, bis [4-(beta-epithiopropylthio) cyclohexyl] compounds having two aliphatic cyclic skeleton such sulfides and the like.

  Examples of the compound having an aromatic skeleton include 1,3 or 1,4-bis (β-epithiopropylthio) benzene, 1,3 or 1,4-bis (β-epithiopropylthiomethyl) benzene, 1, A compound having one aromatic skeleton such as 3 or 1,4-bis (β-epithiopropyldithiomethyl) benzene, bis [4- (β-epithiopropylthio) phenyl] methane, 2,2- Bis [4- (β-epithiopropylthio) phenyl] propane, bis [4- (β-epithiopropylthio) phenyl] sulfide, bis [4- (β-epithiopropylthio) phenyl] sulfone, 4, Examples thereof include compounds having two aromatic skeletons such as 4′-bis (β-epithiopropylthio) biphenyl. Furthermore, compounds in which at least one of hydrogens in the β-epithiopropyl group of these compounds is substituted with a methyl group are also specific examples.

(D) As an organic compound having an epithioalkylseleno group, an epoxy alkyl of an epoxy compound derived from a selenium compound such as metal selenium, alkali metal selenide, alkali metal selenol, alkyl (aryl) selenol, hydrogen selenide, and epihalohydrin Examples include compounds in which one or more seleno groups (specifically, β-epoxypropylseleno groups) are substituted with epithioalkylseleno groups.
More specifically, an organic compound having a chain aliphatic skeleton, a compound having an aliphatic cyclic skeleton, and a compound having an aromatic skeleton can be given.

  Examples of the organic compound having a chain aliphatic skeleton include bis (β-epithiopropyl) selenide, bis (β-epithiopropyl) diselenide, bis (β-epithiopropyl) triselenide, and bis (β-epithiopropylseleno). ) Methane, 1,2-bis (β-epithiopropylseleno) ethane, 1,3-bis (β-epithiopropylseleno) propane, 1,2-bis (β-epithiopropylseleno) propane, 1- (Β-epithiopropylseleno) -2- (β-epithiopropylselenomethyl) propane, 1,4-bis (β-epithiopropylseleno) butane, 1,3-bis (β-epithiopropylseleno) Butane, 1- (β-epithiopropylseleno) -3- (β-epithiopropylselenomethyl) butane, 1,5-bis (β-epithiopropylseleno) penta 1- (β-epithiopropylseleno) -4- (β-epithiopropylselenomethyl) pentane, 1,6-bis (β-epithiopropylseleno) hexane, 1- (β-epithiopropylseleno) ) -5- (β-epithiopropylselenomethyl) hexane, 1- (β-epithiopropylseleno) -2-[(2-β-epithiopropylselenoethyl) thio] ethane, 1- (β-epi Thiopropylseleno) -2-[[2- (2-β-epithiopropylselenoethyl) selenoethyl] thio] ethane, tetrakis (β-epithiopropylselenomethyl) methane, 1,1,1-tris (β- Epithiopropylselenomethyl) propane, 1,5-bis (β-epithiopropylseleno) -2- (β-epithiopropylselenomethyl) -3-thiapentane, 1,5-bis β-epithiopropylseleno) -2,4-bis (β-epithiopropylselenomethyl) -3-thiapentane, 1- (β-epithiopropylseleno) -2,2-bis (β-epithiopropylseleno) Methyl) -4-thiahexane, 1,5,6-tris (β-epithiopropylseleno) -4- (β-epithiopropylselenomethyl) -3-thiahexane, 1,8-bis (β-epithiopropyl) Seleno) -4- (β-epithiopropylselenomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylseleno) -4,5bis (β-epithiopropylselenomethyl) -3 , 6-dithiaoctane, 1,8-bis (β-epithiopropylseleno) -4,4-bis (β-epithiopropylselenomethyl) -3,6-dithiaoctane, 1,8-bis (β- Pithiopropylseleno) -2,4,5-tris (β-epithiopropylselenomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylseleno) -2,5-bis (β -Epithiopropylselenomethyl) -3,6-dithiaoctane, 1,9-bis (β-epithiopropylseleno) -5- (β-epithiopropylselenomethyl) -5-[(2-β-epithio Propylselenoethyl) selenomethyl] -3,7-dithianonane, 1,10-bis (β-epithiopropylseleno) -5,6-bis [(2-β-epithiopropylselenoethyl) thio] -3,6 , 9-trithiadecane, 1,11-bis (β-epithiopropylseleno) -4,8-bis (β-epithiopropylselenomethyl) -3,6,9-trithiaundecane, 1,11-bis ( β-epithiopropylseleno) -5,7-bis (β-epithiopropylselenomethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropylseleno) -5,7 -[(2-β-epithiopropylselenoethyl) selenomethyl] -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropylseleno) -4,7-bis (β-epithio Propylselenomethyl) -3,6,9-trithiaundecane, tetra [2- (β-epithiopropylseleno) acetylmethyl] methane, 1,1,1-tri [2- (β-epithiopropylseleno) Acetylmethyl] propane, tetra [2- (β-epithiopropylselenomethyl) acetylmethyl] methane, 1,1,1-tri [2- (β-epithiopropylselenomethyl) acetylmethyl Propane, bis (5,6-epithio-3-selenohexyl) selenide, 2,3-bis (6,7-thioepoxy-1-selena-4-selenoheptyl) -1- (3,4-thioepoxy-1- Selenobutyl) propane, 1,1,3,3-tetrakis (4,5-thioepoxy-2-selenopentyl) -2-selenapropane, bis (4,5-thioepoxy-2-selenopentyl) -3,6 9-Triselenaundecane-1,11-bis (3,4-thioepoxy-1-selenobutyl), 1,4-bis (3,4-thioepoxy-1-selenobutyl) -2,3-bis (6,7- Thioepoxy-1-selena-4-selenoheptyl) butane, tris (4,5-thioepoxy-2-selenopentyl) -3-selena-6-thiaoctane-1,8-bis (3,4-thio) Epoxy-1-selenobutyl), bis (5,6-epithio-3-selenohexyl) telluride, 2,3-bis (6,7-thioepoxy-1-tellura-4-selenoheptyl) -1- (3,4 -Thioepoxy-1-selenobutyl) propane, 1,1,3,3-tetrakis (4,5-thioepoxy-2-selenopentyl) -2-tellapropane, bis (4,5-thioepoxy-2-selenopentyl) -3,6,9-triteraundecane-1,11-bis (3,4-thioepoxy-1-selenobutyl), 1,4-bis (3,4-thioepoxy-1-selenobutyl) -2,3-bis (6,7-thioepoxy-1-tella-4-selenoheptyl) butane, tris (4,5-thioepoxy-2-selenopentyl) -3-tella-6-thiaoctane-1,8 Bis (3,4-thioepoxy-1-Serenobuchiru) and the like.

  Examples of the compound having an aliphatic cyclic skeleton include (1,3 or 1,4) -bis (β-epithiopropylseleno) cyclohexane, (1,3 or 1,4) -bis (β-epithiopropylselenomethyl). ) Cyclohexane, bis [4- (β-epithiopropylseleno) cyclohexyl] methane, 2,2-bis [4- (β-epithiopropylseleno) cyclohexyl] propane, bis [4- (β-epithiopropylseleno) ) Cyclohexyl] sulfide, 2,5-bis (β-epithiopropylselenomethyl) -1,4-dithiane, 2,5-bis (β-epithiopropylselenoethylthiomethyl) -1,4-dithiane, ( 2,3,2,5 or 2,6) -bis (3,4-epithio-1-selenobutyl) -1,4-diselenane, (2,3,2,5 or 2,6) Bis (4,5-epithio-2-selenopentyl) -1,4-diselenane, (2,4,2,5 or 5,6) -bis (3,4-epithio-1-selenobutyl) -1,3 Diselenane, (2,4,2,5 or 5,6) -bis (4,5-epithio-2-selenopentyl) -1,3-diselenane, (2,3,2,5,2,6 or 3,5) -bis (3,4-epithio-1-selenobutyl) -1-thia-4-selenane, (2,3,2,5,2,6 or 3,5) -bis (4,5- Epithio-2-selenopentyl) -1-thia-4-selenane, (2,4 or 4,5) -bis (3,4-epithio-1-selenobutyl) -1,3-diselenolane, (2,4 or 4,5) -bis (4,5-epithio-2-selenopentyl) -1,3-diselenolane, (2, 4,2,5 or 4,5) -bis (3,4-epithio-1-selenobutyl) -1-thia-3-selenolane, (2,4,2,5 or 4,5) -bis (4 5-epithio-2-selenopentyl) -1-thia-3-selenolane, 2,6-bis (4,5-epithio-2-selenopentyl-1,3,5-triselenane, bis (3,4-epithio) -1-selenobutyl) tricycloselenaoctane, bis (3,4-epithio-1-selenobutyl) dicycloselenanane, (2,3,2,4,2,5 or 3,4) -bis (3,4 -Epithio-1-selenobutyl) selenophan, (2,3,2,4,2,5 or 3,4) -bis (4,5-epithio-2-selenopentyl) selenophan, 2- (4,5 -Thioepoxy-2-selenopentyl) -5- (3,4 Thioepoxy-1-selenobutyl) -1-selenacyclohexane, (2,3,2,4,2,5,2,6,3,4,3,5 or 4,5) -bis (3,4-thioepoxy- 1-selenobutyl) -1-selenacyclohexane, (2,3,2,4,2,5,2,6,3,4,3,5 or 4,5) -bis (4,5-thioepoxy-2- Selenopentyl) -1-selenacyclohexane, (2,3,2,5 or 2,6) -bis (3,4-epithio-1-selenobutyl) -1,4-diterlan, (2,3,2,5 Or 2,6) -bis (4,5-epithio-2-selenopentyl) -1,4-diterlan, (2,4,2,5 or 5,6) -bis (3,4-epithio-1- Selenobutyl) -1,3-diterlan, (2,4,2,5 or 5,6) -bis 4,5-epithio-2-selenopentyl) -1,3-diterlan, (2,3,2,5,2,6 or 3,5) -bis (3,4-epithio-1-selenobutyl) -1 -Thia-4-tellrane, (2,3,2,5,2,6 or 3,5) -bis (4,5-epithio-2-selenopentyl) -1-thia-4-tellane, (2, 4 or 4,5) -bis (3,4-epithio-1-selenobutyl) -1,3-ditellolane, (2,4 or 4,5) -bis (4,5-epithio-2-selenopentyl)- 1,3-ditellolane, (2,4,2,5 or 4,5) -bis (3,4-epithio-1-selenobutyl) -1-thia-3-tellurolane, (2,4,2,5 or 4,5) -bis (4,5-epithio-2-selenopentyl) -1-thia-3-tellurolane, 2,6-bis (4,5-epithio-2-selenopentyl-1,3,5-triterulan, bis (3,4-epithio-1-selenobutyl) tricyclotellaoctane, bis (3,4-epithio- 1-selenobutyl) dicyclotellanonane, (2,3,2,4,2,5 or 3,4) -bis (3,4-epithio-1-selenobutyl) tellurophan, (2,3,2,4, 2,5 or 3,4) -bis (4,5-epithio-2-selenopentyl) tellurophane, 2- (4,5-thioepoxy-2-selenopentyl) -5- (3,4-thioepoxy-1- Selenobutyl) -1-tellulacyclohexane, (2,3,2,4,2,5,2,6,3,4,3,5 or 4,5) -bis (3,4-thioepoxy-1-selenobutyl) -1-tellulacyclohexane, 2,3,2,4,2,5,2,6,3,4,3,5 or 4,5) -bis (4,5-thioepoxy-2-selenopentyl) -1-telluracyclohexane It is done.

Examples of the compound having an aromatic skeleton include (1,3 or 1,4) -bis (β-epithiopropylseleno) benzene, (1,3 or 1,4) -bis (β-epithiopropylselenomethyl). Benzene, bis [4- (β-epithiopropylseleno) phenyl] methane, 2,2-bis [4- (β-epithiopropylseleno) phenyl] propane, bis [4- (β-epithiopropylseleno) Phenyl] sulfide, bis [4- (β-epithiopropylseleno) phenyl] sulfone, 4,4′-bis (β-epithiopropylseleno) biphenyl, and the like.
Furthermore, compounds in which at least one hydrogen of the β-epithiopropyl group of these compounds is substituted with a methyl group are also included.

(E) As an organic compound having an epithioalkyltelluro group, epoxyalkyl of an epoxy compound derived from a tellurium compound such as metal tellurium, alkali metal telluride, alkali metal tellurol, alkyl (aryl) tellurol, hydrogen telluride and epihalohydrin The compound which substituted one or more of the tellurium group (specifically (beta) -epoxypropyl tellurium group) with the epithioalkyltelluro group is mentioned.
More specifically, an organic compound having a chain aliphatic skeleton, a compound having an aliphatic cyclic skeleton, and a compound having an aromatic skeleton can be given.

  Examples of the organic compound having a chain aliphatic skeleton include bis (β-epithiopropyl) telluride, bis (β-epithiopropyl) ditelluride, bis (β-epithiopropyl) tritellide, and bis (β-epithiopropyltelluro). ) Methane, 1,2-bis (β-epithiopropyltelluro) ethane, 1,3-bis (β-epithiopropyltelluro) propane, 1,2-bis (β-epithiopropyltelluro) propane, 1- (Β-epithiopropyltelluro) -2- (β-epithiopropyltelluromethyl) propane, 1,4-bis (β-epithiopropyltelluro) butane, 1,3-bis (β-epithiopropyltelluro) Butane, 1- (β-epithiopropyltelluro) -3- (β-epithiopropyltelluromethyl) butane, 1,5-bis (β-epithiopropyltelluro) pentane 1- (β-epithiopropyltelluro) -4- (β-epithiopropyltelluromethyl) pentane, 1,6-bis (β-epithiopropyltelluro) hexane, 1- (β-epithiopropyltelluro) ) -5- (β-epithiopropyltelluromethyl) hexane, 1- (β-epithiopropyltelluro) -2-[(2-β-epithiopropyltelluroethyl) thio] ethane, 1- (β-epi Thiopropyltelluro) -2-[[2- (2-β-epithiopropyltelluroethyl) telluroethyl] thio] ethane, tetrakis (β-epithiopropyltelluromethyl) methane, 1,1,1-tris (β- Epithiopropyltelluromethyl) propane, 1,5-bis (β-epithiopropyltelluro) -2- (β-epithiopropyltelluromethyl) -3-thiapentane, 1,5-bis β-epithiopropyltelluro) -2,4-bis (β-epithiopropyltelluromethyl) -3-thiapentane, 1- (β-epithiopropyltelluro) -2,2-bis (β-epithiopropyltelluro) Methyl) -4-thiahexane, 1,5,6-tris (β-epithiopropyltelluro) -4- (β-epithiopropyltelluromethyl) -3-thiahexane, 1,8-bis (β-epithiopropyl) Tellurium) -4- (β-epithiopropyltelluromethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropyltelluro) -4,5bis (β-epithiopropyltelluromethyl) -3 , 6-dithiaoctane, 1,8-bis (β-epithiopropyltelluro) -4,4-bis (β-epithiopropyltelluromethyl) -3,6-dithiaoctane, 1,8-bis (β- Pithiopropyltelluro) -2,4,5-tris (β-epithiopropyltelluromethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropyltelluro) -2,5-bis (β -Epithiopropyltelluromethyl) -3,6-dithiaoctane, 1,9-bis (β-epithiopropyltelluro) -5- (β-epithiopropyltelluromethyl) -5-[(2-β-epithio Propyltelluroethyl) selenomethyl] -3,7-dithianonane, 1,10-bis (β-epithiopropyltelluro) -5,6-bis [(2-β-epithiopropyltelluroethyl) thio] -3,6 , 9-trithiadecane, 1,11-bis (β-epithiopropyltelluro) -4,8-bis (β-epithiopropyltelluromethyl) -3,6,9-trithiaundecane, 1,11-bis ( β-epithiopropyltelluro) -5,7-bis (β-epithiopropyltelluromethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropyltelluro) -5,7 -[(2-β-epithiopropyltelluroethyl) selenomethyl] -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropyltelluro) -4,7-bis (β-epithio Propyltelluromethyl) -3,6,9-trithiaundecane, tetra [2- (β-epithiopropyltelluro) acetylmethyl] methane, 1,1,1-tri [2- (β-epithiopropyltelluro) Acetylmethyl] propane, tetra [2- (β-epithiopropyltelluromethyl) acetylmethyl] methane, 1,1,1-tri [2- (β-epithiopropyltelluromethyl) acetylmethyl Propane, bis (5,6-epithio-3-tellurohexyl) selenide, 2,3-bis (6,7-thioepoxy-1-selena-4-telloheptyl) -1- (3,4-thioepoxy-1-tellulobutyl) Propane, 1,1,3,3-tetrakis (4,5-thioepoxy-2-tellopentyl) -2-selenapropane, bis (4,5-thioepoxy-2-tellopentyl) -3,6,9-triselena Undecane-1,11-bis (3,4-thioepoxy-1-tellulobutyl), 1,4-bis (3,4-thioepoxy-1-tellulobutyl) -2,3-bis (6,7-thioepoxy-1- Selena-4-telluroheptyl) butane, tris (4,5-thioepoxy-2-telluropentyl) -3-selena-6-thiaoctane-1,8-bis (3,4-thio) Epoxy-1-tellulobutyl), bis (5,6-epithio-3-tellurohexyl) telluride, 2,3-bis (6,7-thioepoxy-1-tellla-4-telluroheptyl) -1- (3,4-thioepoxy) -1-tellulobutyl) propane, 1,1,3,3-tetrakis (4,5-thioepoxy-2-tellopentyl) -2-tellapropane, bis (4,5-thioepoxy-2-tellopentyl) -3,6 , 9-triteraoundedecane-1,11-bis (3,4-thioepoxy-1-tellulobutyl), 1,4-bis (3,4-thioepoxy-1-tellulobutyl) -2,3-bis (6,7 -Thioepoxy-1-tellla-4-telluroheptyl) butane, tris (4,5-thioepoxy-2-tellopentyl) -3-tella-6-thiaoctane-1,8 Bis (3,4-thioepoxy-1-Terurobuchiru) and the like.

  Examples of the compound having an aliphatic cyclic skeleton include (1,3 or 1,4) -bis (β-epithiopropyltelluro) cyclohexane, (1,3 or 1,4) -bis (β-epithiopropyltelluromethyl). ) Cyclohexane, bis [4- (β-epithiopropyltelluro) cyclohexyl] methane, 2,2-bis [4- (β-epithiopropyltelluro) cyclohexyl] propane, bis [4- (β-epithiopropyltelluro) ) Cyclohexyl] sulfide, 2,5-bis (β-epithiopropyltelluromethyl) -1,4-dithiane, 2,5-bis (β-epithiopropyltelluroethylthiomethyl) -1,4-dithiane, ( 2,3,2,5 or 2,6) -bis (3,4-epithio-1-tellulobutyl) -1,4-diselenane, (2,3,2,5 or 2,6) Bis (4,5-epithio-2-telluropentyl) -1,4-diselenane, (2,4,2,5 or 5,6) -bis (3,4-epithio-1-tellulobutyl) -1,3- Diselenane, (2,4,2,5 or 5,6) -bis (4,5-epithio-2-telluropentyl) -1,3-diselenane, (2,3,2,5,2,6 or 3, 5) -Bis (3,4-epithio-1-tellulobutyl) -1-thia-4-selenane, (2,3,2,5,2,6 or 3,5) -bis (4,5-epithio- 2-tellopentyl) -1-thia-4-selenane, (2,4 or 4,5) -bis (3,4-epithio-1-tellulobutyl) -1,3-diselenolane, (2,4 or 4,5 ) -Bis (4,5-epithio-2-terlopentyl) -1,3-diselenolane, (2, 4,2,5 or 4,5) -bis (3,4-epithio-1-tellulobutyl) -1-thia-3-selenolane, (2,4,2,5 or 4,5) -bis (4 5-epithio-2-tellopentyl) -1-thia-3-selenolane, 2,6-bis (4,5-epithio-2-tellopentyl-1,3,5-triselenane, bis (3,4-epithio-1) -Tellulobutyl) tricycloselenaoctane, bis (3,4-epithio-1-tellurobutyl) dicycloselenanane, (2,3 or 2,4 or 2,5 or 3,4) -bis (3,4-epithio -1-tellulobutyl) selenophan, (2,3,2,4,2,5 or 3,4) -bis (4,5-epithio-2-tellopentyl) selenophan, 2- (4,5-thioepoxy- 2-telluropentyl) -5 3,4-thioepoxy-1-tellulobutyl) -1-selenacyclohexane, (2,3,2,4,2,5,2,6,3,4,3,5 or 4,5) -bis (3 4-thioepoxy-1-tellulobutyl) -1-selenacyclohexane, (2,3,2,4,2,5,2,6,3,4,3,5 or 4,5) -bis (4,5- Thioepoxy-2-tellulopentyl) -1-selenacyclohexane, (2,3,2,5 or 2,6) -bis (3,4-epithio-1-tellulobutyl) -1,4-diterlan, (2,3, 2,5 or 2,6) -bis (4,5-epithio-2-telluropentyl) -1,4-diterlan, (2,4, 2,5 or 5,6) -bis (3,4-epithio- 1-tellurobutyl) -1,3-diterlan, (2,4,2,5 or 5,6 -Bis (4,5-epithio-2-telluropentyl) -1,3-diterlan, (2,3,2,5,2,6 or 3,5) -bis (3,4-epithio-1-tellulobutyl) -1-thia-4-tellrane, (2,3,2,5,2,6 or 3,5) -bis (4,5-epithio-2-telluropentyl) -1-thia-4-tellane, (2 , 4 or 4,5) -bis (3,4-epithio-1-tellulobutyl) -1,3-ditellurolane, (2,4 or 4,5) -bis (4,5-epithio-2-telluropentyl)- 1,3-ditellolane, (2,4,2,5 or 4,5) -bis (3,4-epithio-1-tellulobutyl) -1-thia-3-tellurolane, (2,4,2,5 or 4,5) -Bis (4,5-epithio-2-terlopentyl) -1-thia-3-ter Lorane, 2,6-bis (4,5-epithio-2-tellopentyl-1,3,5-triterulan, bis (3,4-epithio-1-tellulobutyl) tricyclotellaoctane, bis (3,4-epithio) -1-tellulobutyl) dicyclotelllanonane, (2,3,2,4,2,5 or 3,4) -bis (3,4-epithio-1-tellulobutyl) tellophane, (2,3,2,4 , 2,5 or 3,4) -bis (4,5-epithio-2-terlopentyl) tellurophane, 2- (4,5-thioepoxy-2-terlopentyl) -5- (3,4-thioepoxy-1-tellulobutyl ) -1-tellulacyclohexane, (2,3,2,4,2,5,2,6,3,4,3,5 or 4,5) -bis (3,4-thioepoxy-1-tellulobutyl)- 1-Telluracyclohe Sun, (2,3,2,4,2,5,2,6,3,4,3,5 or 4,5) -bis (4,5-thioepoxy-2-telluropentyl) -1-tellulacyclohexane, etc. Is mentioned.

  Examples of the compound having an aromatic skeleton include (1,3 or 1,4) -bis (β-epithiopropyltelluro) benzene, (1,3 or 1,4) -bis (β-epithiopropyltelluromethyl). Benzene, bis [4- (β-epithiopropyltelluro) phenyl] methane, 2,2-bis [4- (β-epithiopropyltelluro) phenyl] propane, bis [4- (β-epithiopropyltelluro) Phenyl] sulfide, bis [4- (β-epithiopropyltelluro) phenyl] sulfone, 4,4′-bis (β-epithiopropyltelluro) biphenyl, and the like. Furthermore, compounds in which at least one of hydrogens in the β-epithiopropyl group of these compounds is substituted with a methyl group are also specific examples.

  Furthermore, organic compounds having an unsaturated group are also included in the above (a) to (e), and vinylphenylthioglycidyl ether, vinylbenzylthioglycidyl ether, thioglycidyl methacrylate, thioglycidyl acrylate, allylthioglycidyl ether, etc. Can be mentioned.

  Among these exemplified compounds, (c) an organic compound having an epithioalkylthio group is more preferable, and bis (β-epithiopropyl) sulfide is particularly preferable.

“Inorganic compound (B) having sulfur atom and / or selenium atom”
The inorganic compound (B) having a sulfur atom and / or selenium atom is an inorganic compound having a sulfur atom and / or selenium atom. The inorganic compound suitably used in the present invention is a compound as described in “Standard Chemical Glossary of Terms” (edited by the Chemical Society of Japan (1991) Maruzen), which contains a compound not containing carbon and carbon. Also refers to relatively simple compounds. For example, carbon disulfide and potassium thiocyanate, which are relatively simple compounds containing carbon, are treated as inorganic compounds. In the optical resin composition of the present invention, the refractive index of the optical lens can be further increased by increasing the content of the inorganic compound (B) having a sulfur atom and / or selenium atom.

  The inorganic compound (B) having a sulfur atom and / or selenium atom used in the present invention is not particularly limited as long as it is an inorganic compound having at least one sulfur atom and / or selenium atom, but the sulfur atom in the inorganic compound And / or the ratio of the weight of selenium atoms is preferably 30% or more. When this ratio is less than 30%, the effect of increasing the refractive index of the optical lens is reduced.

  Specific examples of the inorganic compound having a sulfur atom include sulfur, hydrogen sulfide, carbon disulfide, selenocarbon sulfide, ammonium sulfide, sulfur dioxide, sulfur trioxide and other sulfur oxides, thiocarbonate, sulfuric acid and salts thereof, sulfuric acid Hydrogen salt, sulfite, hyposulfite, persulfate, thiocyanate, thiosulfate, halides such as sulfur dichloride, thionyl chloride, thiophosgene, boron sulfide, nitrogen sulfide, silicon sulfide, phosphorus sulfide, arsenic sulfide, Examples thereof include metal sulfides and metal hydrosulfides. Among these, sulfur, carbon disulfide, phosphorus sulfide, selenium sulfide, metal sulfide and metal hydrosulfide are preferable, sulfur, carbon disulfide and selenium sulfide are more preferable, and sulfur is particularly preferable.

Sulfur having a purity of 98% or more is suitable. If the purity is less than 98%, the lens tends to cloud due to the influence of impurities, but if it is 98% or more, the cloudiness is eliminated, which is preferable. The purity of sulfur as the sulfur-containing inorganic compound (B) is more preferably 99.0% or more, further preferably 99.5% or more, and most preferably 99.9% or more. Among impurities contained in sulfur, oil, acid content, ash content, arsenic, chloride, sulfide, and metal are components that cloud the lens. Therefore, such oil, acid content, and ash content are preferably 1% by weight or less in sulfur. Oil, acid content, and ash content do not copolymerize with other monomers, and therefore remain in the lens after polymerization and curing, causing fogging. Therefore, these are more preferably 0.1% by weight or less.
The sulfur purity, oil, acid content, ash content, and arsenic are measured according to JIS K6222-1 standard, and chloride and sulfide are measured with a standard solution according to JIS K8088 standard. Apply. The main components of metals detected by atomic absorption analysis are copper, lead, iron, nickel and the like.

  Moreover, as sulfur, it is preferable to use fine powder finer than 10 mesh. In the case of grains larger than 10 mesh, it is difficult to completely dissolve the sulfur, so that it is difficult to produce a lens. More preferably, it is fine powder finer than 30 mesh, and most preferably fine powder finer than 60 mesh.

As for sulfur production methods, there are sublimation purification methods from natural sulfur ores, mining by underground sulfur melting methods, recovery methods using hydrogen sulfide obtained from petroleum and natural gas desulfurization processes, etc. as raw materials. The sulfur used in the present invention may be produced by any method as long as a purity of 98% or more is ensured.
In general, commercially available sulfur includes finely divided sulfur, colloidal sulfur, precipitated sulfur, crystalline sulfur, sublimated sulfur, etc. depending on the shape and purification method. In the present invention, a purity of 98% or more is ensured. Any sulfur may be used as long as it is fine, but finely divided sulfur with fine particles is preferred.

Specific examples of the inorganic compound having a selenium atom include selenium, hydrogen selenide, selenium dioxide, carbon diselenide, and ammonium selenide except for the selenosulfuric sulfide and selenium sulfide, which are listed as specific examples of the inorganic compound having a sulfur atom. Selenium oxides such as selenium dioxide, selenic acid and salts thereof, selenous acid and salts thereof, hydrogen selenate, selenosulfuric acid and salts thereof, selenopyrosulfuric acid and salts thereof, halogens such as selenium tetrabromide and selenium oxychloride Compounds, selenocyanate, boron selenide, phosphorus selenide, arsenic selenide, metal selenide and the like. Among these, selenium, carbon diselenide, phosphorus selenide, and metal selenide are preferable, and selenium and carbon diselenide are more preferable.
These inorganic compounds having a sulfur atom and inorganic compounds having a selenium atom may be used alone or in combination of two or more.

“Compounds having one or more mercapto groups in one molecule (C)”
The compound (C) having one or more mercapto groups in one molecule may have a sulfide bond in addition to the mercapto group, and examples thereof include an aliphatic polythiol compound and an aromatic polythiol compound. Among these, Preferably, it is a polythiol compound with a high sulfur content rate, and these may be used independently and may be used in mixture of 2 or more types.

  Specific examples of the aromatic polythiol compound (C) having one or more mercapto groups in one molecule include 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4-bis (mercaptomethyl) benzene, 1,2-bis (mercaptoethyl) benzene, 1,3-bis ( Mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2, 3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris (me Captomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,3-di (p-methoxyphenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2, 4-di (p-mercaptophenyl) pentane, 1,2-bis (mercaptoethylthio) benzene, 1,3-bis (mercaptoethylthio) benzene, 1,4-bis (mercaptoethylthio) benzene, 1,2 , 3-Tris (mercaptomethylthio) benzene, 1,2,4-tris (mercaptomethylthio) benzene, 1,3 , 5-Tris (mercaptomethylthio) benzene, 1,2,3-tris (mercaptoethylthio) benzene, 1,2,4-tris (mercaptoethylthio) benzene, 1,3,5-tris (mercaptoethylthio) In addition to aromatic polythiol compounds such as benzene and mercapto groups, aromatic polythiol compounds containing sulfur atoms can be mentioned.

  Among these aromatic polythiol compounds, compounds represented by the following general formula (2) are particularly preferably used.

In general formula (2), p, q, and r each independently represent 0 or an integer of 1 or more, and when 0, that is, xylylene thiol is most preferable. In addition, as xylylene dithiol, any of o-xylylene dithiol, m-xylylene dithiol, and p-xylylene dithiol may be sufficient.
In addition, even when p, q, and r in the general formula (2) are all 1 or more, the functional group having a mercapto group is o-, m-, p- with respect to the benzene ring. Any arrangement may be adopted.
Furthermore, the functional group which has a mercapto group may have three or more with respect to a benzene ring instead of two. That is, this compound (C) may have three or more mercapto groups.
As the compound represented by the general formula (2), the glass transition temperature (Tg) decreases when the molecular chain is too long, and the Abbe number decreases when there are too many benzene rings. , Both are preferably 0 or 1.

Specific examples of the aliphatic polythiol compound that is the compound (C) having one or more mercapto groups in one molecule include the following compounds.
Methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiol, 1,2,3 -Propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane- 2,3-dithiol, 1,1-bis (mercaptomethyl) cyclohexane, bis (2-mercaptoethyl ester) thiomalate, 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto- 1-propanol (3-mercaptopropionate), die Lenglycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2-bis (mercaptomethyl) -1,3-propanedithiol, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane bis (2-mercaptoacetate), Trimethylolpropane bis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), tetrakis (mercapto) Chill) aliphatic polythiol compound such as methane.

  Dimercaptoethyl sulfide, hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropio) Nate), hydroxypropyl sulfide bis (2-mercaptoacetate), hydroxypropyl sulfide bis (3-mercaptopropionate), hydroxymethyl disulfide bis (2-mercaptoacetate), hydroxymethyl disulfide bis (3-mercaptopropionate) , Hydroxyethyl disulfide bis (2-mercaptoacetate), hydroxyethyl disulfide bis (3-mercaptopropionate), hydride Xypropyl disulfide bis (2-mercaptoacetate), hydroxypropyl disulfide bis (3-mercaptopropionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate) ), 1,4-dithian-2,5-diol bis (2-mercaptoacetate), 1,4-dithian-2,5-diol bis (3-mercaptopropionate), bis (2-mercaptoethyl) thiodiglycolate Ester), bis (2-mercaptoethyl ester) thiodipropionate, bis (2-mercaptoethyl ester) 4,4-thiodibutyrate, bis (2-mercaptoethyl ester) dithiodiglycolate, bis (dithiodipropionate) 2-mercapto Thiol ester), 4,4-dithiodibutyric acid bis (2-mercaptoethyl ester), thiodiglycolic acid bis (2,3-dimercaptopropyl ester), thiodipropionic acid bis (2,3-dimercaptopropyl ester) Bis (2,3-dimercaptopropyl ester) dithioglycolate, bis (2,3-dimercaptopropyl ester) dithiodipropionate, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1 , 2,2-Tetrakis (mercaptomethylthio) ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, 1,2,5-trimercapto-4-thiapentane, 3,3-dimercaptomethyl- 1,5-dimercapto-2,4-dithiapentane, 3-mercaptomethyl-1 , 5-dimercapto-2,4-dithiapentane, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3,6-dimercaptomethyl-1,9-dimercapto-2,5,8-trithianonane, 3,7-dimercaptomethyl-1,9-dimercapto-2,5,8-trithianonane, 4,6-dimercaptomethyl-1,9-dimercapto-2,5,8-trithianonane, 3-mercaptomethyl-1 , 6-dimercapto-2,5-dithiahexane, 3-mercaptomethylthio-1,5-dimercapto-2-thiapentane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 1,1,3,3-tetrakis (Mercaptomethylthio) propane, 1,4,8,11-tetramercapto-2,6,10-trithiaounde Can, 1,4,9,12-tetramercapto-2,6,7,11-tetrathiadecane, 2,3-dithia-1,4-butanedithiol, 2,3,5,6-tetrathia-1, 7-heptanedithiol, 2,3,5,6,8,9-hexathia-1,10-decanedithiol, 4,5-bis (mercaptomethylthio) -1,3-dithiolane, 4,6-bis (mercaptomethylthio) ) -1,3-dithiane, 2-bis (mercaptomethylthio) methyl-1,3-dithietane, 2- (2,2-bis (mercaptomethylthio) ethyl) -1,3-dithietane, 2-mercaptomethyl-6 -An aliphatic polythiol compound containing a sulfur atom in addition to a mercapto group such as mercapto-1,4-dithiacycloheptane.

  2,5-bis (mercaptomethyl) -1,4-dithiane, 2,5-bis (2-mercaptoethyl) -1,4-dithiane, 2,5-bis (3-mercaptopropyl) -1,4- Dithian, 2- (2-mercaptoethyl) -5-mercaptomethyl-1,4-dithiane, 2- (2-mercaptoethyl) -5- (3-mercaptopropyl) -1,4-dithiane, 2-mercaptomethyl -5- (3-mercaptopropyl) -1,4-dithiane, 2,4-bis (mercaptomethyl) -1,3-dithiolane, 2-mercaptomethyl-5-mercapto-1,3-dithiolane, 2,2 -Bis (mercaptomethyl) -1,3-dithiolane, 2- (3-mercaptopropyl) -4-mercaptomethyl-1,3-dithiolane, 2,2-bis (mercaptomethyl) -1, 3,5-trithiane, 2,4,5-tris (mercaptomethyl) -1,3-dithiolane, 2,2-bis (mercaptomethyl) -5-mercapto-1,3-dithiolane, 2- (1,2 -Dimercaptoethyl) -4-mercaptomethyl-1,3-dithiolane, 2- (1,2-dimercaptoethyl) -4-mercapto-1,3,5-trithiane, 2- (3-mercaptopropyl)- 4,5-bis (mercaptomethyl) -1,3-dithiolane, 2,2,4,5-tetrakis (mercaptomethyl) -1,3-dithiolane, 2- (1,2-dimercaptoethyl) -4, And cyclic compounds such as 5-bis (mercaptomethyl) -1,3-dithiolane.

  Compound (A) having one or more structures represented by the general formula (1) in one molecule, inorganic compound (B) having a sulfur atom and / or selenium atom, and one or more mercapto groups in one molecule In the optical resin composition comprising the compound (C) having 25 to 96% by weight of the compound (A), 0.1 to 30% by weight of the compound (B), and 0.1 to 0.1% of the compound (C). It is preferable to contain in the range of -40 weight%.

  Regarding the compounding ratio of the inorganic compound (B) having a sulfur atom and / or selenium atom which is a refractive index adjusting component, the addition amount is not particularly limited as long as the refractive index is 1.72 or more, but preferably 0. 0.1 to 30% by weight, more preferably 5 to 20% by weight. When the amount (incorporation) of the inorganic compound (B) having a sulfur atom and / or selenium atom is increased (for example, more than 30% by weight), the appearance of yellowing increases, light resistance decreases, cloudiness, etc. after heating This is because problems such as an increase in defects may occur. Moreover, it is because the refractive index of the plastic lens obtained will become lower than 1.72, for example when there are too few compounding quantities (for example, less than 0.1 weight%).

Moreover, about the compound (C) which has one or more mercapto groups in 1 molecule, it is preferable to set it as 0.1 to 40 weight%, and it is more preferable to set it as 4 to 10 weight%. When the compounding ratio of the compound (C) is too large, the heat resistance is lowered, and when it is too small, the light resistance is lowered.
In addition, about the compound (A) which has 1 or more of epithio groups in 1 molecule, the preferable compounding ratio of the said inorganic compound (B) which has the said sulfur atom and / or a selenium atom, and a mercapto group in said 1 molecule. A blending ratio obtained by subtracting a preferred blending ratio of the compound (C) having one or more, that is, a blending ratio of (A) = 100 wt% − (a blending ratio of (B) + a blending ratio of (C)) Become.

  By selecting the compound to be blended and the blending ratio thereof, the refractive index can be adjusted to 1.72 to 1.76, more preferably 1.73 to 1.75.

"Additive"
The optical resin composition of the present invention contains various additives in addition to the compound (A), the inorganic compound (B) having the sulfur atom and / or selenium atom, and the compound (C).
For example, in order to reduce yellowing due to the inorganic compound (B) having a sulfur atom and / or selenium atom, the compound (D) which is not the compound (A) or the compound (C) but has one or more disulfide bonds (D ) Is effectively blended. The amount of the compound (D) added is 0.3 parts by weight when the total amount of the compound (A), the inorganic compound (B) having a sulfur atom and / or selenium atom, and the compound (C) is 100 parts by weight. It is preferable to use ~ 20 parts by weight. However, since the compound (D) is not a component that crosslinks with other monomers, the glass transition temperature (Tg) decreases when added in a large amount, and further, the Abbe number decreases when a compound containing an aromatic ring is selected. Therefore, it is more preferable to use 0.5 to 5 parts by weight.

Moreover, it turned out that what has a specific structure is preferable among this compound (D) when the high refractive index of the plastic lens obtained, low yellow, and handling of the compound (D) are considered.
That is, the compound (D) preferably has an aromatic ring in order to maintain the high refractive index of the optical material, and the molecular weight thereof is preferably less than 300 in order to realize a low yellow color of the optical material. From the viewpoint of being easy to do, those having a molecular weight of 150 or more are preferred as those that are liquid or solid and have a weak odor.

  Specific examples of such a compound (D) include dimethyl disulfide, diethyl disulfide, di n-propyl disulfide, di n-butyl disulfide, di n-hexyl disulfide, di n-octyl disulfide, di n-decyl disulfide, di n-dodecyl disulfide, di-propyl disulfide, di-t-butyl disulfide, diallyl disulfide, bis (2-hydroxyethyl) disulfide, bis (3-carboxypropyl) disulfide, dicyclohexyl disulfide, diphenyl disulfide, di-p-toluyl disulfide, Dichlorodiphenyl disulfide, bis (2,4,5-trichlorodiphenyl) disulfide, dinaphthyl disulfide, bis (6-hydroxy-2-naphthyl) disulfide, difurfuryl disulfide Rufido, dipyridyl disulfide, dithio dimorpholine, tetra n- butyl disulfide and the like, may be used these alone or in combination of two or more. Among these compounds (D), diphenyl disulfide, di-p-toluyl disulfide, dichlorodiphenyl disulfide, dinaphthyl disulfide, difurfuryl disulfide, dipyridyl disulfide and the like are preferable, and diphenyl disulfide is more preferable.

  The optical resin composition of the present invention can be appropriately mixed with an ultraviolet absorber, a preliminary reaction catalyst, a reaction modifier, a curing catalyst, a dye or pigment, and other additives as necessary.

"UV absorber"
The ultraviolet absorber is not particularly limited as long as it is a substance capable of absorbing or diffusing ultraviolet rays. For example, benzophenone-based, benzotriazole-based, cyanoacrylate-based, and sterically hindered amines described in JP-A-2004-315556 UV absorbers of the type are mentioned, and benzotriazole type is preferable. These ultraviolet absorbers may be used alone or in combination of two or more.

  The content of the ultraviolet absorber in the optical resin composition of the present invention is preferably 0.1 to 5% by weight and more preferably 0.5 to 1.7% by weight with respect to 100% by weight. preferable. When the content of the ultraviolet absorber is at least the above lower limit, the optical material tends to be excellent in ultraviolet cut rate and weather resistance. On the other hand, by setting it to the upper limit or less, the heat resistance of the optical material is improved and the yellowness tends to be reduced.

"Curing catalyst"
The optical lens of the present invention can be obtained by injecting the optical resin composition of the present invention into a mold such as glass or metal (lens molding mold) and polymerizing and curing by heating. At this time, it is preferable to add a curing catalyst to the optical resin composition for sufficient curing.

Examples of the curing catalyst include tin compounds, amines, phosphines, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, secondary iodonium salts, ores described in JP-A-2004-315556. Acids, Lewis acids, organic acids, silicic acids, tetrafluoroboric acids, peroxides, azo compounds, condensates of aldehydes and ammonia compounds, guanidines, thiouric acids, thiazoles, sulfenamides, thiuram , Quaternary ammonium salts are preferable, and triethylbenzylammonium chloride is more preferable.
These curing catalysts may be used alone or in combination of two or more.

  The addition amount of the curing catalyst is preferably 0.0001 to 10.0% by weight and preferably 0.001 to 5.0% by weight with respect to 100% by weight of the optical resin composition of the present invention. Is more preferable.

"Reaction modifier"
In the optical resin composition of the present invention, a reaction modifier may be added in order to improve workability at the time of injection into the lens molding mold. The reaction modifier is not particularly limited as long as it exhibits the effect of preparing the reaction (polymerization), and conventionally known ones can be used. Among these, halides are preferable, chlorides are more preferable, trichloro compounds or dichloro compounds are more preferable, dialkyltin dichloride compounds and alkyltin trichloride compounds are particularly preferable, and dibutyltin dichloride is most preferable.

"Dyes and pigments"
If necessary, a dye or pigment may be added to the optical resin composition of the present invention in order to prevent poor initial color tone, yellowing or redness. The dyes and pigments are not particularly limited as long as they are substances that can prevent poor initial color tone, yellowing, and redness. For example, dyes for optical materials such as bluing agents that are commercially available for spectacle lens materials and the like Pigments can be used.

"Other additives"
The optical resin composition of the present invention may further contain an antioxidant, an internal mold release agent, an internal adhesion improver, and various other additives as necessary.

In the method for producing an optical lens of the present invention, a compound (A) having at least one structure represented by the general formula (1) in one molecule (hereinafter referred to as compound (A)), a sulfur atom and / or Optical resin comprising an inorganic compound (B) having a selenium atom (hereinafter referred to as compound (B)) and a compound (C) having at least one mercapto group in one molecule (hereinafter referred to as compound (C)). A method for producing an optical lens, in which a composition is injected into a molding mold having a pair of glass molds, and the optical resin composition is polymerized and cured, comprising: a side surface portion of the molding mold before or after injection; It has the process of heat-insulating a peripheral part with a heat insulating material, The thermal resistance of the said heat insulating material is 0.010 m < ² > K / W or more, It is characterized by the above-mentioned.

Examples of the method for polymerizing and curing the optical resin composition comprising the compound (A), the compound (B), and the compound (C) include a method in which the optical resin composition is preliminarily reacted.
As a method for preliminarily reacting the optical resin composition, a preliminary reaction catalyst is added before the curing catalyst is added to further advance the preliminary reaction of the optical resin composition, and a curing catalyst other than the preliminary reaction catalyst is used. And a method of increasing the viscosity by heating after the addition. In the preliminary reaction, components such as the compound (A), the compound (B), and the compound (C) are mixed, and a part of the monomer in the optical resin composition is polymerized by heating. The preliminary reaction is preferably performed under stirring, and may be performed at normal pressure or may be performed while degassing under reduced pressure.

  When mixing each of the above components, all of them may be mixed at the same time while stirring in the same container, or each component may be added and mixed in stages, or several components may be mixed and mixed. After preparing the individual mixtures, these mixtures may be mixed in the same container. When the components are mixed stepwise or divided into a plurality of mixtures, the mixing order can be appropriately determined in consideration of operability and reactivity. The mixing conditions such as temperature and time are not particularly limited as long as the obtained optical resin composition is sufficiently uniform, and may be a condition that does not cause an undesirable reaction between the components.

  The temperature of the preliminary reaction is preferably 0 to 100 ° C, more preferably 10 to 90 ° C, and further preferably 20 to 80 ° C. The time for the preliminary reaction is preferably 10 to 180 minutes, more preferably 20 to 150 minutes, and further preferably 30 to 120 minutes. By performing the preliminary reaction at a temperature and time in such a range, the viscosity of the optical resin composition can be increased and the viscosity can be adjusted.

  The thickening of the optical resin composition in the preliminary reaction depends on the reaction progress of the monomer component in the resin composition. Therefore, as a method of adjusting the viscosity of the optical resin composition to a desired value by a preliminary reaction, in addition to the above-described temperature and time control, the viscosity can be controlled by the method of adding each component in the resin composition. it can. In the optical resin composition of the present invention, the epithio group of the compound (A) and the mercapto group of the compound (C) react and polymerize by heating. The amount of the compound (C) added during the preliminary reaction can be arbitrarily determined in consideration of the balance of physical properties such as light resistance, oxidation resistance and heat resistance of the optical resin finally obtained.

  In the preliminary reaction, a catalyst (preliminary reaction catalyst) may or may not be added. The preliminary reaction catalyst is not particularly limited as long as it contributes to the polymerization reaction of the optical resin composition of the present invention, and the same catalysts as those mentioned above for the curing catalyst can be used. The amount of the preliminary reaction catalyst added varies depending on the temperature and time of the preliminary reaction, the ratio of the compound (A) and the compound (C), and is not particularly limited. However, the compound (A) and the compound during the preliminary reaction are not limited. When the total weight of (C) is 100 parts by weight, it is preferably 0.0001 to 5.0 parts by weight, more preferably 0.001 to 2.0 parts by weight.

  Curing catalysts other than the pre-reaction catalyst should be added to the optical resin composition after the pre-reaction to prevent the polymerization reaction from proceeding excessively during the pre-reaction and making it difficult to inject into the mold after the pre-reaction. Is preferred. However, when the viscosity of the resin composition is increased after the curing catalyst is added to adjust the viscosity, if the heating temperature and heating time are set lower than the temperature of the preliminary reaction, excessive Polymerization reaction can be prevented. The temperature for thickening the optical resin composition to which the curing catalyst is added is preferably 0 to 50 ° C, and preferably 15 to 45 ° C. In that case, the heating time is preferably 10 to 240 minutes, more preferably 30 to 120 minutes.

  The preliminary reaction may be performed only once, or may be reheated once or twice or more. Further, two or more methods for increasing the viscosity of the optical resin composition as described above may be combined or continuously performed. By performing the preliminary reaction in this way, it is possible to prevent the occurrence of precipitates when the components of the optical resin composition are mixed, so that the manufactured optical lens has a uniform characteristic and a good appearance. .

  The optical lens of the present invention can be obtained by injecting the optical resin composition thus prepared into a mold (lens molding mold) such as glass or metal and polymerizing and curing by heating. The temperature at which the prepared optical resin composition is poured into the lens molding mold is not particularly limited, but is preferably 10 to 30 ° C, and more preferably 15 to 25 ° C.

  The optical resin composition of the present invention is removed under reduced pressure before, during, or after mixing the above components in order to prevent bubbles from being generated during polymerization and curing in a lens molding mold. When gas operation is performed, it is preferable from the point which prevents generation | occurrence | production at the time of the bubble in cast polymerization hardening after that. The degree of decompression at this time is preferably about 0.1 to 700 mmHg (0.1 to 700 Torr), more preferably 0.5 to 300 mmHg (0.5 to 300 Torr). Furthermore, in order to further improve the quality of the optical lens of the present invention, the above-mentioned components or optical resin compositions obtained by mixing and / or pre-reacting these components are filtered and purified through a filter having a pore size of 0.05 to 3 μm. Is preferred.

  The optical resin composition thus prepared is poured into a molding mold having a pair of glass molds, and then subjected to thermal polymerization and curing using an electric furnace or the like. When thermosetting and curing, the curing time is preferably 0.1 to 100 hours, and preferably 1 to 72 hours. The curing temperature is preferably −10 to 160 ° C., and preferably 0 to 140 ° C. Thermal polymerization and curing may be carried out by holding at a predetermined curing temperature for a predetermined time, but operations such as temperature increase (0.1 to 100 ° C./h) and temperature decrease (0.1 to 100 ° C./h) are performed. May be combined as appropriate.

The method for producing an optical lens of the present invention includes a step of heat-insulating a side surface portion and a peripheral edge portion of the molding mold with a heat insulating material before or after injecting the optical resin composition into the molding mold. .
One of the causes of striae in the lens is thermal convection of the optical resin composition injected into the molding mold. The greater the movement of thermal convection, the more the traces of thermal convection remain as striae during polymerization curing of the optical resin composition.
Therefore, in the present invention, by the heat insulation treatment, the temperature distribution in the molding mold is kept uniform, and the occurrence of striae due to thermal convection is reduced.
The thermal resistance of the heat insulating material is a 0.010m ² K / W or more, preferably at least ^{0.020m 2 K / W, 0.050m 2} K / W or more is more preferable.

  The heat insulating material is not particularly limited as long as the thermal resistance is within the above range, and examples thereof include Aeroflex (manufactured by Aeroflex), Hemisar (manufactured by NICHIAS), urethane foam, and the like.

  In addition to the tape member described above, a gasket is preferably used as the heat insulating material for heat-treating the side surface and the peripheral edge of the molding mold. The gasket is preferably made of plastic, and a gasket molded product of a polyolefin-based thermoplastic resin is more preferably used. In order to achieve a heat insulating effect, it is particularly preferable to use a polyolefin-based elastomer from the viewpoint of moldability, flexibility, heat resistance, monomer stability, price, etc., among the polyolefin-based thermoplastic resins. Specific examples of polyolefin elastomers include polyethylene elastomers composed of low density polyethylene, polypropylene elastomers in which rubber components are finely dispersed in polypropylene homopolymers, ethylene-vinyl acetate copolymers and ethylene-alkyl acrylate copolymers. Can be mentioned.

  The heat-resistant temperature of the heat insulating material is preferably 100 ° C. or higher in consideration of the curing temperature of the optical resin composition described above.

When heat-insulating using a tape member, it is preferable that 5-d / 4 [mm] (d is a diameter of a glass mold) is heat-insulated from the side part of the said shaping | molding mold.
FIG. 1 is a schematic cross-sectional view of one embodiment of a molding mold and a heat insulating material used in the method for producing an optical lens of the present invention. The molding mold 5 includes glass molds 2 and 4, and the side surface portion 5 c and the peripheral edge portions 5 a and 5 b of the molding mold are covered with the heat insulating material 1. After injecting the optical resin composition 3 into the molding mold, as shown in FIG. 1, the side surface portion 5c and the peripheral portions 5a and 5b of the molding mold are heat-insulated using a heat insulating material. The range (L shown in FIG. 1) to be heat-insulated is preferably 5 to d / 4 [mm] from the side surface portion 5c of the molding mold from the viewpoint of heat insulation efficiency. In addition, although d is a diameter of a glass mold, 20 or more are preferable and about 60 is more preferable from the point of an optical lens.
The glass mold 2 has a larger curvature than the glass mold 3. Therefore, in order to insulate the glass mold 2 to the same extent as the glass mold 3, the length of the heat insulating material covering the peripheral edge portion 5b of the glass mold 2 is made longer than the heat insulating material covering the peripheral edge portion 5a of the glass mold 3. It is preferable.
Further, in order to suppress thermal convection of the optical resin composition in the molding mold, the molding mold may be held at an angle of 60 ° to 120 ° with respect to the horizontal plane during the polymerization curing of the optical resin composition. Good. For example, the molding mold may be held at an angle of 90 ° with respect to the horizontal plane during the polymerization and curing of the optical resin composition.

  The cured product thus polymerized and cured is released from the mold. The released cured product can be used as it is as the optical lens of the present invention, but it is preferable to perform an annealing treatment at a temperature of 50 to 150 ° C. for 10 minutes to 5 hours in order to remove distortion of the optical material.

  The obtained optical lens is usually used after being processed into a desired shape (for example, a spectacle lens shape). Further, if necessary, the optical lens may be used as a base material, and various coating layers may be formed on one side or both sides before or after processing into a desired shape. Examples of the coating layer include a primer layer, a hard coat layer, an antireflection layer, an antifogging coat layer, and an antifouling layer. Only one such coating layer may be formed, but two or more layers may be laminated to form a multilayer coating layer.

The constituent material of the primer layer is not particularly limited, and examples thereof include urethane resin, epoxy resin, polyester resin, melanin resin, and polyvinyl acetal.
The above primer composition has various filming properties such as various leveling agents for the purpose of improving coatability or ultraviolet absorbers and antioxidants for the purpose of improving weather resistance, dyes and pigments, photochromic dyes and photochromic pigments, etc. Known additives for adding a function such as enhancement can be used in combination.

  A primer layer can be formed by applying or solidifying the primer composition to a substrate. Examples of the coating method include known methods such as spin coating and dipping. It can also be formed by a dry method such as a CVD method or a vacuum deposition method. If necessary, the surface of the optical lens may be subjected to pretreatment such as alkali treatment, plasma treatment, or ultraviolet treatment. The film thickness after hardening of a primer layer is 0.1-10 micrometers, Preferably it is 0.2-3 micrometers. When the thickness of the primer layer is 0.1 μm or more, the impact resistance is excellent, and when it is 10 μm or less, the heat resistance and the surface accuracy are excellent.

The hard coat layer is a high refractive index inorganic material such as titanium oxide, zirconium oxide, etc. for organosilicon compounds, etc., to impart wear resistance, moisture resistance, warm water resistance, heat resistance, weather resistance, etc. to the optical lens surface. A hard coat liquid to which oxide fine particles and the like are added is applied and cured.
Further, the optical material may be colored by using a dyeable hard coat layer. After the hard coat layer is formed on the surface of the substrate, disperse dyes, sublimation dyes, reactive dyes, basic dyes, acid dyes, etc. are immersed in the hard coat layer, and the surface of the hard coat layer or the entire hard coat is colored. . Alternatively, a dye is dispersed in advance in the hard coat liquid, the hard coat liquid is applied and cured, and a colored hard coat layer is formed on the substrate surface.
Furthermore, you may form the hard-coat layer which has the photochromic performance colored blue by light irradiation. The photochromic performance is not particularly limited as long as it exhibits a blue photochromic performance, but it can be formed by a method in which a hard coat layer contains a blue photochromic compound. Examples of the blue photochromic compound include titanium oxide particles and / or titanium oxide-containing composite particles, and it is preferably formed on the surface of the optical material as a hard coat layer that can be relatively thick. Moreover, you may provide photochromic performance to layers other than a hard-coat layer.

  The hard coat layer is formed by applying a hard coat solution on an optical lens and then curing, and examples of the curing method include a thermal curing method, an effect method using a catalyst, and a curing method using energy beam irradiation. In general, the thickness of the cured film of the hard coat layer is preferably 0.3 to 30 μm after drying, and the refractive index of the obtained cured film is the refractive index of the optical lens before lamination of the hard coat layer. The difference is preferably in the range of ± 0.1.

Further, if necessary, a single-layer or multilayer antireflection film layer made of an inorganic oxide such as SiO ₂ or TiO ₂ may be formed on the hard coat layer. The antireflection film layer is preferably a multilayer antireflection film. In that case, a low refractive index film and a high refractive index film are alternately laminated. Examples of the high refractive index film include ZnO, TiO ₂ , CeO ₂ , Sb ₂ O ₅ , SnO ₂ , ZrO ₂ , ZrO ₂ , and Ta ₂ O ₅ , and examples of the low refractive index film include an SiO ₂ film. Is mentioned. Examples of the method for forming the antireflection film layer include dry methods such as vacuum deposition, sputtering, ion plating, ion beam assist, and CVD.

  On the antireflection film layer, an antifogging coating film layer or an antifouling film layer can be formed as necessary.

According to the method for producing an optical lens of the present invention, a molding in which an optical resin composition is injected using a heat insulating material having a thermal resistance of 0.010 m ² K / W or more when the optical resin composition is polymerized and cured. Manufacturing method capable of producing an optical lens with little striae with high productivity even when a lens, a strength lens, or a semi-finished lens having a large volume per sheet is manufactured by heat-treating the mold for use, and An optical lens obtained by the manufacturing method can be provided.

EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to a following example.
The physical properties of Examples and Comparative Examples were evaluated as follows.
[Evaluation of striae level]
The mercury lamp light source was transmitted through the optical lens, the transmitted light was projected onto a white plate, and the appearance striae level was evaluated in 6 stages from 0 to 5 based on the sample shown in FIG. Those having an appearance striae level of 2 or more were defined as commercializable levels. Evaluation was performed n times, and the average value of the striae level was calculated. The standard of the striae level shown in FIG. 2 will be described below.
α band: Range with a radius of 15 mm from the geometric center of the lens β band: Range other than α Level 5: Appearance cannot be confirmed visually.
Level 4: There is one thin streak in the periphery of the β-band away from the lens center.
Level 3: There are 2 to 3 thin streaks in the vicinity of the β band away from the lens center. However, even if there is only one, it corresponds to level 3.
Level 2: Crosses the boundary between the α band and the β band, but there are three or less striae at locations away from the center of the lens.
Level 1: completely straddles the α and β bands, and has a deep striae.
Level 0: There is a striae that crosses the center of the lens regardless of the darkness.
[Production of optical resin composition]
A is 785 parts by weight of bis (β-epithiopropyl) sulfide (Mitsubishi Gas Chemical Co., Ltd., trade name: IU-11A) as A, 143 parts by weight of sulfur powder (reagent with a purity of 98% or more) as B, part of C And 25 parts by weight of xylylene thiol as a UV absorber and 14 parts by weight of 2- (4-butoxy-2-hydroxyphenyl) -2H-benzotriazole (manufactured by Daiwa Kasei Co., Ltd., trade name: DAINSORB T-53) And stirred at 60 ° C. until dissolved.
Subsequently, 2 parts by weight of 2-mercapto-1-methylimidazole was added as a preliminary reaction catalyst to the mixed solution, and a preliminary reaction was performed at 60 ° C. for 50 minutes, followed by cooling to 20 ° C.
Next, as the remainder of C, 46 parts by weight of xylylene thiol, 0.2 parts by weight of triethylbenzylammonium chloride as a curing catalyst and 2 parts by weight of dibutyltin dichloride as a reaction modifier are added, and an optical resin composition It was.

Example 1
The optical resin composition is injected into a cavity in which a pair of glass molds are held by a tape, and the peripheral portion is wound with a heat insulating material (Aeroflex manufactured by Aeroflex Co., Ltd.) having a thermal resistance of 0.242 m ² K / W after the injection. After the polymerization pattern was installed in the polymerization furnace, the temperature was raised from 20 ° C. to 60 ° C. in 24 hours, held at 60 ° C. for 7 hours, then heated to 100 ° C. in 4 hours, and held at 100 ° C. for 5 hours. And cured by polymerization. The striae of the obtained lenses were evaluated, and the results are shown in Table 1.

(Example 2)
Polymerization and curing were performed in the same manner as in Example 2 except that the glass mold was held with a polyolefin-based elastomer (thermoplastic resin WSB manufactured by Sumitomo Chemical Co., Ltd.) so as to have a thermal resistance of 0.014 m ² K / W. The striae of the obtained lenses were evaluated, and the results are shown in Table 1.

(Example 3)
Polymerization and curing were carried out in the same manner as in Example 4 except that the glass mold was held with a polyolefin-based elastomer (thermoplastic resin WSB manufactured by Sumitomo Chemical Co., Ltd.) so as to have a thermal resistance of 0.010 m ² K / W. The striae of the obtained lenses were evaluated, and the results are shown in Table 1.

(Comparative Example 1)
The glass mold was polymerized and cured in the same manner as in Example 1 except that the glass mold was held with a commercially available PET film tape (Slion Tape No. 6263-51, manufactured by Slion Tech Co., Ltd.) so as to have a thermal resistance of 0.0002 m ² K / W. The striae of the obtained lenses were evaluated, and the results are shown in Table 1.

(Comparative Example 2)
The glass mold was polymerized and cured in the same manner as in Example 1 except that the glass mold was held with a commercially available PET film tape (Slion Tape No. 6263-51 manufactured by Slion Tech Co., Ltd.) so as to have a thermal resistance of 0.0003 m ² K / W. The striae of the obtained lenses were evaluated, and the results are shown in Table 1.

As shown in Table 1, no striae was observed in the obtained plastic lenses in Examples 1 to 3, which were heat-insulated using a heat-insulating material having a thermal resistance of 0.010 m ² K / W or more.

  From the above results, according to the method of manufacturing an optical lens of the present invention, an optical lens with little striae is obtained even when a lens, a strength lens, and a semi-finished lens having a large volume per sheet are manufactured. Obviously it can be.

DESCRIPTION OF SYMBOLS 1 Heat insulating material 2, 4 Glass mold 3 Optical resin composition 5 Mold 5a, 5b Peripheral part 5c Side part

Claims (11)

Compound (A) having at least one structure represented by the following general formula (1) in one molecule, inorganic compound (B) having a sulfur atom and / or selenium atom, and one mercapto group in one molecule An optical lens manufacturing method in which an optical resin composition comprising the compound (C) having the above is injected into a molding mold having a pair of glass molds, and the optical resin composition is polymerized and cured. Or a step of heat-insulating the side surface and the peripheral edge of the molding mold with a heat insulating material after injection, and the heat resistance of the heat insulating material is 0.010 m ² K / W or more. Production method.

[Wherein, R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms, R ² , R ³ and R ⁴ each independently represents a hydrocarbon group having 1 to 10 carbon atoms or hydrogen, and Y represents O, S, Se or Te is represented, and l = 0 to 5, m = 0 or 1, and n = 1 to 5. ]   The method for manufacturing an optical lens according to claim 1, wherein the heat-resistant temperature of the heat insulating material is 100 ° C. or higher.   The method for producing an optical lens according to claim 1, wherein 5 to d / 4 [mm] (d is a diameter of the glass mold) is heat-insulated from a side surface portion of the molding mold.   The compound (A) is 25 to 96% by weight, the compound (B) is 0.1 to 30% by weight, and the compound (C) is 0.1 to 40% by weight. The manufacturing method of the optical lens as described in any one.   The manufacturing method of the optical lens of Claim 4 which further contains dye and / or a pigment.   6. The method for producing an optical lens according to claim 4, wherein at least one coating layer having a photochromic property of being colored blue by light irradiation is provided on one side or both sides of the optical lens. The method for producing an optical lens according to claim 4, wherein at least one primer layer for imparting impact strength is provided on one side or both sides of the optical lens.   The manufacturing method of the optical lens as described in any one of Claims 4-7 which has a hard-coat layer and an antireflection layer on the surface of the said optical lens.   The method for producing an optical lens according to claim 8, wherein the hard coat layer contains composite oxide particles mainly composed of titanium oxide and an organosilicon compound as main components.   The method for manufacturing an optical lens according to claim 8, wherein the antireflection layer is formed of a multilayer inorganic oxide layer.   The optical lens obtained with the manufacturing method as described in any one of Claims 1-10.

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