JP2005338109A - Sulfur-atom-containing resin optical material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To satisfy demands for a higher yield of plastic lens production and for provision of a high-quality material in the field of optical materials of a spectacle lens, etc., having a high refractive index and a high Abbe's number. <P>SOLUTION: An optical material is provided which comprises a sulfur-atom-containing resin whose moisture absorption at a temperature of 60°C and a humidity of 90% in one day is ≤1.0×10<SP>-3</SP>%. The optical material has a high refractive index and a high Abbe's number and contributes to a higher yield of plastic lens production and to provision of a high-quality material. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a sulfur atom-containing resin material suitably used in the resin field such as an optical material that requires a high refractive index and high transparency.

In recent years, plastic lenses are rapidly spreading to optical elements such as spectacle lenses and camera lenses because they are lighter and harder to break than inorganic lenses and can be dyed.
The performance required for these plastic lenses is high refractive index and high Abbe number as optical performance, and high heat resistance, high impact resistance and low specific gravity as physical properties.

  Currently, polythiourethane resins in which sulfur atoms are introduced into the resin are known as resins that satisfy these required performances to some extent. The polythiourethane resin is a resin having an excellent balance such as high refractive index and good impact resistance (see, for example, Patent Document 1 and Patent Document 2).

  Further, in response to demands for higher refractive index and higher Abbe number, methods for improving the sulfur content of polythiol compounds used in polythiourethanes have also been proposed (for example, Patent Document 3 and Patent Document 4). Patent Document 5 and Patent Document 6).

On the other hand, a method using an episulfide compound has been proposed as a material pursuing a high refractive index and a high Abbe number, although required physical properties relating to strength such as impact resistance are not satisfied. (For example, see Patent Document 7 and Patent Document 8)
JP-A-60-199016 JP-A-63-46213 Japanese Patent Laid-Open No. 02-270859 Japanese Patent Laid-Open No. 03-236386 JP 07-252207 A JP 2001-342172 A Japanese Patent Application Laid-Open No. 09-110979 JP 11-322930 A

  According to the methods of these patent documents, excellent performance as a plastic lens such as a high refractive index, a high Abbe number, and a low specific gravity can be realized. However, in the resin obtained by these methods, particularly plastic lenses, when dyeing does not proceed uniformly and dyeing spots occur, or when a subsequent process such as washing, dyeing or coating is performed, for example, the lens frequency May change, contributing to a decrease in yield in lens manufacturing. Therefore, it has been demanded to develop a material with a high yield that is less likely to cause a frequency change in the subsequent process and that is less likely to cause staining spots.

As a result of diligent investigation focusing on the physical properties of the resin in order to solve the above-mentioned problems, the inventors have found that the moisture absorption rate of the resin at a temperature of 60 ° C., a humidity of 90%, and a day is 1.0 × 10 ^−3. % Of the sulfur atom-containing resin is found to be excellent in a high yield in which the frequency change is difficult to occur in the subsequent process and dyeing spots are not easily generated.

That is, the present invention
[1] The present invention relates to an optical material made of a sulfur atom-containing resin having a temperature of 60 ° C., a humidity of 90%, and a daily moisture absorption of 1.0 × 10 ⁻³ % or less. Here, “consisting of a sulfur atom-containing resin” means that a part of the optical material is composed of the sulfur atom-containing resin, and the entire optical material is composed of the sulfur atom-containing resin. The case is intended to include both.

The following [2] to [6] are each one of preferred embodiments of the present invention.
[2] The optical material according to [1], wherein the sulfur atom-containing resin is a thermosetting resin.
[3] The optical material according to [1] or [2], wherein the resin refractive index is 1.60 or more.
[4] The optical material according to [1], wherein the sulfur atom-containing resin is an episulfide resin. [5] The optical material according to [4], wherein the sulfur atom-containing resin is a thiourethane resin.
[6] The optical material according to any one of [1] to [6], wherein the sulfur atom-containing resin is obtained from a polymerized and purified organism containing single sulfur.
[7] A plastic lens made of the optical material according to any one of [1] to [6]. Here, “consisting of an optical material” includes both the case where a part of the plastic lens is made of the optical material and the case where the whole plastic lens is made of the optical material. The purpose.

  The present invention contributes to the improvement of the yield and performance of plastic lenses in the field of optical materials such as spectacle lenses and the provision of high-quality substrates.

Hereinafter, the present invention will be described in detail. First, the moisture absorption rate of the present invention will be described.
The moisture absorption rate in the present invention is measured in accordance with the measurement method of water absorption rate of Japanese Industrial Standard JIS K7209, except that the test piece is not placed in distilled water but placed in a constant temperature and humidity control device at a temperature of 60 ° C. and a humidity of 90%. Say what you did. The test period is one day, and the test piece is a square with a side of 50 ± 1 mm and a thickness of 3 ± 0.2 mm.

As a result of intensive studies by the present inventors, it is preferable that the moisture absorption rate is 1.0 × 10 ⁻³ % or less as a high-performance substrate capable of reducing the occurrence of frequency changes and the occurrence of stained spots, 0.9 × 10 ⁻³ % or less is more preferable. If it is 0.8 × 10 ⁻³ % or less, a more preferable result may be given.

The optical material of the present invention is composed of a sulfur atom-containing resin, but in order to adjust its moisture absorption rate to 1.0 × 10 ⁻³ % or less, conventionally known methods used for various resins are used. It can be used as appropriate.

  For example, by limiting the structure of the polymer chain constituting the resin, the moisture absorption rate of the resin can be appropriately increased or decreased. More specifically, in the sulfur atom-containing resin in the present invention, the moisture absorption rate of the resin can be increased or decreased by increasing or decreasing the content of sulfur atoms present in the resin. If the sulfur content in the sulfur atom-containing resin increases, the moisture absorption rate of the resin tends to decrease, and if the sulfur content decreases, the moisture absorption rate tends to increase.

In a material system using a compound having a dithioacetal skeleton or a dithioketal skeleton as in the examples of the present invention, in order to reduce the moisture absorption rate to 1.0 × 10 ⁻³ % or less, addition of a resin modifier or the like Although it may vary depending on the influence of the agent, it is usually preferable to select the compound of the monomer raw material and the mixing ratio so that the content of sulfur atoms present in the resin is 50% by weight or more. It is more preferably 55% by weight or more, and further preferably 60% by weight or more. The preferred sulfur atom content varies depending on the material system, but can be determined by conventionally known data and / or relatively simple experiments.

  Further, the moisture absorption rate of the resin can be appropriately adjusted by adding various resin modifiers as described later.

As described above, from the viewpoint of suppressing frequency change and dyeing spots, it is preferable that the resin has a low moisture absorption rate. However, if the moisture absorption rate is extremely low, it may be difficult to dye or take a long time. There is. From the viewpoint of ease of dyeing, the moisture absorption rate of the resin is usually 0.05 × 10 ⁻³ % or more, preferably 0.08 × 10 ⁻³ % or more, more preferably 0.10 × 10 ⁻³ %. The above is preferable.

  Then, it describes about the sulfur atom containing resin optical material in this invention. The sulfur atom-containing resin in the present invention may be a resin having a sulfur atom in a polymer chain such as a sulfide bond, a disulfide bond, a thiourethane bond or a thioester bond, as long as a sulfur atom is introduced into the polymer chain. Means that. In the case of the present invention, even if the polymer chain does not have a sulfur atom, a resin which is present in the resin in a state where sulfur is dissolved is also treated as a sulfur atom-containing resin.

  Examples of the resin having a sulfide bond or disulfide bond in the polymer chain include those obtained by producing a polymer using a compound having a sulfide bond or disulfide bond in the molecule as a raw material. In addition, there is a case where a sulfide bond is formed by polymerization without having a sulfide bond in advance. Typical examples thereof include resins obtained by polymerizing and curing polyolefin compounds or polyepoxy compounds and polythiol compounds, and resins obtained by ring-opening polymerization of polyepisulfide compounds and polythietane compounds.

Here, a specific example is given. In the present invention, specific examples of polyolefin compounds that can be used in producing a sulfur atom-containing resin include benzyl acrylate, benzyl methacrylate, butoxyethyl acrylate, butoxymethyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxymethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, phenyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethyleneglycol Dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethylene glycol bisglycidyl acrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, 2,2-bis (4-acryloxyethoxyphenyl) propane, 2,2-bis (4-methacryloxyethoxyphenyl) propane, 2,2-bis (4-acryloxy) Ethoxyphenyl) propane, 2,2-bis (4-methacryloxydiethoxyphenyl) propane, bisphenol Diacrylate, bisphenol F dimethacrylate, 1,1-bis (4-acryloxyethoxyphenyl) methane, 1,1-bis (4-methacryloxyethoxyphenyl) methane, 1,1-bis (4-acryloxydiethoxy) Phenyl) methane, 1,1-bis (4-methacryloxydiethoxyphenyl) methane, dimethyloltricyclodecane diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, glycerol diacrylate, glycerol dimethacrylate, pentaerythritol Triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, methylthioacrylate, methylthiomethacrylate, phenylthioacrylate, benzylthio (Meth) acrylate compounds such as methacrylate, xylylene dithiol diacrylate, xylylene dithiol dimethacrylate, mercaptoethyl sulfide diacrylate, mercaptoethyl sulfide dimethacrylate,

  Allyl compounds such as allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate, diethylene glycol bisallyl carbonate, styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinylbenzene, 3,9-divinylspirobi (m -Dioxane), vinyl compounds such as divinyl sulfide and divinyl disulfide, and diisopropenylbenzene are exemplified, but the compound is not limited to the exemplified compounds.

  In the present invention, among these exemplified compounds, those containing a sulfur atom in the molecule are preferred.

  Next, specific examples of usable polyepoxy compounds include polyhydric phenol compounds such as bisphenol A glycidyl ether and polyhydric compounds such as phenolic epoxy compounds obtained by condensation reaction of epihalohydrin compounds and hydrogenated bisphenol A glycidyl ether. Polyhydric compounds such as alcohol-based epoxy compounds obtained by condensation of alcohol compounds and epihalohydrin compounds, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 1,2-hexahydrophthalic acid diglycidyl ester, etc. Glycidyl ester epoxy compounds obtained by condensation of organic acid compounds and epihalohydrin compounds, amine epoxy compounds obtained by condensation of secondary amine compounds and epihalohydrin compounds, etc. And the like b hexene diepoxide and an aliphatic polyvalent epoxy compound.

Specific examples of the sulfide group-containing epoxide compound and the ether group-containing epoxide compound include 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-methylpropane, 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) pen 1,5-bis (2,3-epoxypropylthio) -2-methylpentane, 1,5-bis (2,3-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-epoxy Propylchi Methyl) -3-thiapentane, 1,5-bis (2,3-epoxypropylthio) -2,4-bis (2,3-epoxypropylthiomethyl) -3-thiapentane, 1- (2,3-epoxy Propylthio) -2,2-bis (2,3-epoxypropylthiomethyl) -4-thiahexane, 1,5,6-tris (2,3-epoxypropylthio) -4- (2,3-epoxypropyl) Thiomethyl) -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-epoxypropylthio) -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 -Bis (2,3-epoxypropylthio) -4,7-bis (2,3-epoxypropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epoxypropyl) Chain aliphatic 2,3-epoxypropylthio compounds such as (thio) -5,7-bis (2,3-epoxypropylthiomethyl) -3,6,9-trithiaundecane, and

  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 A 2,3-epoxypropylthio compound, and

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 2 such as phenyl] sulfide, bis [4- (2,3-epoxypropylthio) phenyl] sulfone, 4,4′-bis (2,3-epoxypropylthio) biphenyl , 3-epoxypropylthio compound,
Monofunctional epoxy compounds such as ethylene oxide, propylene oxide, glycidol, epichlorohydrin,

Bis (2,3-epoxypropyl) ether, bis (2,3-epoxypropyloxy) methane, 1,2-bis (2,3-epoxypropyloxy) ethane, 1,2-bis (2,3-epoxy) Propyloxy) propane, 1,3-bis (2,3-epoxypropyloxy) propane, 1,3-bis (2,3-epoxypropyloxy) -2-methylpropane, 1,4-bis (2,3 -Epoxypropyloxy) butane, 1,4-bis (2,3-epoxypropyloxy) -2-methylbutane, 1,3-bis (2,3-epoxypropyloxy) butane, 1,5-bis (2, 3-epoxypropyloxy) pentane, 1,5-bis (2,3-epoxypropyloxy) -2-methylpentane, 1,5-bis (2,3-epoxypropyloxy) 3-thiapentane, 1,6-bis (2,3-epoxypropyloxy) hexane, 1,6-bis (2,3-epoxypropyloxy) -2-methylhexane, 3,8-bis (2,3- Epoxypropyloxy) -3,6-dithiaoctane, 1,2,3-tris (2,3-epoxypropyloxy) propane, 2,2-bis (2,3-epoxypropyloxy) -1,3-bis ( 2,3-epoxypropyloxymethyl) propane, 2,2-bis (2,3-epoxypropyloxymethyl) -1- (2,3-epoxypropyloxy) butane, 1,5-bis (2,3- Epoxypropyloxy) -2- (2,3-epoxypropyloxymethyl) -3-thiapentane, 1,5-bis (2,3-epoxypropyloxy) -2,4-bis (2, -Epoxypropyloxymethyl) -3-thiapentane, 1- (2,3-epoxypropyloxy) -2,2-bis (2,3-epoxypropyloxymethyl) -4-thiahexane, 1,5,6-tris (2,3-epoxypropyloxy) -4- (2,3-epoxypropyloxymethyl) -3-thiahexane, 1,8-bis (2,3-epoxypropyloxy) -4- (2,3-epoxy Propyloxymethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epoxypropyloxy) -4,5-bis (2,3-epoxypropyloxymethyl) -3,6-dithiaoctane, 1, 8-bis (2,3-epoxypropyloxy) -4,4-bis (2,3-epoxypropyloxymethyl) -3,6-dithiaoctane, 1,8-bis ( 2,3-epoxypropyloxy) -2,5-bis (2,3-epoxypropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epoxypropyloxy) -2,4 5-tris (2,3-epoxypropyloxymethyl) -3,6-dithiaoctane, 1,1,1-tris [[2- (2,3-epoxypropyloxy) ethyl] thiomethyl] -2- (2, 3-epoxypropyloxy) ethane, 1,1,2,2-tetrakis [[2- (2,3-epoxypropyloxy) ethyl] thiomethyl] ethane, 1,11-bis (2,3-epoxypropyloxy) -4,8-bis (2,3-epoxypropyloxymethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epoxypropyloxy) -4,7-bis 2,3-epoxypropyloxymethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epoxypropyloxy) -5,7-bis (2,3-epoxypropyloxymethyl) Chain aliphatic 2,3-epoxypropyloxy compounds such as -3,6,9-trithiaundecane, and

  1,3-bis (2,3-epoxypropyloxy) cyclohexane, 1,4-bis (2,3-epoxypropyloxy) cyclohexane, 1,3-bis (2,3-epoxypropyloxymethyl) cyclohexane, 1 , 4-bis (2,3-epoxypropyloxymethyl) cyclohexane, 2,5-bis (2,3-epoxypropyloxymethyl) -1,4-dithiane, 2,5-bis [[2- (2, Cyclic epoxy such as 3-epoxypropyloxy) ethyl] thiomethyl] -1,4-dithiane, 2,5-bis (2,3-epoxypropyloxymethyl) -2,5-dimethyl-1,4-dithiane 2,3-epoxypropyloxy compounds, and

  1,2-bis (2,3-epoxypropyloxy) benzene, 1,3-bis (2,3-epoxypropyloxy) benzene, 1,4-bis (2,3-epoxypropyloxy) benzene, 1, 2-bis (2,3-epoxypropyloxymethyl) benzene, 1,3-bis (2,3-epoxypropyloxymethyl) benzene, 1,4-bis (2,3-epoxypropyloxymethyl) benzene, bis [4- (2,3-epoxypropyloxy) phenyl] methane, 2,2-bis [4- (2,3-epoxypropyloxy) phenyl] propane, bis [4- (2,3-epoxypropyloxy) Phenyl] sulfide, bis [4- (2,3-epoxypropyloxy) phenyl] sulfone, 4,4′-bis (2,3-epoxypropyloxy) It can be exemplified aromatic 2,3-epoxypropyloxy compounds such biphenyl, but is not limited only to the exemplified compounds.

  In the present invention, among these exemplified compounds, those containing a sulfur atom in the molecule are preferred.

Next, specific examples of usable polythiol compounds include 1,1-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), diethylene glycol 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-mercapto Ace ), Ethylene glycol bis (3-mercaptopropionate), trimethylolpropane bis (2-mercaptoacetate), trimethylolpropane bis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), Aliphatic polythiol compounds such as pentaerythritol tetrakis (3-mercaptopropionate) and tetrakis (mercaptomethyl) methane;

  1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 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, 1,3,3 5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mer Puttoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,3-di (p-methoxyphenyl) propane-2,2-dithiol, Aromatic polythiols such as 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) ) Aromatic polythiol compounds containing sulfur atoms in addition to mercapto groups such as benzene, 1,3,5-tris (mercaptoethylthio) benzene, and their nuclear alkylates,

Bis (mercaptomethyl) sulfide, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) sulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) Methane, bis (3-mercaptopropylthio) methane, 1,2-bis (mercaptomethylthio) ethane, 1,2-bis (2-mercaptoethylthio) ethane, 1,2-bis (3-mercaptopropyl) ethane, 1,3-bis (mercaptomethylthio) propane, 1,3-bis (2-mercaptoethylthio) propane, 1,3-bis (3-mercaptopropylthio) propane, 1,2,3-tris (mercaptomethylthio) Propane, 1,2,3-tris (2- Lucaptoethylthio) propane, 1,2,3-tris (3-mercaptopropylthio) propane, 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane, 4,8-dimercaptomethyl -1,11-mercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1 , 11-mercapto-3,6,9-trithiaundecane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3 -Dimercaptopropyl) sulfide, bis (1,3-dimercaptopropyl) sulfide, 2,5-di Lucapto-1,4-dithiane, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, bis (mercaptomethyl) disulfide, bis (Mercaptoethyl) disulfide, aliphatic polythiol compounds containing sulfur atoms in addition to mercapto groups such as bis (mercaptopropyl) disulfide, and esters of these thioglycolic acid and mercaptopropionic acid,

  Hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate), 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), hydroxypropyl 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), thiodiglycolic acid bis (2-mercaptoethyl ester), thiodi Propionic acid bis (2-mercaptoethyl ester), 4,4-thiodibutyric acid bis (2-mercaptoethyl ester), dithiodiglycolic acid bis (2-mercaptoethyl ester), dithiodipropionic acid bis (2-mercaptoethyl ester) ), 4,4-dithio Dibutyl acid bis (2-mercaptoethyl ester), thiodiglycolic acid bis (2,3-dimercaptopropyl ester), thiodipropionic acid bis (2,3-dimercaptopropyl ester), dithioglycolic acid bis (2, 3-dimercaptopropyl ester), dithiodipropionic acid bis (2,3-dimercaptopropyl ester) and other mercapto groups, aliphatic polythiol compounds containing a sulfur atom and an ester bond, and 3,4-thiophenedithiol , Heterocyclic compounds containing a sulfur atom in addition to a mercapto group such as 2,5-dimercapto-1,3,4-thiadiazole,

  2-mercaptoethanol, 3-mercapto-1,2-propanediol, glycerol di (mercaptoacetate), 1-hydroxy-4-mercaptocyclohexane, 2,4-dimercaptophenol, 2-mercaptohydroquinone, 4-mercaptophenol, 3,4-dimercapto-2-propanol, 1,3-dimercapto-2-propanol, 2,3-dimercapto-1-propanol, 1,2-dimercapto-1,3-butanediol, pentaerythritol tris (3-mercapto Propionate), pentaerythritol mono (3-mercaptopropionate), pentaerythritol bis (3-mercaptopropionate), pentaerythritol tris (thioglycolate), dipentaerythritol pentakis (3 Mercaptopropionate), hydroxymethyl - tris (mercaptoethylthiomethyl) methane, compounds containing 1-hydroxyethyl-thio-3-mercaptoethyl hydroxy group other than the mercapto group of thio benzene,

1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiacyclohexane, 1, 1,5,5-tetrakis (mercaptomethylthio) -3-thiapentane, 1,1,6,6-tetrakis (mercaptomethylthio) -3,4-dithiahexane, 2,2-bis (mercaptomethylthio) ethanethiol, 2- (4,5-Dimercapto-2-thiapentyl) -1,3-dithiacyclopentane, 2,2-bis (mercaptomethyl) -1,3-dithiacyclopentane, 2,5-bis (4,4- Bis (mercaptomethylthio) -2-thiabutyl) -1,4-dithiane, 2,2-bis (mercaptomethylthio) -1,3-propa Dithiol, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3,6-bis (mercaptomethylthio) -1,9-dimercapto-2,5,8-trithianonane, 4,6-bis (mercapto) Methylthio) -1,9-dimercapto-2,5,8-trithianonane, 3-mercaptomethylthio-1,6-dimercapto-2,5-dithiahexane, 2- (2,2-bis (mercaptomethylthio) ethyl) -1 , 3-dithietane, 1,1,9,9-tetrakis (mercaptomethylthio) -5- (3,3-bis (mercaptomethylthio) -1-thiapropyl) 3,7-dithianonane, tris (2,2-bis ( Mercaptomethylthio) ethyl) methane, tris (4,4-bis (mercaptomethylthio) -2-thiabutyl) me , Tetrakis (2,2-bis (mercaptomethylthio) ethyl) methane, tetrakis (4,4-bis (mercaptomethylthio) -2-thiabutyl) methane, 3,5,9,11-tetrakis (mercaptomethylthio) -1 , 13-dimercapto-2,6,8,12-tetrathiatridecane, 3,5,9,11,15,17-hexakis (mercaptomethylthio) -1,19-dimercapto-2,6,8,12, 14,18-hexathiononadecane, 9- (2,2-bis (mercaptomethylthio) ethyl) -3,5,13,15-tetrakis (mercaptomethylthio) -1,17-dimercapto-2,6,8, 10,12,16-hexathiaheptadecane, 3,4,8,9-tetrakis (mercaptomethylthio) -1,11-dimercapto-2 , 5,7,10-tetrathiaundecane, 3,4,8,9,13,14-hexakis (mercaptomethylthio) -1,16-dimercapto-2,5,7,10,12,15-hexathiahexadecane 8- {bis (mercaptomethylthio) methyl} -3,4,12,13-tetrakis (mercaptomethylthio) -1,15-dimercapto-2,5,7,9,11,14-hexathiapentadecane, 4, 6-bis {3,5-bis (mercaptomethylthio) -7-mercapto-2,6-dithiaheptylthio} -1,3-dithiane, 4- {3,5-bis (mercaptomethylthio) -7-mercapto -2,6-dithiaheptylthio} -6-mercaptomethylthio-1,3-dithiane, 1,1-bis {4- (6-mercaptomethylthio) -1,3-dithi Nilthio} -3,3-bis (mercaptomethylthio) propane, 1,3-bis {4- (6-mercaptomethylthio) -1,3-dithianylthio} -1,3-bis (mercaptomethylthio) propane, 1- { 4- (6-Mercaptomethylthio) -1,3-dithianylthio} -3- {2,2-bis (mercaptomethylthio) ethyl} -7,9-bis (mercaptomethylthio) -2,4,6,10-tetra Thiaundecane, 1- {4- (6-mercaptomethylthio) -1,3-dithianylthio} -3- {2- (1,3-dithietanyl)} methyl-7,9-bis (mercaptomethylthio) -2,4 , 6,10-tetrathiaundecane, 1,5-bis {4- (6-mercaptomethylthio) -1,3-dithianylthio} -3- {2- (1,3-dithieta L)} methyl-2,4-dithiapentane, 4,6-bis [3- {2- (1,3-dithietanyl)} methyl-5-mercapto-2,4-dithiapentylthio] -1,3- Dithiane, 4,6-bis {4- (6-mercaptomethylthio) -1,3-dithianylthio} -1,3-dithiane, 4- {4- (6-mercaptomethylthio) -1,3-dithianylthio} -6 -{4- (6-mercaptomethylthio) -1,3-dithianylthio} -1,3-dithiane, 3- {2- (1,3-dithietanyl)} methyl-7,9-bis (mercaptomethylthio) -1 , 11-dimercapto-2,4,6,10-tetrathiaundecane, 9- {2- (1,3-dithietanyl)} methyl-3,5,13,15-tetrakis (mercaptomethylthio) -1,17- Zimmerka Put-2,6,8,10,12,16-hexathiaheptadecane, 3- {2- (1,3-dithietanyl)} methyl-7,9,13,15-tetrakis (mercaptomethylthio) -1, 17-dimercapto-2,4,6,10,12,16-hexathiaheptadecane, 3,7-bis {2- (1,3-dithietanyl)} methyl-1,9-dimercapto-2,4
, 6,8-tetrathianonane, 4- {3,4,8,9-tetrakis (mercaptomethylthio) -11-mercapto-2,5,7,10-tetrathiaundecyl} -5-mercaptomethylthio-1 , 3-dithiolane, 4,5-bis {3,4-bis (mercaptomethylthio) -6-mercapto-2,5-dithiahexylthio} -1,3-dithiolane, 4- {3,4-bis ( Mercaptomethylthio) -6-mercapto-2,5-dithiahexylthio} -5-mercaptomethylthio-1,3-dithiolane, 4- {3-bis (mercaptomethylthio) methyl-5,6-bis (mercaptomethylthio) -8-mercapto-2,4,7-trithiaoctyl} -5-mercaptomethylthio-1,3-dithiolane, 2- [bis {3,4-bis (mercaptomethyl) E) -6-mercapto-2,5-dithiahexylthio} methyl] -1,3-dithietane, 2- {3,4-bis (mercaptomethylthio) -6-mercapto-2,5-dithiahexylthio } Mercaptomethylthiomethyl-1,3-dithietane, 2- {3,4,8,9-tetrakis (mercaptomethylthio) -11-mercapto-2,5,7,10-tetrathiaundecylthio} mercaptomethylthiomethyl- 1,3-dithietane, 2- {3-bis (mercaptomethylthio) methyl-5,6-bis (mercaptomethylthio) -8-mercapto-2,4,7-trithiaoctyl} mercaptomethylthiomethyl-1,3- Dithietane, 4,5-bis [1- {2- (1,3-dithietanyl)}-3-mercapto-2-thiapropylthio] -1,3-di Oran, 4- [1- {2- (1,3-dithietanyl)}-3-mercapto-2-thiapropylthio] -5- {1,2-bis (mercaptomethylthio) -4-mercapto-3-thiabutylthio } -1,3-dithiolane, 2- [bis {4- (5-mercaptomethylthio-1,3-dithiolanyl) thio}] methyl-1,3-dithietane, 4- {4- (5-mercaptomethylthio-1) , 3-dithiolanyl) thio} -5- [1- {2- (1,3-dithietanyl)}-3-mercapto-2-thiapropylthio] -1,3-dithiolane, and dithioacetals such as these oligomers Or a compound having a dithioketal skeleton,

  Tris (mercaptomethylthio) methane, tris (mercaptoethylthio) methane, 1,1,5,5-tetrakis (mercaptomethylthio) -2,4-dithiapentane, bis [4,4-bis (mercaptomethylthio) -1,3 -Dithiabutyl] (mercaptomethylthio) methane, tris [4,4-bis (mercaptomethylthio) -1,3-dithiabutyl] methane, 2,4,6-tris (mercaptomethylthio) -1,3,5-trithiacyclohexane 2,4-bis (mercaptomethylthio) -1,3,5-trithiacyclohexane, 1,1,3,3-tetrakis (mercaptomethylthio) -2-thiapropane, bis (mercaptomethyl) methylthio-1,3 5-trithiacyclohexane, tris [(4-mercaptomethyl-2,5-dithi Cyclohexyl-1-yl) methylthio] methane, 2,4-bis (mercaptomethylthio) -1,3-dithiacyclopentane, 2-mercaptoethylthio-4-mercaptomethyl-1,3-dithiacyclopentane, 2 -(2,3-dimercaptopropylthio) -1,3-dithiacyclopentane, 4-mercaptomethyl-2- (2,3-dimercaptopropylthio) -1,3-dithiacyclopentane, 4- Mercaptomethyl-2- (1,3-dimercapto-2-propylthio) -1,3-dithiacyclopentane, tris [2,2-bis (mercaptomethylthio) -1-thiaethyl] methane, tris [3,3- Bis (mercaptomethylthio) -2-thiapropyl] methane, tris [4,4-bis (mercaptomethylthio) -3-thiabutyl] me 2,4,6-tris [3,3-bis (mercaptomethylthio) -2-thiapropyl] -1,3,5-trithiacyclohexane, tetrakis [3,3-bis (mercaptomethylthio) -2-thiapropyl ] Compounds having ortho-trithioformate skeleton such as methane and further oligomers thereof,

3,3′-di (mercaptomethylthio) -1,5-dimercapto-2,4-dithiapentane, 2,2′-di (mercaptomethylthio) -1,3-dithiacyclopentane, 2,7-di (mercapto) Methyl) -1,4,5,9-tetrathiaspiro [4,4] nonane, 3,
Examples include 9-dimercapto-1,5,7,11-tetrathiaspiro [5,5] undecane, and compounds having an orthotetrathiocarbonate skeleton such as these oligomers, but are limited to these exemplified compounds. It is not something. These exemplary compounds may be used alone or in combination of two or more.

    Of these compounds, it is preferable to select an aliphatic polythiol compound rather than an aromatic one in consideration of the optical properties of the resulting resin, particularly the Abbe number. Further, in view of optical properties, particularly refractive index requirements, it is more preferable to select a compound having a sulfur atom in addition to a thiol group such as a sulfide bond and / or a disulfide bond. A dithioacetal skeleton, a dithioketal skeleton, an orthotrithioformate skeleton More preferably, a compound having an orthotetrathiocarbonate skeleton is selected. In order to increase the three-dimensional crosslinkability in consideration of the heat resistance of the resulting resin, it is particularly preferable to select one or more polythiol compounds having three or more functionalities.

  As the most preferred polythiol in the above points, 2,5-bis (mercaptomethyl) -1,4-dithiane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl -1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1 , 11-dimercapto-3,6,9-trithiaundecane, 1,1,1,1-tetrakis (mercaptomethyl) methane, 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2 , 2-tetrakis (mercaptomethylthio) ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, 2- (2,2-bis (me Captomethylthio) ethyl) -1,3-dithietane is a compound selected from at least one compound having three or more functional groups, and at least one compound having at least one compound selected from two or more functional groups. It is done.

Subsequently, specific examples of the polyepisulfide compound that can be used in the production of the sulfur atom-containing resin in the present invention include bis (1,2-epithioethyl) sulfide, bis (1,2-epithioethyl) disulfide, bis (epi Epithioethyl compounds such as thioethylthio) methane, bis (epithioethylthio) benzene, bis [4- (epithioethylthio) phenyl] sulfide, bis [4- (epithioethylthio) phenyl] methane, bis (2 , 3-epithiopropyl) sulfide, bis (2,3-epithiopropyl) disulfide, bis (2,3-epithiopropylthio) methane, 1,2-bis (2,3-epithiopropylthio) ethane 1,2-bis (2,3-epithiopropylthio) propane, 1,3-bis (2,3-epithiop) Pyrthio) propane, 1,3-bis (2,3-epithiopropylthio) -2-methylpropane, 1,4-bis (2,3-epithiopropylthio) butane, 1,4-bis (2, 3-epithiopropylthio) -2-methylbutane, 1,3-bis (2,3-epithiopropylthio) butane, 1,5-bis (2,3-epithiopropylthio) pentane, 1,5- Bis (2,3-epithiopropylthio) -2-methylpentane, 1,5-bis (2,3-epithiopropylthio) -3-thiapentane, 1,6-bis (2,3-epithiopropyl) Thio) hexane, 1,6-bis (2,3-epithiopropylthio) -2-methylhexane, 3,8-bis (2,3-epithiopropylthio) -3,6-dithiaoctane, 1,2 , 3-Tris (2,3-epithio Lopyrthio) propane, 2,2-bis (2,3-epithiopropylthio) -1,3-bis (2,3-epithiopropylthiomethyl) propane, 2,2-bis (2,3-epithio) Propylthiomethyl) -1- (2,3-epithiopropylthio) butane, 1,5-bis (2,3-epithiopropylthio) -2- (2,3-epithiopropylthiomethyl) -3 -Thiapentane, 1,5-bis (2,3-epithiopropylthio) -2,4-bis (2,3-epithiopropylthiomethyl) -3-thiapentane, 1- (2,3-epithiopropyl) Thio) -2,2-bis (2,3-epithiopropylthiomethyl) -4-thiahexane, 1,5,6-tris (2,3-epithiopropylthio) -4- (2,3-epi Thiopropylthiomethyl) -3-thiahexahex 1,8-bis (2,3-epithiopropylthio) -4- (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithio) Propylthio) -4,5-bis (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropylthio) -4,4-bis (2 , 3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropylthio) -2,5-bis (2,3-epithiopropylthiomethyl) -3 , 6-dithiaoctane, 1,8-bis (2,3-epithiopropylthio) -2,4,5-tris (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,1, 1-tris [[2- (2,3-epithiopropylthiol ) Ethyl] thiomethyl] -2- (2,3-epithiopropylthio) ethane, 1,1,2,2-tetrakis [[2- (2,3-epithiopropylthio) ethyl] thiomethyl] ethane, , 11-bis (2,3-epithiopropylthio) -4,8-bis (2,3-epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (2, 3-epithiopropylthio) -4,7-bis (2,3-epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epithiopropylthio) Chain aliphatic 2,3-epithiopropylthio compounds such as -5,7-bis (2,3-epithiopropylthiomethyl) -3,6,9-trithiaundecane, and

  1,3-bis (2,3-epithiopropylthio) cyclohexane, 1,4-bis (2,3-epithiopropylthio) cyclohexane, 1,3-bis (2,3-epithiopropylthiomethyl) Cyclohexane, 1,4-bis (2,3-epithiopropylthiomethyl) cyclohexane, 2,5-bis (2,3-epithiopropylthiomethyl) -1,4-dithiane, 2,5-bis [[ 2- (2,3-epithiopropylthio) ethyl] thiomethyl] -1,4-dithiane, 2,5-bis (2,3-epithiopropylthiomethyl) -2,5-dimethyl-1,4- Cycloaliphatic 2,3-epithiopropylthio compounds such as dithiane, and

  1,2-bis (2,3-epithiopropylthio) benzene, 1,3-bis (2,3-epithiopropylthio) benzene, 1,4-bis (2,3-epithiopropylthio) benzene 1,2-bis (2,3-epithiopropylthiomethyl) benzene, 1,3-bis (2,3-epithiopropylthiomethyl) benzene, 1,4-bis (2,3-epithiopropyl) Thiomethyl) benzene, bis [4- (2,3-epithiopropylthio) phenyl] methane, 2,2-bis [4- (2,3-epithiopropylthio) phenyl] propane, bis [4- ( 2,3-epithiopropylthio) phenyl] sulfide, bis [4- (2,3-epithiopropylthio) phenyl] sulfone, 4,4′-bis (2,3-epithiopropylthio) biphenyl, etc. Aromatic , 3-epithiopropylthio compound,

Bis (2,3-epithiopropyldithio) methane, bis (2,3-epithiopropyldithio) ethane, bis (6,7-epithio-3,4-dithiaheptyl) sulfide, bis (6,7-epithio- 3,4-dithiaheptyl) disulfide, 1,4-dithian-2,5-bis (2,3-epithiopropyldithiomethyl), 1,3-bis (2,3-epithiopropyldithiomethyl) benzene, , 6-Bis (2,3-epithiopropyldithiomethyl) -2- (2,3-epithiopropyldithioethylthio) -4-thiahexane, 1,2,3-tris (2,3-epithiopropyl) Dithio) propane, 1,1,1,1-tetrakis (2,3-epithiopropyldithiomethyl) methane, 1,3-bis (2,3-epithiopropyldithio) -2-thiapro 1,4-bis (2,3-epithiopropyldithio) -2,3-dithiabutane, 1,1,1-tris (2,3-epithiopropyldithio) methane, 1,1,1-tris (2,3-epithiopropyldithiomethylthio) methane, 1,1,2,2-tetrakis (2,3-epithiopropyldithio) ethane, 1,1,2,2-tetrakis (2,3-epithio) Propyldithiomethylthio) ethane, 1,1,3,3-tetrakis (2,3-epithiopropyldithio) propane, 1,1,3,3-tetrakis (2
, 3-epithiopropyldithiomethylthio) propane, 2- [1,1-bis (2,3-epithiopropyldithio) methyl] -1,3-dithietane, 2- [1,1-bis (2,3 A compound having a 2,3-epithiopropyldithio skeleton, such as -epithiopropyldithiomethylthio) methyl] -1,3-dithietane,

  Monofunctional episulfide compounds such as ethylene sulfide, propylene sulfide, 3-mercaptopropylene sulfide, 4-mercaptobutene sulfide, epithiochlorohydrin,

  Bis (2,3-epithiopropyl) ether, bis (2,3-epithiopropyloxy) methane, 1,2-bis (2,3-epithiopropyloxy) ethane, 1,2-bis (2, 3-epithiopropyloxy) propane, 1,3-bis (2,3-epithiopropyloxy) propane, 1,3-bis (2,3-epithiopropyloxy) -2-methylpropane, 1,4 -Bis (2,3-epithiopropyloxy) butane, 1,4-bis (2,3-epithiopropyloxy) -2-methylbutane, 1,3-bis (2,3-epithiopropyloxy) butane 1,5-bis (2,3-epithiopropyloxy) pentane, 1,5-bis (2,3-epithiopropyloxy) -2-methylpentane, 1,5-bis (2,3-epi Thiopropyloxy) 3-thiapentane, 1,6-bis (2,3-epithiopropyloxy) hexane, 1,6-bis (2,3-epithiopropyloxy) -2-methylhexane, 3,8-bis (2, 3-epithiopropyloxy) -3,6-dithiaoctane, 1,2,3-tris (2,3-epithiopropyloxy) propane, 2,2-bis (2,3-epithiopropyloxy) -1 , 3-bis (2,3-epithiopropyloxymethyl) propane, 2,2-bis (2,3-epithiopropyloxymethyl) -1- (2,3-epithiopropyloxy) butane, 1, 5-bis (2,3-epithiopropyloxy) -2- (2,3-epithiopropyloxymethyl) -3-thiapentane, 1,5-bis (2,3-epithiopropyloxy) -2, 4-bis (2, -Epithiopropyloxymethyl) -3-thiapentane, 1- (2,3-epithiopropyloxy) -2,2-bis (2,3-epithiopropyloxymethyl) -4-thiahexane, 1,5, 6-Tris (2,3-epithiopropyloxy) -4- (2,3-epithiopropyloxymethyl) -3-thiahexane, 1,8-bis (2,3-epithiopropyloxy) -4- (2,3-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropyloxy) -4,5-bis (2,3-epithiopropyloxymethyl) 3,6-dithiaoctane, 1,8-bis (2,3-epithiopropyloxy) -4,4-bis (2,3-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8- Screw( 2,3-epithiopropyloxy) -2,5-bis (2,3-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropyloxy) -2 , 4,5-tris (2,3-epithiopropyloxymethyl) -3,6-dithiaoctane, 1,1,1-tris [[2- (2,3-epithiopropyloxy) ethyl] thiomethyl]- 2- (2,3-epithiopropyloxy) ethane, 1,1,2,2-tetrakis [[2- (2,3-epithiopropyloxy) ethyl] thiomethyl] ethane, 1,11-bis (2 , 3-epithiopropyloxy) -4,8-bis (2,3-epithiopropyloxymethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epithiopropyloxy) ) -4,7-Bis 2,3-epithiopropyloxymethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epithiopropyloxy) -5,7-bis (2,3-epithiopropyl) Chain aliphatic 2,3-epithiopropyloxy compounds such as (oxymethyl) -3,6,9-trithiaundecane, and

1,3-bis (2,3-epithiopropyloxy) cyclohexane, 1,4-bis (2,3-epithiopropyloxy) cyclohexane, 1,3-bis (2,3-epithiopropyloxymethyl) Cyclohexane, 1,4-bis (2,3-epithiopropyloxymethyl) cyclohexane, 2,5-bis (2,3-epithiopropyloxymethyl) -1,4-dithiane, 2,5-bis [[ 2- (2,3-epithiopropyloxy) ethyl] thiomethyl] -1,4-dithiane, 2,5-bis (2,3-epithiopropyloxymethyl) -2,5-dimethyl-1,4- Cycloaliphatic 2,3-epithiopropyloxy compounds such as dithiane, and

  1,2-bis (2,3-epithiopropyloxy) benzene, 1,3-bis (2,3-epithiopropyloxy) benzene, 1,4-bis (2,3-epithiopropyloxy) benzene 1,2-bis (2,3-epithiopropyloxymethyl) benzene, 1,3-bis (2,3-epithiopropyloxymethyl) benzene, 1,4-bis (2,3-epithiopropyl) Oxymethyl) benzene, bis [4- (2,3-epithiopropyloxy) phenyl] methane, 2,2-bis [4- (2,3-epithiopropyloxy) phenyl] propane, bis [4- ( 2,3-epithiopropyloxy) phenyl] sulfide, bis [4- (2,3-epithiopropyloxy) phenyl] sulfone, 4,4′-bis (2,3-epithiopropyloxy) It can be exemplified aromatic 2,3-epithiopropyl oxy compounds such biphenyl, but is not limited only to the exemplified compounds.

Among the exemplified compounds, preferred compounds include bis (1,2-epithioethyl) sulfide, bis (1,2-epithioethyl) disulfide, bis (2,3-epithiopropyl) sulfide, and bis (2,3-epithiopropyl). Thio) methane and bis (2,3-epithiopropyl) disulfide, bis (2,3-epithiopropyldithio) methane, bis (2,3-epithiopropyldithio) ethane, bis (6,7-epithio- 3,4-dithiaheptyl) sulfide, bis (6,7-epithio-3,4-dithiaheptyl) disulfide, 1,4-dithian-2,5-bis (2,3-epithiopropyldithiomethyl), 1,3 -Bis (2,3-epithiopropyldithiomethyl) benzene, 1,6-bis (2,3-epithiopropyldithiomethyl) -2 (2,3-epithiopropyldithioethylthio) -4-thiahexane, 1,2,3-tris (2,3-epithiopropyldithio) propane, 1,1,1,1-tetrakis (2,3- Epithiopropyldithiomethyl) methane, 1,3-bis (2,3-epithiopropyldithio) -2-thiapropane, 1,4-bis (2,3-epithiopropyldithio) -2,3-dithiabutane, 1,1,1-tris (2,3-epithiopropyldithio) methane, 1,1,1-tris (2,3-epithiopropyldithiomethylthio) methane, 1,1,2,2-tetrakis (2 , 3-epithiopropyldithio) ethane, 1,1,2,2-tetrakis (2,3-epithiopropyldithiomethylthio) ethane, 1,1,3,3-tetrakis (2,3-epithiopropyl) Thio) propane, 1,1,3,3-tetrakis (2,3-epithiopropyldithiomethylthio) propane, 2- [1,1-bis (2,3-epithiopropyldithio) methyl] -1,3 -Dithietane, 2- [1,1-bis (2,3-epithiopropyldithiomethylthio) methyl] -1,3-dithietane, and more preferable compounds are bis (1,2-epithioethyl) sulfide, bis ( 1,2-epithioethyl) disulfide, and bis (2,3-epithiopropyl) disulfide, bis (2,3-epithiopropyldithio) methane, bis (2,3-epithiopropyldithio) ethane, bis (6 , 7-epithio-3,4-dithiaheptyl) sulfide, bis (6,7-epithio-3,4-dithiaheptyl) disulfide, 1,4-dithia 2,5-bis (2,3-epithiopropyldithiomethyl), 1,3-bis (2,3-epithiopropyldithiomethyl) benzene, 1,6-bis (2,3-epithiopropyl) Dithiomethyl) -2- (2,3-epithiopropyldithioethylthio) -4-thiahexane, 1,2,3-tris (2,3-epithiopropyldithio) propane, 1,1,1,1- Tetrakis (2,3-epithiopropyldithiomethyl) methane, 1,3-bis (2,3-epithiopropyldithio) -2-thiapropane, 1,4-bis (2,3-epithiopropyldithio)- 2,3-dithiabutane, 1,1,1-tris (2,3-epithiopropyldithio) methane, 1,1,1-tris (2,3-epithiopropyldithiomethylthio)
Methane, 1,1,2,2-tetrakis (2,3-epithiopropyldithio) ethane, 1,1,2,2-tetrakis (2,3-epithiopropyldithiomethylthio) ethane, 1,1,3 , 3-tetrakis (2,3-epithiopropyldithio) propane, 1,1,3,3-tetrakis (2,3-epithiopropyldithiomethylthio) propane, 2- [1,1-bis (2,3 -Epithiopropyldithio) methyl] -1,3-dithietane and 2- [1,1-bis (2,3-epithiopropyldithiomethylthio) methyl] -1,3-dithietane.

  Examples of the resin having a thiourethane bond or a thioester bond in the polymer chain include a polymer produced from a compound having a thiourethane bond or a thioester bond in the molecule. About the compound which has a thioester bond, what is necessary is just to use the compound which has a thioester bond among the above-mentioned exemplary compounds. In addition, there is a case where a thiourethane bond is formed by polymerization without having a thiourethane bond in advance. A typical example thereof is a resin obtained by polymerizing and curing the aforementioned polythiol compound and polyisocyanate compound.

  In the present invention, specific examples of polyiso (thio) cyanate compounds that can be used for producing a sulfur atom-containing resin include hexamethylene diisocyanate, 2,2-dimethylpentane diisocyanate, and 2,2,4-trimethyl. Hexane diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecatriisocyanate, 1, 3,6-hexamethylene triisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, lysine diisocyanatomethyl ester, lysine triisocyanate Xylylene diisocyanate, (Isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, α, α, α ', α'-tetramethylxylylene diisocyanate, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis Aliphatic polyisocyanate compounds such as (isocyanatomethyl) diphenyl ether, bis (isocyanatoethyl) phthalate, mesityrylene triisocyanate, 2,6-di (isocyanatomethyl) furan,

  Isophorone diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2-dimethyldicyclohexylmethane diisocyanate, 2, 5-bis (isocyanatomethyl) bicyclo- [2,2,1] -heptane, 2,6-bis (isocyanatomethyl) bicyclo- [2,2,1] -heptane, 3,8-bis (isocyanato Fats such as methyl) tricyclodecane, 3,9-bis (isocyanatomethyl) tricyclodecane, 4,8-bis (isocyanatomethyl) tricyclodecane, 4,9-bis (isocyanatomethyl) tricyclodecane Cyclic polyisocyanate compounds,

Phenylene diisocyanate, tolylene diisocyanate, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate , Biphenyl diisocyanate, toluidine diisocyanate, 4,4-diphenylmethane diisocyanate, 3,3-dimethyldiphenylmethane-4,4-diisocyanate, bibenzyl-4,4-diisocyanate, bis (isocyanatophenyl ) Ethylene, 3,3-dimethoxybiphenyl-4,4-diisocyanate, phenylisocyanatoethyl isocyanate, hexahydrobenzene diiso Annatto, aromatic polyisocyanate compound such as hexahydroterephthalic diphenylmethane-4,4-diisocyanate,

  Bis (isocyanatomethyl) sulfide, bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, bis (isocyanatohexyl) sulfide, bis (isocyanatomethyl) sulfone, bis (isocyanatomethyl) disulfide, bis ( Isocyanatoethyl) disulfide, bis (isocyanatopropyl) disulfide, bis (isocyanatomethylthio) methane, bis (isocyanatoethylthio) methane, bis (isocyanatoethylthio) ethane, bis (isocyanatomethylthio) ethane, 1, Sulfur-containing aliphatic isocyanate compounds such as 5-diisocyanato-2-isocyanatomethyl-3-thiapentane,

  Diphenyl sulfide-2,4-diisocyanate, diphenyl sulfide-4,4-diisocyanate, 3,3-dimethoxy-4,4-diisocyanatodibenzylthioether, bis (4-isocyanatomethylbenzene) sulfide, Aromatic sulfide isocyanate compounds such as 4,4-methoxybenzenethioethylene glycol-3,3-diisocyanate,

  Diphenyl disulfide-4,4-diisocyanate, 2,2-dimethyldiphenyl disulfide-5,5-diisocyanate, 3,3-dimethyldiphenyl disulfide-5,5-diisocyanate, 3,3-dimethyldiphenyl disulfide 6,6-diisocyanate, 4,4-dimethyldiphenyl disulfide-5,5-diisocyanate, 3,3-dimethoxydiphenyl disulfide-4,4-diisocyanate, 4,4-dimethoxydiphenyl disulfide-3 Aromatic disulfide-based isocyanate compounds such as 1,3-diisocyanate, sulfur-containing heterocyclic compounds such as 2,5-diisocyanatothiophene, 2,5-bis (isocyanatomethyl) thiophene,

  In addition, 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, 4,5-bis (isocyanatomethyl) -1,3-dithiolane, 4, Examples thereof include 5-bis (isocyanatomethyl) -2-methyl-1,3-dithiolane, but are not limited to the exemplified compounds. In addition, halogen-substituted products such as chlorine-substituted products, bromine-substituted products, alkyl-substituted products, alkoxy-substituted products, nitro-substituted products, prepolymer-modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, and burette-modified products. Bodies, dimerization or trimerization reaction products can also be used.

  Further, specific examples of the isothiocyanate compound include methyl isothiocyanate, ethyl isothiocyanate, n-propyl thioisocyanate, isopropyl isothiocyanate, n-butyl isothiocyanate, sec-butyl isothiocyanate, tert- Butyl isothiocyanate, pentyl isothiocyanate, hexyl isothiocyanate, heptyl isothiocyanate, octyl isothiocyanate, decyl isothiocyanate, lauryl isothiocyanate, myristyl isothiocyanate, octadecyl isothiocyanate, 3-pentyl isothiocyanate Narate, 2-ethylhexyl isothiocyanate, 2,3-dimethylcyclohexyl isothiocyanate, 2-methoxyphenyl isothiocyanate, 4-methoxyphenyl Nyl isothiocyanate, α-methylbenzyl isothiocyanate, phenylethyl isothiocyanate, phenyl isothiocyanate, o-, m-, or p-tolyl isothiocyanate, cyclohexyl isothiocyanate, benzyl isothiocyanate, isothiocyanate Monofunctional isothiocyanate compounds such as natomethylbicycloheptane,

  Aliphatic polyisothiocyanate compounds such as 1,6-diisothiocyanatohexane and p-phenyleneisopropylidenediisothiocyanate,

Cycloaliphatic diisothiocyanate, alicyclic polyisothiocyanate compounds such as diisothiocyanatomethylbicycloheptane,

  1,2-diisothiocyanatobenzene, 1,3-diisothiocyanatobenzene, 1,4-diisothiocyanatobenzene, 2,4-diisothiocyanatotoluene, 2,5-diisothiocyanato-m Xylene, 4,4-diisothiocyanato-1,1-biphenyl, 1,1-methylenebis (4-isothiocyanatobenzene), 1,1-methylenebis (4-isothiocyanato-2-methylbenzene), 1, 1-methylenebis (4-isothiocyanato-3-methylbenzene), 1,1- (1,2-ethanediyl) bis (isothiocyanatobenzene), 4,4-diisothiocyanatobenzophenone, 4,4-diisothiocyana -3,3-dimethylbenzophenone, diphenyl ether-4,4-diisothiocyanate, diphenylamine-4,4-di Aromatic isothiocyanate compounds such as soothiocyanate, further 1,3-benzenedicarbonyldiisothiocyanate, 1,4-benzenedicarbonyldiisothiocyanate, (2,2-pyridine) -4,4-di Examples include carbonyl isothiocyanate compounds such as carbonyl diisothiocyanate, but are not limited to the exemplified compounds.

  Specific examples of the isothiocyanate compound containing one or more sulfur atoms in addition to the isothiocyanato group include thiobis (3-isothiocyanatopropane), thiobis (2-isothiocyanatoethane), dithiobis (2- Sulfur-containing aliphatic isothiocyanate compounds such as isothiocyanatoethane), 1-isothiocyanato-4-[(2-isothiocyanato) sulfonyl] benzene, thiobis (4-isothiocyanatobenzene), sulfonylbis (4-isothiocyanato) Benzene), sulfur-containing aromatic isothiocyanate compounds such as dithiobis (4-isothiocyanatobenzene), 2,5-diisothiocyanatothiophene, 2,5-diisothiocyanato-1,4-dithiane, etc. Although sulfur heterocyclic compounds etc. are mentioned, it is not limited to an exemplary compound. Furthermore, halogen-substituted products such as chlorine-substituted products and bromine-substituted products, alkyl-substituted products, alkoxy-substituted products, nitro-substituted products and prepolymer-modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, and burette-modified products. Bodies, dimerization or trimerization reaction products, and the like can also be used.

  Furthermore, the isothiocyanate compound which has an isocyanato group is also mentioned. Aliphatic and alicyclic compounds such as 1-isocyanato-6-isothiocyanatohexane, 1-isocyanato-4-isothiocyanatocyclohexane, 1-isocyanato-4-isothiocyanatobenzene, 4-methyl-3-isocyanato- Aromatic compounds such as 1-isothiocyanatobenzene, heterocyclic compounds such as 2-isocyanato-4,6-diisothiocyanato-1,3,5-triazine, and 4-isocyanato-4′-isothi In addition to isothiocyanato groups such as isocyanatodiphenyl sulfide and 2-isocyanato-2′-isothiocyanatodiethyl disulfide, compounds containing sulfur atoms are not limited to the exemplified compounds. Furthermore, halogen-substituted products such as chlorine-substituted products and bromine-substituted products, alkyl-substituted products, alkoxy-substituted products, nitro-substituted products and prepolymer-modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, and burette-modified products. Bodies, dimerization or trimerization reaction products, and the like can also be used.

Next, modification of the sulfur atom-containing resin of the present invention will be described. Adjustment of optical properties such as refractive index and Abbe number of the sulfur atom-containing resin of the present invention, hue, light resistance and weather resistance, heat resistance, impact resistance, hardness, specific gravity, linear expansion coefficient, polymerization shrinkage, water absorption In order to improve resin properties and handling properties, such as adjusting various physical properties such as hygroscopicity, chemical resistance, viscoelasticity, and adjusting transmittance and transparency, known compounds and the like are used as stabilizers and resin modifiers. Adding as a quality agent may be preferable for the purpose of obtaining a good resin. Examples of compounds added to improve stability such as polymerization stability and thermal stability include compounds such as polymerization retarders, polymerization inhibitors, oxygen scavengers, and antioxidants, but are limited to those described. I don't mean.

  Specific examples of the resin modifier include known thietane compounds, dithietane compounds, trithietane compounds, thiolane compounds, dithiolane compounds, trithiolane compounds, dithian compounds, trithiane compounds, amine compounds, hydroxy compounds including phenolic compounds, mercapto Organic acids, organic acids and anhydrides, amino acids and mercaptoamines, episulfide compounds and epoxy compounds other than the main components constituting the sulfur atom-containing resin of the present invention, thiol compounds, iso (thio) cyanate Examples thereof include compounds, olefin compounds including (meth) acrylates, cyclic organic compounds having inorganic atoms or sulfur atoms or selenium atoms. Among these resin modifiers, olefins including epoxy compounds, iso (thio) cyanate compounds, and (meth) acrylates are more preferable for overcoming the brittleness of the resulting resin and improving impact resistance. Amine compounds, thiol compounds, and phenol compounds are preferred for improving the hue of the resulting resin. Among these, a compound having one or more SH groups is more preferable. A compound having two or more SH groups and having a sulfide bond is more preferable. Cyclic organic compounds and inorganic compounds having a sulfur atom or a selenium atom are preferred for improving the refractive index of the resin. preferable. The addition amount of simple sulfur is preferably 3 to 30% by weight based on the entire raw material composition. Considering the heat resistance and brittleness of the resulting resin, it is preferable to use 5 to 25% by weight.

  Furthermore, the above-mentioned several types of resin modifiers may be used alone or in combination of two or more. The amount of the resin modifier added varies depending on the structure of the compound constituting the raw material composition and cannot be generally limited, but is usually in the range of 0.001 wt% to 50 wt% with respect to the raw material composition. It is possible to add. Considering optical properties of the obtained resin, it is preferable that the addition amount is 0.005 wt% to 25 wt%. If it is 0.01 wt%-15 wt%, it is more preferable.

  The type and amount of the curing catalyst for obtaining the sulfur atom-containing resin of the present invention, the type and proportion of the monomer vary depending on the structure of the compound constituting the raw material composition, and cannot be generally limited. Types of amines other than resin modifiers, phosphines, organic acids and salts thereof, esters, anhydrides, inorganic acids, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, secondary iodonium salts Lewis acids, radical polymerization catalysts, cationic polymerization catalysts and the like are usually used.

Specific examples of the curing catalyst include triethylamine, tri-n-butylamine, tri-n-hexylamine, N, N-diisopropylethylamine, triethylenediamine, triphenylamine, N, N-dimethylethanolamine, N, N-diethylethanolamine. N, N-dibutylethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-dimethylbenzylamine, N, N-diethylbenzylamine, tribenzylamine, N-methyldibenzylamine, N, N-dimethyl Cyclohexylamine, N, N-diethylcyclohexylamine, N, N-dimethylbutylamine, N-methyldicyclohexylamine, N-methylmorpholine, N-isopropylmorpholine, pyridine, quinoline, N, N-dimethylanily N, N-diethylaniline, α-, β-, or γ-picoline, 2,2′-bipyridyl, 1,4-dimethylpiperazine, dicyandiamide, tetramethylethylenediamine, hexamethylenetetramine, 1,8-diazabicyclo (5 , 4,0) -7-undecene, 2,4,6-tris (N, N-dimethylaminomethyl)
Aliphatic and aromatic tertiary amines such as phenol,

  Trimethylphosphine, triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tribenzylphosphine, 1,2-bis (diphenylphosphino) ethane, 1,2-bis (dimethylphosphine) Fino) phosphines such as ethane,

  Trifluoroacetic acid, trichloroacetic acid, trifluoroacetic anhydride, ethyl trifluoroacetate, sodium trifluoroacetate, trihalogenoacetic acid and its ester, anhydride, salt, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoro Trihalogenomethanesulfonic acid and its esters, anhydrides, salts, hydrochloric acid, sulfuric acid, nitric acid and the like, such as lomethanesulfonic anhydride, ethyl trifluoromethanesulfonate, sodium trifluoromethanesulfonate,

Quaternary ammonium salts such as tetramethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide,

Quaternary phosphonium salts such as tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide,

Tertiary sulfonium salts such as trimethylsulfonium bromide and tributylsulfonium bromide, secondary iodium salts such as diphenyliodonium bromide, dimethyltin dichloride, dibutyltin dichloride, dibutyltin dilaurate, dibutyltin diacetate, tetrachlorotin, dibutyltin oxide , Diacetoxytetrabutyl distanoxane, zinc chloride, acetylacetone zinc, aluminum chloride, aluminum fluoride, triphenylaluminum, acetylacetone aluminum, isopropoxide aluminum, tetrachlorotitanium and its complex, tetraiodotitanium, dichlorotitanium diisopropoxy , Titanium-based alkoxides such as titanium isopropoxide, calcium acetate, boron trifluoride, boron trifluoride diethyl ether complex, boron trifluoride Lysine complex, boron trifluoride ethylamine complex, boron trifluoride acetic acid complex, boron trifluoride phosphate complex, boron trifluoride t-butylmethyl ether complex, boron trifluoride dibutyl ether complex, boron trifluoride THF complex Lewis acids such as boron trifluoride methylsulfide complexes, boron trifluoride phenol complexes, etc., boron trifluoride complexes and boron trichloride complexes, etc.

  2,2′-azobis (2-cyclopropylpropionitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile) ), Radical polymerization catalysts such as t-butylperoxy-2-ethylhexanoate, n-butyl-4,4′-bis (t-butylperoxy) valerate, t-butylperoxybenzoate,

Diphenyliodonium hexafluorophosphoric acid, diphenyliodonium hexafluoroarsenic acid, diphenyliodonium hexafluoroantimony, triphenylsulfonium tetrafluoroboric acid, triphenylsulfonium hexafluorophosphoric acid, triphenylsulfonium hexafluoroarsenic acid, (tolylcumyl) iodonium tetrakis (pentafluoro) Examples thereof include cationic polymerization catalysts such as phenyl) borate, but are not limited to the exemplified compounds.

  The above curing catalysts may be used alone or in admixture of two or more. When two or more of these curing catalysts having different reactivity are used in combination, the handling properties of the monomer, the optical properties of the resulting resin, the hue It is preferable because transparency and optical distortion (pulse separation) may be improved.

  Among the above compounds, preferred are tertiary amine compounds and phosphine compounds, quaternary ammonium salts, quaternary phosphonium salts, dimethyltin dichloride, dibutyltin dichloride, dibutyltin dilaurate, dibutyltin diacetate, tetrachlorotin, dibutyl. Organotin compounds such as tin oxide, diacetoxytetrabutyl distanoxane, diphenyliodonium hexafluorophosphoric acid, diphenyliodonium hexafluoroarsenic acid, diphenyliodonium hexafluoroantimony, triphenylsulfonium tetrafluoroboric acid, triphenylsulfonium hexafluorophosphoric acid Cation heavy, such as triphenylsulfonium hexafluoroarsenate, (tolylcumyl) iodonium tetrakis (pentafluorophenyl) borate Is the catalysts.

  Although the addition amount of a curing catalyst is used in 0.001-10 wt% with respect to the total weight of a raw material composition, it is preferable to use it in 0.005-5 wt%. More preferably, it is used in the range of 0.01 to 1 wt%. If the addition amount of the curing catalyst is within this range, it is possible to produce a resin that is cured well, the pot life is maintained, and the resin obtained has good transparency and optical properties. There is. The curing catalyst may be added directly to the episulfide compound of the present invention, or may be added after being dissolved or dispersed in another compound constituting the raw material composition, but added after being dissolved or dispersed in another compound. May give better results. Furthermore, when a curing catalyst is added, a preferable result may be obtained if it is carried out in a nitrogen atmosphere or a dry gas atmosphere. Furthermore, in order to further draw out the performance of the obtained resin, it is preferable that the amount of unreacted functional groups remaining in the resin is 0.5 wt% or less with respect to the total weight of the resin. More preferably, it is 0.3 wt% or less.

  When molding the sulfur atom-containing resin of the present invention, as in the known molding method depending on the purpose, other stabilizers, resin modifiers, chain extenders, cross-linking agents, HALS systems are representative. Light stabilizers, UV absorbers typified by benzotriazoles, antioxidants typified by hindered phenols, colorants, dyes typified by anthraquinone disperse dyes, bluing agents, fillers, silicones Various substances such as an external mold release agent or internal mold release agent typified by a system, and an adhesion improver may be added.

  Examples of the internal release agent used in the present invention may be any as long as they have a releasability effect and do not impair physical properties such as transparency of the resin. Preferably, a surfactant is used. Is used. Surfactants that are preferably used as mold release agents are broadly classified into ionic surfactants and nonionic surfactants, and ionic surfactants are classified into anionic surfactants and cationic surfactants. The Examples of the anionic surfactant include sulfate ester, sulfonate ester, and phosphate ester. Among these, phosphate ester surfactants are preferable, and acidic phosphate ester anionic surfactants are particularly preferable. Is preferred.

In addition, the internal mold release agent as used herein includes those exhibiting a mold release effect among the above-described various catalysts, and may include, for example, quaternary ammonium salts and quaternary phosphonium salts. These internal release agents may be used alone or in combination of two or more. These are appropriately selected from the monomer combination, polymerization conditions, economy, and ease of handling. The amount of the internal mold release agent used is usually in the range of 1 to 10,000 ppm based on the total weight of the gun composition, either alone or as a mixture of two or more. When the addition amount is 1 ppm or more, the release ability is good, and when it is 10000 ppm or less, release from the mold during the casting polymerization is suppressed, and deterioration of surface accuracy of the lens surface and white turbidity of the obtained lens are prevented. Can do. The addition amount of various additives other than the internal mold release agent that enables the above addition varies depending on the type, structure, and effect of each additive and cannot be generally limited, but usually the total weight of the raw material composition Is used in the range of 0.001 to 10 wt%, but is preferably used in the range of 0.01 to 5 wt%. The dye is preferably used in the range of 1 ppb to 100 ppm instead of this range. Within these ranges, a well cured resin can be produced, and a resin having good transparency and optical properties may be obtained.

  A typical polymerization method for obtaining the sulfur atom-containing resin (for example, a plastic lens) of the present invention includes cast polymerization. That is, the raw material composition of the sulfur atom-containing resin of the present invention is injected between molding molds held by gaskets or tapes. The injection operation is preferably performed in a normal atmosphere as long as there is no particular problem, but better results may be obtained if it is performed in a nitrogen atmosphere or a dry gas atmosphere. The inside of the mold may be replaced with nitrogen gas or dry gas in advance. Here, if necessary, the raw material composition may be mixed with a curing catalyst and a resin modifier, or may be preliminarily subjected to operations such as depressurization at 10 kPa or less such as a defoaming operation, filter filtration and the like. Next, it is cured by heating in a heatable apparatus such as an oven or water, and the sulfur atom-containing resin can be taken out.

  The polymerization method and polymerization conditions for obtaining the sulfur atom-containing resin of the present invention can be appropriately selected depending on the type and amount of the curing catalyst used and the type and ratio of the monomer.

  The heat polymerization conditions of the raw material composition of the present invention injected into the molding mold vary depending on the composition and structure of the raw material composition, and are largely dependent on the type of resin modifier, the type of curing catalyst, the shape of the molding mold, etc. However, the polymerization temperature is about -50 to 200 ° C, preferably -20 to 150 ° C. It is more preferable in the temperature range of 0 ° C to 130 ° C. The polymerization time is 0.01 to 100 hours, preferably 0.05 to 50 hours. More preferably, it is performed for 0.1 to 25 hours. In some cases, it is possible to perform polymerization by combining the temperature conditions with programs such as low temperature, temperature increase, and temperature decrease.

  Furthermore, the raw material composition of the sulfur atom-containing resin of the present invention can shorten the polymerization time by irradiating energy rays such as electron beams and ultraviolet rays. In this case, a curing catalyst such as a radical polymerization catalyst or a cationic polymerization catalyst described as the above-described curing catalyst may be added. Moreover, about the cured resin taken out, you may perform processes, such as annealing, as needed. The annealing conditions vary depending on the structure of the compound constituting the raw material composition to be cured, the structure of the resin to be obtained, and the like, and cannot be generally limited, but are usually performed at 30 ° C to 200 ° C and performed at 50 ° C to 150 ° C. preferable. More preferably, it is carried out at 70 ° C to 130 ° C.

  Furthermore, the sulfur atom-containing resin of the present invention can be obtained as a molded article of various forms by changing the molding mold at the time of casting polymerization, and has a high refractive index such as a spectacle lens, a camera lens, and a light emitting diode (LED). And can be used for various applications that require a resin that takes advantage of transparency. In particular, it is suitable as an optical material such as a spectacle lens and a camera lens.

  In the lens using the sulfur atom-containing resin of the present invention thus obtained, if necessary, antireflection, imparting high hardness, improving abrasion resistance, improving chemical resistance, imparting antifogging properties, or fashionability. In order to improve the application, physical or chemical treatments such as surface polishing, antistatic treatment, hard coat treatment, non-reflective coat treatment, and dyeing treatment can be performed.

Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to the following examples. Of the performance tests of the obtained sulfur atom-containing resin, the optical properties and physical properties were evaluated by the following test methods.
Refractive index (ne) Abbe number (νe): Measured at 20 ° C. using a Purfrich refractometer.
-Heat resistance: Tg in the TMA penetration method (50 g load, pin tip 0.5 mmφ) was regarded as heat resistance.
-Resin transparency: Observed visually under a high-pressure mercury lamp. Cloudy ones were marked with x, and ones with excellent transparency were marked with ◯.
-Moisture absorption rate: It measured according to the measuring method of the water absorption rate of Japanese Industrial Standard JISK7209 except putting a test piece in the constant temperature and humidity control apparatus of temperature 60 degreeC and humidity 90% without putting in a distilled water. The measurement period was one day, and the test piece was a square with a side of 50 ± 1 mm and a thickness of 3 ± 0.2 mm.
・ Frequency change: After confirming the power of the lens with a power meter, the prepared lens is immersed in a dye bath (the solution described in the column of dyed spots below) for 10 minutes, dried at room temperature, and then coated. Assuming that, annealing was performed at 120 ° C. for 3 hours, and the temperature was kept constant at room temperature for 30 minutes, and the power of the lens was confirmed again with a power meter. The 10 lenses produced had 1 or more changes in the medium power.
-Dyeing spots: As a dyeing bath, to 1 L of pure water, 1.5 g of dispersed dye "MLP-Blue" manufactured by Mitsui BASF, 2.0 g of "MLP-Yellow", 1.5 g of MLP-Blue, benzyl alcohol 3 as a carrier 0.0 g was dissolved and a solution kept at 90 ° C. was prepared. Using this dyeing solution, the above immersion treatment was performed, and then a high-pressure mercury lamp for a projector was applied to visually check the stained spots. The case where there were one or more stained spots in the 10 lenses produced was evaluated as x, and the case where none was present as ◯.

[Example 1]
270 g of 1,1,3,3-tetrakis (2,3-epithiopropyldithiomethylthio) propane and 30.0 g of 1,1,3,3-tetrakis (mercaptomethylthio) propane in a beaker at room temperature of 20 ° C., UV absorption After mixing and dissolving 0.3 g of Biosorb 583 (manufactured by Kyodo Pharmaceutical Co., Ltd.) as an agent, 0.6 g of N, N-dimethylcyclohexylamine was added as a curing catalyst and the mixture was degassed for 0.4 hours under reduced pressure. Then, it inject | poured into the mold type | mold (-6.0D, 10 sheets) which consists of a glass mold and a gasket. The mold was gradually heated from 30 ° C. to 120 ° C. and polymerized in 24 hours. After the polymerization was completed, the mixture was gradually cooled and the resin was taken out from the mold. The obtained resin was excellent in transparency and good in appearance without distortion.
When the optical properties of the obtained resin were measured, the refractive index was ne = 1.77 and νe = 30. The moisture absorption rate was 0.25 × 10 ⁻³ %. The frequency change was ○. The stained spots were also good. The results are summarized in Table 1.

[Example 2]
In a beaker at room temperature of 20 ° C., 40.0 g of 1,1,3,3-tetrakis (mercaptomethylthio) propane, 35.0 g of m-xylylene diisocyanate, 0.015 g of dimethyltin diacetate as a curing catalyst, and as an ultraviolet absorber After mixing 0.3 g of Biosorb 583 (manufactured by Kyodo Yakuhin Co., Ltd.) to make a uniform solution, 225 g of 1,1,3,3-tetrakis (2,3-epithiopropyldithiomethylthio) propane and tetra as an internal mold release agent 0.1 g of n-butylphosphonium bromide was added and mixed. The obtained mixed liquid was degassed under reduced pressure for 0.4 hours, and then poured into a mold mold (-6.0D, 10 sheets) composed of a glass mold and a gasket. The mold was gradually heated from 30 ° C. to 120 ° C. and polymerized in 24 hours. After the polymerization was completed, the mixture was gradually cooled and the resin was taken out from the mold. The obtained resin was excellent in transparency and good in appearance without distortion.
When the optical properties of the obtained resin were measured, the refractive index was ne = 1.75 and νe = 30. The moisture absorption rate was 0.69 × 10 ⁻³ %. The frequency change was ○. The stained spots were also good. The results are summarized in Table 1.

[Example 3]
In a beaker at room temperature of 20 ° C., 30.0 g of 1,1,3,3-tetrakis (mercaptomethylthio) propane, 25.0 g of m-xylylene diisocyanate, 0.010 g of dimethyltin diacetate as a curing catalyst, and as an ultraviolet absorber Biosorb 583 (manufactured by Kyodo Pharmaceutical Co., Ltd.)
After mixing 0.3 g to make a uniform solution, 225 g of 1,1,3,3-tetrakis (2,3-epithiopropyldithiomethylthio) propane, 20.0 g of sulfur and tetra n-butyl as an internal mold release agent 0.1 g phosphonium bromide was added and mixed. The obtained mixed liquid was degassed under reduced pressure for 0.4 hours, and then poured into a mold mold (-6.0D, 10 sheets) composed of a glass mold and a gasket. The mold was gradually heated from 30 ° C. to 120 ° C. and polymerized in 24 hours. After the polymerization was completed, the mixture was gradually cooled and the resin was taken out from the mold. The obtained resin was excellent in transparency and good in appearance without distortion.
When the optical properties of the obtained resin were measured, the refractive index was ne = 1.76 and νe = 30. The moisture absorption rate was 0.43 × 10 ⁻³ %. The frequency change was ○. The stained spots were also good. The results are summarized in Table 1.

[Comparative Example 1]
140 g of 1,3-bis (isocyanatomethyl) cyclohexane, 0.15 g of dimethyltin dichloride as a curing catalyst, 0.3 g of Biosorb 583 (manufactured by Kyodo Yakuhin) as an ultraviolet absorber and JP-506 (Johoku Chemical) as an internal mold release agent 0.3 g) was mixed to obtain a uniform solution, and then 95 g of 2,5-dimercaptomethyl-1,4-dithiane and 65 g of pentaerythritol tetrakis (thioglycolate) were mixed to obtain a uniform solution. The obtained mixed solution was degassed under reduced pressure for 1.0 hour, and then poured into a mold die (-6.0D, 10 sheets) composed of a glass mold and a gasket. The mold was gradually heated from 30 ° C. to 120 ° C. and polymerized in 24 hours. After the polymerization was completed, the mixture was gradually cooled and the resin was taken out from the mold. The obtained resin was excellent in transparency and good in appearance without distortion.

When the optical properties of the obtained resin were measured, the refractive index was ne = 1.60 and νe = 40. The moisture absorption rate was 2.8 × 10 ⁻³ %. The frequency change was x. The stained spots were also x. The results are summarized in Table 1.

Claims (7)

An optical material comprising a sulfur atom-containing resin having a temperature of 60 ° C., a humidity of 90%, and a moisture absorption rate of 1.0 × 10 ⁻³ % or less per day. The optical material according to claim 1, wherein the sulfur-containing resin is a thermosetting resin. The optical material according to claim 1 or 2, having a refractive index of 1.60 or more. The optical material according to claim 1, wherein the sulfur atom-containing resin is an episulfide resin. The optical material according to claim 4, wherein the sulfur atom-containing resin is a thiourethane resin. The optical material according to any one of claims 1 to 6, wherein the sulfur atom-containing resin is obtained from a polymerizable composition containing single sulfur. A plastic lens made of the optical material according to claim 1.