JP5236713B2 - Method for producing sulfur-containing cyclic compound - Google Patents

Description

The present invention relates to a method for producing a sulfur-containing cyclic compound that can be suitably used in the field of resins such as optical materials that require a high refractive index and high transparency .

  In recent years, plastic lenses are rapidly becoming popular in optical materials such as eyeglass 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, but as physical and chemical properties, it has good impact resistance, easy dyeing, and heat resistance. That is, there is no problem, and the specific gravity is low. In other words, the lens manufacturing method and the monomer compound are safe for the human body and easy to handle.

  Among these performances, high heat resistance and low specific gravity have been realized at a high level even in current high refractive index plastic lenses. Currently, as a resin widely used for these purposes, a polythiourethane resin, a sulfur-containing O- (meth) acrylate resin, or a thio (meth) acrylate resin in which a sulfur atom is introduced into the resin is known. The polythiourethane resin is a resin having an excellent balance such as high refractive index, good impact resistance and dyeability. In addition, various methods have been proposed as having a high refractive index and a high Abbe number.

  The present inventors previously proposed a method of using a sulfur-containing cyclic compound as a method that exceeds the various methods for high refractive index, high Abbe number, and high impact resistance. (See Patent Document 1)

JP 2003-327583 A

  There is no limit to the proposal of new compounds that can improve the brittleness and impact resistance of plastic lenses with the high refractive index and high Abbe number, and further increase the refractive index, high Abbe number, and high impact resistance. The proposal of the material which has is called for.

  Therefore, the present inventors have studied materials that can meet the demands for higher refractive index and higher Abbe number after utilizing the previously proposed sulfur-containing cyclic compounds.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have a higher refractive index of a resin obtained by curing a sulfur-containing cyclic compound having a structure represented by the formula (1), and an Abbe number. As a result, the present invention has been found to be excellent in brittleness and impact resistance.
That is, the present invention
[1] one or more compounds selected from the group consisting of methylenebisthiocyanate, bis (thiocyanatomethyl) sulfide, and bis (thiocyanatomethyl) disulfide;
A compound having a mercapto group and a thietanyl group in the molecular structure;
A process for producing a sulfur-containing cyclic compound having a structure represented by the following formula (1), comprising a step of reacting the raw material under alkaline conditions in a reaction solvent .

(In the formula, a, b, c and d each independently represent an integer of 0 or 1.)
[2] One or more compounds selected from the group consisting of methylene bis-thiocyanate, bis (thiocyanatomethyl) sulfide, and bis (thiocyanatomethyl) disulfide are methylene bis-thiocyanate. 1].
[3] The compound having a mercapto group and a thietanyl group in the molecular structure is one or more selected from the group consisting of 3-mercaptothietane, 3- (mercaptomethylthio) thietane and 3- (mercaptomethyldithio) thietane The method according to [1] or [2], which is a compound.
[4] The method according to any one of [1] to [3], wherein the compound having a mercapto group and a thietanyl group in the molecular structure is 3-mercaptothietane.
[5] The method according to any one of [1] to [4], wherein the reaction solvent is an alcohol compound.
[6] The sulfur-containing cyclic compound is 1,4-bis (3-thietanyl) -1,3,4-trithiabutane, 1,5-bis (3-thietanyl) -1,2,4,5-tetrathiapentane. 1,6-bis (3-thietanyl) -1,3,4,6-tetrathiahexane, 1,6-bis (3-thietanyl) -1,3,5,6-tetrathiahexane, 1,7 -Bis (3-thietanyl) -1,2,4,5,7-pentathiaheptane, 1,7-bis (3-thietanyl) -1,2,4,6,7-pentathiaheptane The method according to any one of [1] to [5].
[7] The method according to any one of [1] to [6], wherein a sulfur atom content in the molecule of the sulfur-containing cyclic compound is 61% or more .

  According to the present invention, a compound useful as a raw material for a novel optical material in the field of high refractive index can be obtained. In addition, the resin obtained by polymerization and curing has high optical properties and high impact resistance, particularly in the field of eyeglass lenses. Contributes to higher refractive index and thinner thickness.

  Hereinafter, the present invention will be described in detail. First, the sulfur-containing cyclic compound of the present invention will be described.

  The sulfur-containing cyclic compound of the present invention is represented by the following general formula (1).

(In the formula, a, b, c and d each independently represent an integer of 0 or 1.)
Specific examples of preferable compounds having the structure represented by the formula (1) include 1,4-bis (3-thietanyl) -1,3,4-trithiabutane, 1,5-bis (3-thietanyl)- 1,2,4,5-tetrathiapentane, 1,6-bis (3-thietanyl) -1,3,4,6-tetrathiahexane, 1,6-bis (3-thietanyl) -1,3 5,6-tetrathiahexane, 1,7-bis (3-thietanyl) -1,2,4,5,7-pentathiaheptane, 1,7-bis (3-thietanyl) -1,2,4 Examples include 6,7-pentathiaheptane, but are not limited to these exemplary compounds. Among these exemplary compounds, a compound having a sulfur atom content in the molecule of 61% or more is more preferable from the viewpoint of the refractive index of the obtained resin.

  Examples of the method for producing the compound having the structure represented by the formula (1) of the present invention include a method for producing a disulfide bond by reacting a compound having a mercaptan group with a compound having a thiocyanate group. Can be mentioned. Here, as the most preferable compound having a mercapto group, 1,1-methanedithiol, bis (mercaptomethyl) sulfide, bis (mercaptomethyl) disulfide, 3-mercaptothietane, 3- (mercaptomethylthio) thietane, 3- (mercaptomethyldithio) thietane and the like can be mentioned, and the most preferable compounds having a thiocyanate group include methylenebisthiocyanate, bis (thiocyanatomethyl) sulfide, bis (thiocyanatomethyl) disulfide, 3 Examples include -thiocyanatothietane, 3- (thiocyanatomethylthio) thietane, 3- (thiocyanatomethyldithio) thietane, and the like, but are not limited to these exemplified compounds. The compound having a mercapto group and the compound having a thiocyanato group are reacted under alkaline or acidic conditions in the presence or absence of a reaction solvent. The reaction solvent here cannot be generally specified depending on the kind of the compound to be produced, but it is essential that the reaction solvent does not react with the mercapto group or thiocyanato group, and is stable under acidic conditions or alkaline conditions. It is desirable to be. Specifically, a hydrocarbon compound, an aromatic compound, a halogen compound, an ester compound, an ether compound, a ketone compound, an alcohol compound or the like that can dissolve reaction raw materials and reaction products is used. Good results may be obtained. Preferred examples include benzene, toluene, diethyl ether, 1,2-dichloroethane, monochlorobenzene, methanol and the like, but are not limited to the exemplified compounds. Compounds that can be used for alkaline conditions include inorganic alkalis such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, and sodium methylate. And metal alkoxides such as sodium ethylate, organic amines such as triethylamine and pyridine, and organic alkalis such as potassium t-butoxide. Compounds that can be used for acidic conditions include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, propionic acid, phthalic acid, methanesulfonic acid, p-toluenesulfonic acid, etc. Examples include organic acid, monochloroacetic acid, trichloroacetic acid, trifluoroacetic acid, halogenated organic acid such as trifluoromethanesulfonic acid, Lewis triacid such as boron trifluoride diethyl ether complex, and zinc chloride. The reaction temperature is in the range of 0 ° C. to 200 ° C., but considering the stability of the obtained product and the reaction rate, the range of 20 ° C. to 150 ° C. is preferable, and the range of 30 ° C. to 120 ° C. More preferred. Regarding the order of charging the raw materials, it may be charged all at once as long as the reaction temperature can be controlled, but with the thiocyanate compound and the reaction solvent placed on the liquid side, the mercaptan compound and the alkali or acid are mixed, or appropriately dropped in an unmixed state. Reaction may give favorable results. The product obtained by the reaction is extracted to the organic layer side, washed with a polar solvent such as water and alcohol, and removal of reaction by-product impurities, unreacted raw materials and the like improves the performance of the obtained product. This is a preferable operation in terms of improvement. Then, if the excess solvent on the organic layer side is removed, the desired product can be obtained.

  Next, it describes about the polymeric composition containing the sulfur-containing cyclic compound which has a structure represented by Formula (1) of this invention. The constituent requirement of the polymerizable composition of the present invention is to contain a sulfur-containing cyclic compound having a structure represented by the formula (1), but the refractive index of a resin obtained by curing the polymerizable composition, Adjustment of optical properties such as Abbe number, hue, light resistance and weather resistance, heat resistance, impact resistance, hardness, specific gravity, linear expansion coefficient, polymerization shrinkage, water absorption, moisture absorption, chemical resistance, viscoelasticity, etc. Purification and washing for the purpose of improving the resin and handling, such as adjusting the physical properties of the resin, adjusting the transmittance and transparency, adjusting the viscosity of the polymerizable composition, and other handling and handling methods. It is possible to apply techniques and operations commonly used in synthesizing organic compounds such as heat retention, cold retention, filtration, and decompression treatment, and to add known compounds as stabilizers and resin modifiers. It may be preferable for the purpose of obtaining a good resin. Examples of compounds that can be added to improve stability such as long-term storage stability, polymerization stability, and thermal stability include compounds such as polymerization retarders, polymerization inhibitors, oxygen scavengers, and antioxidants. However, the present invention is not limited to those described.

  Purifying the polymerizable composition is a technique used to improve the transparency of the resin obtained by curing, improve the hue, or increase the purity. In the formula (1) of the present invention, A method for purifying a polymerizable composition containing a sulfur-containing cyclic compound having a structure represented can be a known method such as distillation, recrystallization, column chromatography (silica gel method, activated carbon method, ion exchange resin method, etc.). Any method may be used at any timing as long as the extraction is performed, and it is only necessary that the transparency and hue of a resin obtained by curing a composition generally obtained by purification are improved.

  The method of washing the polymerizable composition is a technique used to improve the transparency of the resin obtained by curing or to improve the hue, but when the polymerizable composition is synthesized and taken out or after the synthesis A substance that is washed with a polar and / or non-polar solvent at a timing such as after removal of the resin and inhibits the transparency of the resin, for example, an inorganic salt used when synthesizing a polymerizable composition, or by-product, For example, a method of removing or reducing the amount of ammonium salt or thiourea can be mentioned. The solvent to be used cannot be generally limited by the polymerizable composition itself to be washed or the polarity of the solution containing the polymerizable composition, but the component to be removed can be dissolved and the polymerizable composition to be washed is used. Those which are hardly compatible with itself or a solution containing a polymerizable composition are preferable, and not only one type but also two or more types may be mixed and used. The components removed here vary depending on the purpose and application, but are preferably as small as possible, preferably 5000 ppm. More preferably, it is 1000 ppm or less. More preferably, it is 100 ppm or less.

  The method of keeping, cooling, and filtering the polymerizable composition is a technique used to improve the transparency of the resin obtained by curing or to improve the hue, but it is synthesized and taken out. In general, it is performed at a timing such as at the time of extraction or after removal after synthesis. For example, in the case where the polymerizable composition is crystallized during storage and handling becomes worse, the heat retention is a method in which the polymerizable composition and the resin obtained by curing the polymerizable composition are heated and dissolved within a range in which the performance of the resin does not deteriorate. Is mentioned. The temperature range to be heated and the method for heating and dissolving cannot be generally limited depending on the structure of the compound constituting the polymerizable composition to be handled, but it is usually performed within the freezing point + 50 ° C., preferably within + 20 ° C. In that case, the method etc. which move and melt | dissolve an internal solution by mechanically stirring with the apparatus which can be stirred, or bubbling with an inert gas to a composition, etc. are mentioned. The cold insulation is usually performed for the purpose of enhancing the storage stability of the polymerizable composition, but when the melting point is high and there is a problem in handling after crystallization, it is necessary to consider the storage temperature. Although the cold temperature cannot be generally limited by the structure of the compound constituting the polymerizable composition to be handled and the storage stability, in the case of the polymerizable composition containing the compound having the structure represented by the formula (1), 20 ° C. It may be stored at the following low temperature, and preferably 10 ° C. or lower. However, when the melting point is high, handling at a temperature higher than the freezing point is usually good in use. If dissolution by heating is possible easily, there is no problem even if it is stored below the freezing point.

  In the case of a polymerizable composition used for optical applications, since its extremely high transparency is required, it is usually preferable to filter the polymerizable composition with a filter having a small pore size. The pore size of the filter used here is usually 0.05 to 10 μm, but 0.05 to 5 μm is preferable in consideration of operability and performance. If it is 0.1-5 micrometers, it is more preferable. When the polymerizable composition containing the sulfur-containing cyclic compound of the present invention is filtered without exception, good results are often obtained. As for the temperature at which filtration is performed, a more preferable result may be obtained if it is performed at a low temperature near the freezing point. However, if solidification proceeds during filtration, it may be performed at a temperature that does not hinder the filtration operation. There is.

  The reduced pressure treatment is a technique generally used to remove a solvent, dissolved gas, and odor that lower the performance of a resin obtained by curing a polymerizable composition. The dissolved solvent generally causes a decrease in the refractive index and heat resistance of the resin obtained, so it is necessary to remove it as much as possible. The permissible value of the dissolved solvent cannot be generally limited by the structure of the compound constituting the polymerizable composition to be handled and the structure of the dissolved solvent, but it is usually preferably 1% or less. If it is 5000 ppm or less, it is more preferable. It is preferable to remove the dissolved gas because it has a detrimental effect on the polymerization of the dissolved gas and bubbles mixed into the resulting resin. In particular, it is preferable to remove a gas such as water vapor by bubbling with a dry gas. The dissolved amount cannot be unconditionally limited depending on the structure of the compound constituting the polymerizable composition, the physical property and structure of the dissolved gas, and the type, but for example, in the case of moisture, if it is 1000 ppm or less, the viewpoint of the transparency of the resulting resin Is preferable.

  As resin modifiers, known thietane compounds, dithietane compounds, trithiethane compounds, thiolane compounds, dithiolane compounds, trithiolane compounds, dithiane compounds, trithiane compounds, episulfide compounds and epoxy compounds, amine compounds, thiol compounds, phenols Hydroxy compounds including compounds, iso (thio) cyanate compounds, mercapto organic acids, organic acids and anhydrides, amino acids and mercaptoamines, olefins including (meth) acrylates, sulfur atoms or selenium atoms Examples thereof include cyclic organic compounds and inorganic compounds. 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.

  Here, a compound that can be used as a resin modifier will be specifically described.

Specific examples of the episulfide compound as the resin modifier of the present invention include bis (1,2-epithioethyl) sulfide, bis (1,2-epithioethyl) disulfide, bis (epithioethylthio) methane, bis (epithio). Epithioethyl compounds such as ethylthio) 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-epithiopropylthio) propane, 1,3-bis (2,3-e Thiopropylthio) -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-methyl Pentane, 1,5-bis (2,3-epithiopropylthio) -3-thiapentane, 1,6-bis (2,3-epithiopropylthio) hexane, 1,6-bis (2,3-epi Thiopropylthio) -2-methylhexane, 3,8-bis (2,3-epithiopropylthio) -3,6-dithiaoctane, 1,2,3-tris (2,3-epithiopropylthio) propane , 2,2-bis (2,3- Pithiopropylthio) -1,3-bis (2,3-epithiopropylthiomethyl) propane, 2,2-bis (2,3-epithiopropylthiomethyl) -1- (2,3-epithio Propylthio) butane, 1,5-bis (2,3-epithiopropylthio) -2- (2,3-epithiopropylthiomethyl) -3-thiapentane, 1,5-bis (2,3-epi Thiopropylthio) -2,4-bis (2,3-epithiopropylthiomethyl) -3-thiapentane, 1- (2,3-epithiopropylthio) -2,2-bis (2,3-epi Thiopropylthiomethyl) -4-thiahexane, 1,5,6-tris (2,3-epithiopropylthio) -4- (2,3-epithiopropylthiomethyl) -3-thiahexane, 1,8- Bis (2,3-epithiopropylthio ) -4- (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropylthio) -4,5-bis (2,3-epithio) Propylthiomethyl) -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-epi Thiopropylthio) -2,4,5-tris (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,1,1-tris [[2- (2,3-epithiopropylthio ) Ethyl] thiomethyl] -2- (2,3-epithio) Propylthio) ethane, 1,1,2,2-tetrakis [[2- (2,3-epithiopropylthio) ethyl] thiomethyl] ethane, 1,11-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) -5,7-bis (2,3-epithiopropylthiomethyl) ) -3,6,9-trithiaundecane and other chain aliphatic 2,3-epithiopropylthio compounds, 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 2 , 3-epithiopropylthio compound,
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) Examples include aromatic 2,3-epithiopropyloxy compounds such as biphenyl, but are not limited 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, and more preferred compounds are bis (1,2-epithioethyl) sulfide, bis (1,2-epithioethyl) disulfide, and bis (2,3- Epithiopropyl) disulfide.

  Specific examples of the epoxy compound as the resin modifier of the present invention include phenolic epoxy compounds obtained by condensation reaction of polyphenol compounds such as bisphenol A glycidyl ether and epihalohydrin compounds, hydrogenated bisphenol A glycidyl ether, and the like. Alcohol-based epoxy compounds obtained by condensation of polyhydric 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 polyvalent organic acid compounds and epihalohydrin compounds, amine epoxy compounds obtained by condensation of secondary amine compounds and epihalohydrin compounds, etc. Cyclohexene diepoxide and an aliphatic polyvalent epoxy compound and the like.

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, 1,11 Bis (2,3-epoxypropylthio) -4,7-bis (2,3-epoxypropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epoxypropylthio) ) -5,7-bis (2,3-epoxypropylthiomethyl) -3,6,9-trithiaundecane and the like chain aliphatic 2,3-epoxypropylthio compounds, 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) Examples include aromatic 2,3-epoxypropyloxy compounds such as biphenyl, but are not limited to the exemplified compounds. It is not limited only to these exemplary compounds.

Specific examples of amine compounds that can be added as a resin modifier include ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, ter-butylamine, pentylamine, hexylamine, heptylamine, octyl Amine, decylamine, laurylamine, myristylamine, 3-pentylamine, 2-ethylhexylamine, 1,2-dimethylhexylamine, allylamine, aminomethylbicycloheptane, cyclopentylamine, cyclohexylamine, 2,3-dimethylcyclohexylamine, amino Methylcyclohexane, aniline, benzylamine, phenethylamine, 2,3-, or 4-methylbenzylamine, o-, m-, or p-methylaniline, o-, m- Is p-ethylaniline, aminomorpholine, naphthylamine, furfurylamine, α-aminodiphenylmethane, toluidine, aminopyridine, aminophenol, aminoethanol, 1-aminopropanol, 2-aminopropanol, aminobutanol, aminopentanol, aminohexanol, Methoxyethylamine, 2- (2-aminoethoxy) ethanol, 3-ethoxypropylamine, 3-propoxypropylamine, 3-butoxypropylamine, 3-isopropoxypropylamine, 3-isobutoxypropylamine, 2,2-di Monofunctional primary amine compounds such as ethoxyethylamine,
Ethylenediamine, 1,2-, or 1,3-diaminopropane, 1,2-, 1,3-, or 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7 -Diaminoheptane, 1,8-diaminooctane, 1,10-diaminodecane, 1,2-, 1,3-, or 1,4-diaminocyclohexane, o-, m- or p-diaminobenzene, 3,4 -Or 4,4'-diaminobenzophenone, 3,4- or 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-, or 4,4 '-Diaminodiphenylsulfone, 2,7-diaminofluorene, 1,5-, 1,8-, or 2,3-diaminonaphthalene, 2,3 2,6- or 3,4-diaminopyridine, 2,4- or 2,6-diaminotoluene, m- or p-xylylenediamine, isophoronediamine, diaminomethylbicycloheptane, 1,3-, Alternatively, 1,4-diaminomethylcyclohexane, 2-, or 4-aminopiperidine, 2-, or 4-aminomethylpiperidine, 2-, or 4-aminoethylpiperidine, N-aminoethylmorpholine, N-aminopropylmorpholine, etc. A primary polyamine compound of
Diethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine, diisobutylamine, di-n-pentylamine, di-3-pentylamine, dihexylamine, dioctylamine, di (2-ethylhexyl) amine, methyl Hexylamine, diallylamine, N-methylallylamine, piperidine, pyrrolidine, diphenylamine, N-methylamine, N-ethylamine, dibenzylamine, N-methylbenzylamine, N-ethylbenzylamine, dicyclohexylamine, N-methylaniline, N -Monofunctional secondary amine compounds such as ethylaniline, dinaphthylamine, 1-methylpiperazine, morpholine,
N, N′-dimethylethylenediamine, N, N′-dimethyl-1,2-diaminopropane, N, N′-dimethyl-1,3-diaminopropane, N, N′-dimethyl-1,2-diaminobutane, N, N′-dimethyl-1,3-diaminobutane, N, N′-dimethyl-1,4-diaminobutane, N, N′-dimethyl-1,5-diaminopentane, N, N′-dimethyl-1 , 6-Diaminohexane, N, N′-dimethyl-1,7-diaminoheptane, N, N′-diethylethylenediamine, N, N′-diethyl-1,2-diaminopropane, N, N′-diethyl-1 , 3-diaminopropane, N, N′-diethyl-1,2-diaminobutane, N, N′-diethyl-1,3-diaminobutane, N, N′-diethyl-1,4-diaminobutane, N, N'-diethyl-1,5-di Aminopentane, N, N′-diethyl-1,6-diaminohexane, N, N′-diethyl-1,7-diaminoheptane, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 2,6-dimethyl Piperazine, homopiperazine, 1,1-di- (4-piperidyl) methane, 1,2-di- (4-piperidyl) ethane, 1,3-di- (4-piperidyl) propane, 1,4-di- Secondary polyamine compounds such as (4-piperidyl) butane and tetramethylguanidine can be exemplified, but are not limited to the exemplified compounds. Moreover, the said amine compound may be used individually or in mixture of 2 or more types. Of the exemplified compounds, benzylamine and piperazines are more preferred compounds.

The thiol compounds that can be added as a resin modifier include those containing at least one sulfur atom in addition to the mercapto group. Specific examples thereof include monofunctional thiol compounds such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, octyl mercaptan, dodecyl mercaptan, tert-dodecyl mercaptan, hexadecyl mercaptan, octadecyl mercaptan, cyclohexyl mercaptan, benzyl mercaptan, Aliphatic mercaptan compounds such as ethylphenyl mercaptan, 2-mercaptomethyl-1,3-dithiolane, 2-mercaptomethyl-1,4-dithiane, aromatic mercaptan compounds such as thiophenol and mercaptotoluene,
Examples of the bifunctional or higher polythiol compound 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-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), Trimethylolpropane bis (2-mercaptoacetate), trimethylolpropane bis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis ( - mercaptopropionate), tetrakis (mercaptomethyl) aliphatic such as methane polythiol compound,
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 alkylated products,
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 (mercaptomethyl) H ) -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 (mercaptomethylthio) -6-mercapto-2,5-dithia Hexylthio} 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} mercapto Tylthiomethyl-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-dithiolane, 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-dithio Ranyl) thio} -5- [1- {2- (1,3-dithietanyl)}-3-mercapto-2-thiapropylthio] -1,3-dithiolane and dithioacetal or dithioketal skeletons of these oligomers A compound having
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 an 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, 3,9-dimercapto-1,5,7,11-tetrathiaspiro [5,5] undecane, and oligomers thereof. Examples include compounds having an orthotetrathiocarbonate skeleton, but are not limited to these exemplary compounds. 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. Furthermore, 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, and 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 functions. 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 in the case of three or more functional groups and at least one compound selected from at least one compound and three or more functional compounds in the case of two or more functional groups. It is done.

Specific examples of hydroxy compounds containing phenolic compounds as the resin modifier of the present invention are monofunctional or higher mono- or polyols and also include phenolic hydroxyl groups. Those containing a sulfur atom in the molecule are also included. Specific examples of monofunctional compounds include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, pentanol, isoamyl alcohol, hexanol, heptanol, octanol, nonyl alcohol, decanol, dodecyl alcohol. Cetyl alcohol, isotridecyl alcohol, stearyl alcohol, 2-ethyl-1-hexanol, allyl alcohol, methoxyethanol, ethoxyethanol, phenoxyethanol, cyclopropanol, cyclobutanol, cyclopentanol, cyclohexanol, cyclooctanol, benzyl alcohol, Phenylethyl alcohol, methylcyclohexanol, furfuryl alcohol, tetrahydrofurfuryl Alcohol, methyl lactate, ethyl lactate, aliphatic, such as butyl lactate monofunctional alcohol compounds,
Aromatic monofunctional phenolic compounds such as phenol, cresol, ethylphenol, methoxyphenol, ethoxyphenol, methoxyethylphenol, cumylphenol, phenoxyphenol, tert-butylphenol, naphthol,
Examples of the bifunctional or higher polyol compound include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin, trimethylol ethane, trimethylol propane, butane triol, and 1,2-methyl glycoside. , Pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, erythritol, threitol, mannitol, ribitol, arabinitol, xylitol, allitol, dolcitol, glycol, inositol, hexanetriol, triglycerol, triethylene glycol, polyethylene glycol, tris ( 2-hydroxyethyl) isocyanurate, cyclobutanediol, cyclope Tandiol, cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol, bicyclo [4,3,0] -nonanediol, dicyclohexanediol, tricyclo [5,3,1,1] dodecanediol , Bicyclo [4,3,0] -nonanedimethanol, dicyclohexanediol, tricyclo [5,3,1,1] dodecanediethanol, spiro [3,4] octanediol, butylcyclohexanediol, 1,1-bicyclohexene Silidenediol, cyclohexanetriol, maltitol, lactitol, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxybenzene, benzenetriol, bif Nyltetraol, trihydroxyphenanthrene, bisphenol A, bisphenol F, xylylene glycol, bis (2-hydroxyethoxy) benzene, bisphenol A-bis (2-hydroxyethyl ether), tetrabromobisphenol A, tetrabromobisphenol A-bis (2-hydroxyethyl ether), polyols such as dibromoneopentyl glycol,

  In addition, oxalic acid, glutamic acid, adipic acid, acetic acid, propionic acid, phthalic acid, isophthalic acid, salicylic acid, pyromellitic acid, 3-bromopropionic acid, 2-bromoglycolic acid, dicarboxycyclohexane, butanetetracarboxylic acid, bromophthalate Examples include condensation reaction products of an organic polybasic acid such as an acid and the polyol, and addition reaction products of the polyol and an alkylene oxide such as ethylene oxide and propylene oxide, but are not limited to the exemplified compounds. Furthermore, you may use halogen substituted bodies, such as these chlorine substituted bodies and bromine substituted bodies.

  Examples of the mono- or polyol compound containing a sulfur atom include bis [4- (hydroxyethoxy) phenyl] sulfide, bis [4- (2-hydroxypropoxy) phenyl] sulfide, and bis [4- (2,3- Dihydroxypropoxy) phenyl] sulfide, bis [4- (4-hydroxycyclohexyloxy) phenyl] sulfide, bis [2-methyl-4- (hydroxyethoxy) -6-butylphenyl] sulfide and these compounds on average 3 per hydroxyl group Compounds having an ethylene oxide and / or propylene oxide added thereto, bis (2-hydroxyethyl) sulfide, 1,2-bis (2-hydroxyethylmercapto) ethane, bis (2-hydroxyethyl) disulfide, 1,4 -Dithian-2, -Diol, bis (2,3-dihydroxypropyl) sulfide, tetrakis (4-hydroxy-2-thiabutyl) methane, bis (4-hydroxyphenyl) sulfone (bisphenol S), tetrabromobisphenol S, tetramethylbisphenol S, 4 , 4-thiobis (6-tert-butyl-3-methylphenol), 1,3-bis (2-hydroxyethylthioethyl) cyclohexane and the like, but are not limited to the exemplified compounds. Furthermore, you may use halogen substituted bodies, such as these chlorine substituted bodies and bromine substituted bodies.

Specific examples of the iso (thio) cyanate compounds as the resin modifier of the present invention include methyl isocyanate, ethyl isocyanate, n-propyl isocyanate, isopropyl isocyanate, n-butyl isocyanate, sec-butyl isocyanate. Nert, tert-butyl isocyanate, pentyl isocyanate, hexyl isocyanate, heptyl isocyanate, octyl isocyanate, decyl isocyanate, lauryl isocyanate, myristyl isocyanate, octadecyl isocyanate, 3-pentyl isocyanate, 2-ethylhexyl isocyanate Narate, 2,3-dimethylcyclohexyl isocyanate, 2-methoxyphenyl isocyanate, 4-methoxyphenyl isocyanate, α-methylbenzyl isocyanate DOO, phenylethyl isocyanate, phenyl isocyanate, o-, m-, or p- tolyl isocyanate, cyclohexyl isocyanate, benzyl isocyanate, monofunctional isocyanate compounds such as isocyanate methyl bicycloheptane,
Hexamethylene diisocyanate, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexane 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 (isocyanato Ethyl) carbonate, bis (isocyanatoethyl) ether, lysine diisocyanate methyl ester, lysine triisocyanate, xylylene diisocyanate, bis (isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, α, α, α ', Α'-tetramethylxylylene Diisocyanate, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether, bis (isocyanatoethyl) phthalate, mesityrylene triisocyanate, 2,6-di (isocyanate) Aliphatic polyisocyanate compounds such as natomethyl) 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, and the like can also be used.

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, p-phenyleneisopropylidenediisothiocyanate,
Alicyclic polyisothiocyanate compounds such as cyclohexane diisothiocyanate, 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.

  Specific examples of preferred mercapto organic acid compounds as the resin modifier of the present invention include thioglycolic acid, 3-mercaptopropionic acid, thioacetic acid, thiolactic acid, thiomalic acid, thiosalicylic acid, and the like, but exemplary compounds It is not limited to only. Moreover, the said mercapto organic acid compound may be used individually or in mixture of 2 or more types.

  Specific examples of preferred organic acids and their anhydrides include hydrocarbon-based organic acids such as formic acid, acetic acid, propionic acid, butyric acid, benzoic acid, p-toluenesulfonic acid, methanesulfonic acid, and their halogens, nitro, cyanation Monofunctional organic acids such as trifluoroacetic anhydride, chloroacetic anhydride, dichloroacetic anhydride, trichloroacetic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride Acid, methylnorbornenoic anhydride, methylnorbornanoic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, etc., bifunctional organic acids such as phthalic acid, succinic acid, thiodiglycolic acid, Examples include sulfur-containing organic acids such as thiodipropionic acid and dithiodipropionic acid. The present invention is not limited to.

Specific examples of preferred olefins include benzyl acrylate, benzyl methacrylate, butoxyethyl acrylate, butoxymethyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxymethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, phenoxy. Ethyl acrylate, phenoxyethyl methacrylate, phenyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol 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-acryloxyethoxyphenyl) propane, 2 , 2-bis (4-methacryloxydiethoxyphenyl) propane, bisphenol F diacrylate, bisphenol F dimethacrylate, 1 1-bis (4-acryloxyethoxyphenyl) methane, 1,1-bis (4-methacryloxyethoxyphenyl) methane, 1,1-bis (4-acryloxyethoxyphenyl) 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, benzylthiomethacrylate, xylylenedithiol diacrylate, key (Meth) acrylate compounds such as silylenedithiol 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.

  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 polymerizable composition and cannot be generally limited, but is usually 0.001 wt% to 50 wt% with respect to the polymerizable composition. It is possible to add in a range. 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 polymerizable composition containing the sulfur-containing cyclic compound having the structure represented by the formula (1) of the present invention can be usually cured using a method for polymerizing a known sulfur-containing cyclic compound. Yes, the type and amount of the curing catalyst for obtaining the cured resin, the type and ratio of the monomer vary depending on the structure of the compound constituting the polymerizable composition, and cannot be generally limited, but the type of the curing catalyst As other than the resin modifier of the present invention, amines, 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, aliphatic and aromatic tertiary amines such as 2,4,6-tris (N, N-dimethylaminomethyl) 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 esters, anhydrides, salts, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoro Trihalogenomethanesulfonic acid and its esters, anhydrides, salts, hydrochloric acid, sulfuric acid, nitric acid 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 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 methyl sulfide complex, boron trifluoride phenol complex and other boron trifluoride complexes and boron trichloride complex such as boron trifluoride compounds and complexes thereof,
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, (tricumyl) 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 property 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.

  Of the above compounds, preferred are dimethyltin dichloride, dibutyltin dichloride, dibutyltin dilaurate, dibutyltin diacetate, tetrachlorotin, dibutyltin oxide, organotin compounds such as diacetoxytetrabutyldistanoxane, and trifluoroacetic acid. , Trichloroacetic acid, trifluoroacetic anhydride, ethyl trifluoroacetate, sodium trifluoroacetate, trihalogenoacetic acid and its esters, anhydrides, salts, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoromethanesulfonic acid Anhydrides, trihalogenomethanesulfonic acid such as ethyl trifluoromethanesulfonate, sodium trifluoromethanesulfonate and its esters, anhydrides, salts, boron trifluoride, boron trifluoride diethyl ether complex, three Boron fluoride piperidine 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, trifluoride Lewis acid such as boron-THF complex, boron trifluoride methyl sulfide complex, boron trifluoride complex such as boron trifluoride phenol complex and boron trichloride complex such as boron trichloride complex and complexes thereof, Lewis acid, diphenyl Iodonium hexafluorophosphoric acid, diphenyliodonium hexafluoroarsenic acid, diphenyliodonium hexafluoroantimony, triphenylsulfonium tetrafluoroboric acid, triphenylsulfonium hexafluorophosphoric acid, triphenylsulfonium hexafluoroarsenic acid, (tolylcumyl) yo A de tetrakis (pentafluorophenyl) cationic polymerization catalyst borate, and more preferred are dimethyltin dichloride, trifluoromethanesulfonic acid and anhydrides, esters, various complex salts and boron trifluoride.

  The addition amount of the curing catalyst is used in the range of 0.001 to 10 wt% with respect to the total weight of the polymerizable composition, but is preferably used in the range of 0.005 to 5 wt%. It is more preferable to use 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 sulfur-containing cyclic compound of the present invention or may be added after being dissolved or dispersed in another compound constituting the polymerizable composition, but it may be dissolved or dispersed in another compound. It may be preferable to add after adding. 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 curing a polymerizable composition containing a sulfur-containing cyclic compound having a structure represented by the formula (1) of the present invention and molding a resin, the same as in the known molding method depending on the purpose, Other stabilizers, resin modifiers, chain extenders, crosslinkers, light stabilizers typified by HALS, UV absorbers typified by benzotriazole, antioxidants typified by hindered phenols, Anti-coloring agents, dyes typified by anthraquinone-based disperse dyes, fillers, external mold release agents typified by silicones or acidic phosphate esters, internal mold release agents typified by quaternary ammonium salts, adhesion improvers, etc. Various substances may be added. The amount of the various additives that can be added differs depending on the type, structure, and effect of each additive and cannot be generally limited. It is used in the range of 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 a resin (for example, a plastic lens) obtained by curing the composition of the present invention is cast polymerization. That is, the polymerizable composition of the present invention is injected between molding molds held by a gasket or a tape. 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 polymerizable 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. Then, it can be cured by heating in a heatable apparatus such as an oven or water, and the resin can be taken out.

  The polymerization method and polymerization conditions for obtaining a resin obtained by curing the composition of the present invention cannot be generally limited by the type and amount of the curing catalyst used and the type and ratio of the monomer.

  The heating polymerization conditions of the polymerizable composition of the present invention injected into the molding mold differ depending on the composition and structure of the polymerizable composition containing the compound having the structure represented by the formula (1) of the present invention and are generally limited. The polymerization temperature is about −50 to 200 ° C., but the temperature is about −50 to 200 ° C., but the conditions are largely different depending on the type of resin modifier, the type of curing catalyst, the shape of the molding mold, etc. 150 ° C. is preferred. 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 polymerizable composition of the present invention can shorten the polymerization time by irradiating an energy beam such as an electron beam or an ultraviolet ray. 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 condition varies depending on the structure of the compound constituting the polymerizable composition to be cured, the structure of the resin to be obtained, and the like, and cannot be generally limited, but is usually performed at 30 ° C to 200 ° C, but at 50 ° C to 150 ° C. Preferably it is done. More preferably, it is carried out at 70 ° C to 130 ° C.

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

（式中、ａ、ｂ、ｃ、ｄは、それぞれ独立に０または１の整数を示す。）
［２］含硫環状化合物が１，４−ビス（３−チエタニル）−１，３，４−トリチアブタン、１，５−ビス（３−チエタニル）−１，２，４，５−テトラチアペンタン、１，６−ビス（３−チエタニル）−１，３，４，６−テトラチアヘキサン、１，６−ビス（３−チエタニル）−１，３，５，６−テトラチアヘキサン、１，７−ビス（３−チエタニル）−１，２，４，５，７−ペンタチアヘプタン、１，７−ビス（３−チエタニル）−１，２，４，６，７−ペンタチアヘプタンのいずれかである［１］に記載の化合物。
［３］分子内の硫黄原子含有率が６１％以上である［１］乃至［２］に記載の化合物。
［４］［１］乃至［３］のいずれかに記載の化合物を含有する重合性組成物。
［５］［４］に記載の重合性組成物を硬化させてなる樹脂。
［６］［５］に記載の樹脂からなる光学材料。
［７］［４］に記載の重合性組成物を注型重合することを特徴とする樹脂の製造方法。
［８］メチレンビスチオシアナートを原料として［１］乃至［３］に記載の化合物を製造する方法。 In the lens using the optical material of the present invention thus obtained, if necessary, antireflection, imparting high hardness, improving abrasion resistance, improving chemical resistance, imparting antifogging, imparting fashion, etc. Therefore, physical or chemical treatments such as surface polishing, antistatic treatment, hard coat treatment, non-reflective coating treatment, and dyeing treatment can be performed.
The present invention also includes the following aspects.
[1] A sulfur-containing cyclic compound having a structure represented by the following formula (1).

(In the formula, a, b, c and d each independently represent an integer of 0 or 1.)
[2] The sulfur-containing cyclic compound is 1,4-bis (3-thietanyl) -1,3,4-trithiabutane, 1,5-bis (3-thietanyl) -1,2,4,5-tetrathiapentane, 1,6-bis (3-thietanyl) -1,3,4,6-tetrathiahexane, 1,6-bis (3-thietanyl) -1,3,5,6-tetrathiahexane, 1,7- Either bis (3-thietanyl) -1,2,4,5,7-pentathiaheptane or 1,7-bis (3-thietanyl) -1,2,4,6,7-pentathiaheptane The compound according to [1].
[3] The compound according to [1] or [2], wherein the sulfur atom content in the molecule is 61% or more.
[4] A polymerizable composition containing the compound according to any one of [1] to [3].
[5] A resin obtained by curing the polymerizable composition as described in [4].
[6] An optical material comprising the resin according to [5].
[7] A method for producing a resin, comprising subjecting the polymerizable composition according to [4] to cast polymerization.
[8] A method for producing the compound according to any one of [1] to [3] using methylenebisthiocyanate as a raw material.

Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to the following examples. In addition, the test regarding the thermal stability of the obtained polymerizable composition was carried out by conducting a heat retention test of the polymerizable composition at 40 ° C. under nitrogen, measuring the purity change of the main component, and reducing the purity after one month. Those having 10% or more were designated as stability x those having less than 10% were designated as stability ○. Among the performance tests of the obtained cured resin, the optical properties and impact resistance tests were evaluated by the following test methods.
Refractive index (ne) Abbe number (νe): Measured at 20 ° C. using a Purfrich refractometer.
Impact resistance test: A 16 g iron ball was dropped from a position 127 cm high onto a lens (-3D) with a center thickness of approximately 1.0 mm, and the damaged state of the lens was confirmed. Those in which the lens was damaged were marked with ×, and those that were not damaged were marked with ○.

  To a reactor equipped with a stirrer and a thermometer, 106 g of 3-mercaptothietane and 50 g of methanol were charged, and 200 g of 28% sodium methoxide was added dropwise while maintaining the reaction temperature at 20 ° C. Next, 65 g of methylenebisthiocyanate and 400 g of toluene were charged into the obtained methanol solution, and the mixture was stirred dropwise while maintaining the reaction temperature at 20 to 30 ° C. After completion of the dropwise addition, aging was further performed at 30 ° C. for 2 hours. After completion of the reaction, extraction was performed by charging 200 g of toluene and 500 g of water. Further, the toluene layer was washed three times with water, and the toluene layer was taken out. The taken out toluene layer was concentrated under reduced pressure to obtain 120 g of a residue. When the obtained residue was analyzed by HPLC, it was a mixture of several components. The obtained mixture was purified by passing through a silica gel column using hexane and chloroform as developing solvents to obtain 6 types of compounds. The obtained compounds were identified as the following compounds (a) to (f) and were sulfur-containing cyclic compounds having a chain skeleton. All of the compounds (a) to (f) were thermally stable.

(A) 1,4-bis (3-thietanyl) -1,2,4-trithiabutane (b) 1,5-bis (3-thietanyl) -1,2,4,5-tetrathiapentane (c) 1 , 6-Bis (3-thietanyl) -1,3,4,6-tetrathiahexane (d) 1,6-bis (3-thietanyl) -1,2,4,6-tetrathiahexane (e) 1 , 7-bis (3-thietanyl) -1,2,4,5,7-pentathiaheptane (f) 1,7-bis (3-thietanyl) -1,2,4,6,7-pentathiaheptane Here, the identification data of the obtained six compounds are shown below.
(A) 1,4-bis (3-thietanyl) -1,2,4-trithiabutane

(B) 1,5-bis (3-thietanyl) -1,2,4,5-tetrathiapentane

(C) 1,6-bis (3-thietanyl) -1,3,4,6-tetrathiahexane

（ｄ）１，６ビス（３−チエタニル）−１，２，４，６−テトラチアヘキサン

(D) 1,6bis (3-thietanyl) -1,2,4,6-tetrathiahexane

(E) 1,7-bis (3-thietanyl) -1,2,4,5,7-pentathiaheptane

(F) 1,7-bis (3-thietanyl) -1,2,4,6,7-pentathiaheptane

  30 g of compound (a) and 0.03 g of Biosorb 583 (manufactured by Kyodo Yakuhin Co., Ltd.) are mixed and dissolved in a beaker at room temperature of 20 ° C., and then 0.15 g of boron trifluoride / dibutyl ether complex is charged as a catalyst. The solution was transferred to another beaker while stirring. After the transfer, the mixture was further stirred for 30 minutes to dissolve sufficiently. The obtained mixture was filtered to remove insolubles, and then sufficiently degassed under a reduced pressure of 1.3 kPa or less. Next, the defoamed liquid was poured into a mold formed with a glass mold and a tape. All the operations so far were performed in a nitrogen atmosphere. The completed mold was put into a temperature-programmable polymerization furnace, the temperature was gradually raised from 30 ° C. to 120 ° C., and polymerization was carried out in 20 hours. After cooling to near room temperature, the glass mold was released to obtain a resin. 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 = 1.74 and νe = 32. The impact resistance test was ○. The results are summarized in Table 7.

(Examples 3 to 7)
A resin was obtained in the same manner as in Example 2, except that 30 g of each of the compounds (b) to (f) was used instead of the compound (a). The obtained resin eventually had excellent transparency and good appearance without distortion. The physical properties obtained are summarized in Table 7.

(Examples 8 to 13)
30 g each of compound (a) to compound (f) was used, and 0.15 g of boron trifluoride / dibutyl ether complex as a catalyst was 4,8or4,7or5,7-dimercaptomethyl-1,11-mercapto-3, A resin was obtained in the same manner as in Example 2 except that it was sufficiently dissolved in 1.0 g of 6,9-trithiaundecane. The obtained resin eventually had excellent transparency and good appearance without distortion. The physical properties obtained are summarized in Table 7.

(Comparative Example 1)
As a sulfur-containing cyclic compound, bis (3-thietanylthio) methane described in JP-A No. 2003-327583 was synthesized, and a resin was obtained in the same manner as in Example 2.

  When the optical properties and specific gravity of the obtained resin were measured, the refractive index was ne = 1.72 and νe = 35. Compared with Example 2, the refractive index was inferior.

Claims (7)

One or more compounds selected from the group consisting of methylene bisthiocyanate, bis (thiocyanatomethyl) sulfide, and bis (thiocyanatomethyl) disulfide;
A compound having a mercapto group and a thietanyl group in the molecular structure;
A process for producing a sulfur-containing cyclic compound having a structure represented by the following formula (1), comprising a step of reacting the raw material under alkaline conditions in a reaction solvent.

(In the formula, a, b, c and d each independently represent an integer of 0 or 1.)   The one or more compounds selected from the group consisting of methylene bisthiocyanate, bis (thiocyanatomethyl) sulfide, and bis (thiocyanatomethyl) disulfide are methylene bisthiocyanate. The method described.   The compound having a mercapto group and a thietanyl group in the molecular structure is one or more compounds selected from the group consisting of 3-mercaptothietane, 3- (mercaptomethylthio) thietane and 3- (mercaptomethyldithio) thietane. The method according to claim 1 or 2.   The method according to any one of claims 1 to 3, wherein the compound having a mercapto group and a thietanyl group in the molecular structure is 3-mercaptothietane.   The method according to any one of claims 1 to 4, wherein the reaction solvent is an alcohol compound.   The sulfur-containing cyclic compound is 1,4-bis (3-thietanyl) -1,3,4-trithiabutane, 1,5-bis (3-thietanyl) -1,2,4,5-tetrathiapentane, 6-bis (3-thietanyl) -1,3,4,6-tetrathiahexane, 1,6-bis (3-thietanyl) -1,3,5,6-tetrathiahexane, 1,7-bis ( 3-thietanyl) -1,2,4,5,7-pentathiaheptane, 1,7-bis (3-thietanyl) -1,2,4,6,7-pentathiaheptane, Item 6. The method according to any one of Items 1 to 5.   The method according to any one of claims 1 to 6, wherein a sulfur atom content in a molecule of the sulfur-containing cyclic compound is 61% or more.