JP4520776B2 - High refractive index thietane compound - Google Patents

Description

  The present invention relates to a thietane compound suitably used in the field of resins such as optical materials that require high refractive index and high transparency, and a cured resin thereof.

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 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 a high refractive index and good impact resistance (see, for example, Patent Document 1).

  However, there is a demand for higher refractive index and higher Abbe number, but on the other hand, both the refractive index and Abbe number are contradictory properties that the Abbe number decreases as the refractive index increases. It is very difficult to improve at the same time. Therefore, studies for increasing the refractive index while suppressing the decrease in the Abbe number have been actively conducted.

The most representative proposal among these studies is a method using an episulfide compound. (For example, see Patent Document 2 and Patent Document 3)
A method of using a thietane compound as a compound different from episulfide has been proposed. (For example, see Patent Document 4)
JP-A-63-46213 WO-89 / 10575 publication Japanese Patent Laid-Open No. 9-110979 JP 2003-327583 A

  According to the methods of Patent Documents 3 and 4, it is considered that a high refractive index can be realized while having a relatively high Abbe number. Patent Document 4 exemplifies a number of novel thietane compounds, and the production method thereof is also described in detail. However, the cured resin obtained from the novel compound described in the patent document has a refractive index of about 1.74 and is not a satisfactory material at the present time when a higher refractive index is required. Therefore, development of materials having higher refractive index and higher Abbe number is required.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have succeeded in producing a novel thietane compound, and further, the refractive index of a resin obtained by curing the compound is higher, and the Abbe number In addition, the present inventors have found that excellent optical properties and physical properties such as high impact resistance and high physical properties can be obtained.

That is, the present invention relates to [ 1 ] a thietane compound having a structure represented by the following formula (3).

(Wherein, a, b, c and d each represents an integer of 0 or 1, satisfying 2 ≦ a + b + c + d ≦ 4. R1 may be a straight chain or branched thiated with 1 to 4 carbon atoms . Represents a hydrocarbon group, a cyclic hydrocarbon group having 3 to 6 carbon atoms which may be thiated, a 1,4-dithian group, an arylene group or an aralkylene group , and these groups may be substituted or unsubstituted When a + b + c + d = 2, R1 may represent a direct bond R2- R9 is a hydrogen atom, or a substituted or unsubstituted straight or branched straight or branched carbon having 1 to 4 carbon atoms that may be thiated . Represents a hydrocarbon group or a cyclic hydrocarbon group having 3 to 6 carbon atoms. )
[ 2 ] The thietane compound of [1] having a structure represented by the following formula (4).

(In the formula, n represents an integer of 2 to 4. R10 is a linear or branched hydrocarbon group having 1 to 4 carbon atoms which may be thiated, or a cyclic group having 3 to 6 carbon atoms. Represents an optionally substituted hydrocarbon group, 1,4-dithiane group, arylene group, or aralkylene group , and these groups may be substituted or unsubstituted, and when n = 2, R10 represents a direct bond. R11 and R12 are each a hydrogen atom, a substituted or unsubstituted linear or branched hydrocarbon group having 1 to 4 carbon atoms or a cyclic hydrocarbon group having 3 to 6 carbon atoms, which may be thiated. In addition, the carbon number here indicates the number of carbon after thialation when it is thialated.)

[3 ] The thietane compound is 1,4-bis (3-thietanyldithio) -2,3-dithiabutane, 1,1,1-tris (3-thietanyldithiomethylthio) methane, 1,1,2,2-tetrakis (3-thietanyldithiomethylthio) ethane, 1,1,3,3-tetrakis (3-thietanyldithiomethylthio) propane, or 2- [1,1-bis (3-thietanyldithiomethylthio) methyl] The thietane compound according to [1] or [2], which is any of -1,3-dithietane.
[ 4 ] A polymerizable composition containing the thietane compound according to any one of [1] to [ 3 ].
[ 5 ] The polymerizable composition as described in [ 4 ], further containing a single sulfur.
[ 6 ] A resin obtained by curing the polymerizable composition as described in [ 4 ] or [ 5 ].
[ 7 ] An optical material comprising the resin according to [ 6 ].
[ 8 ] A method for producing a resin, comprising a step of subjecting the polymerizable composition according to [ 4 ] or [ 5 ] to cast polymerization.
[ 9 ] A method for producing the thietane compound according to any one of [1] to [ 3 ], using bis (3-thietanyl) disulfide and a compound having a mercaptomethylthio group as raw materials.
[10 ] The production method according to [9], wherein a compound having an alcoholic hydroxyl group and / or an alkaline aqueous solution is used as a cleaning solvent.
It is about each.

  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, and the optical properties of a resin obtained by polymerization and curing are very high and the impact resistance is also high. Contributes to higher refractive index and thinner thickness.

Hereinafter, the present invention will be described in detail. First, the thietane compound of the present invention will be described.
The thietane compound of the present invention is a compound having 2 to 4 disulfide bonds and 2 to 4 thietanyl groups in the molecule, and relates to a thietane compound having a molecular weight of 1000 or less.

  Here, the disulfide bond means a —S—S— bond among the C—S—S—C bonds. The thietanyl group is a hydrocarbon group having a four-membered ring structure, and means a group in which one of the four carbons is substituted with sulfur. For example, a thietanyl group in which the carbon at the 3-position is substituted with sulfur is referred to as a 3-thietanyl group. When the molecular weight is 1000 or less, for example, unlike a compound having a disulfide bond and a thietanyl group at the end of a long-chain alkyl structure, it is advantageous for satisfying the purpose of high refractive index and high Abbe number. Moreover, when handling property at the time of manufacturing a resin or an optical material is taken into consideration, the molecular weight is desirably 1000 or less. Therefore, the molecular weight is more preferably 950 or less, and even more preferably 900 or less. The molecular weight is preferably 250 or more in consideration of the possibility that the workability is more stable due to the relationship with volatility and the like. If it is 280 or more, it is more preferable.

  Specifically, the thietane compound of the present invention preferably has a structure represented by the following general formula (1).

(In the formula, R1 represents a linear or branched hydrocarbon group having 1 to 4 carbon atoms which may be thiated, a cyclic hydrocarbon group having 3 to 6 carbon atoms which may be thiated, 1, Represents a 4-dithian group, an arylene group, an aralkylene group, or a direct bond, R1 may be substituted or unsubstituted, and R2 to R9 may be a hydrogen atom or a substituted or unsubstituted straight chain that may be thiated. Represents a chain or branched hydrocarbon group having 1 to 4 carbon atoms or a cyclic hydrocarbon group having 3 to 6 carbon atoms, a, b, c and d each represents an integer of 0 or 1, and 2 ≦ a + b + c + d ≦ 4 Meet)

  Here, the substituted or unsubstituted C1-C4 hydrocarbon group represented by R1 includes a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkenyl group, an aryl group and an aralkyl group. Is included. R1 is preferably a methylene group, an ethylene group, or a propylene group.

The hydrogen atom represented by R2 to R9 or the substituted or unsubstituted hydrocarbon group having 1 to 4 carbon atoms includes a linear, branched or cyclic alkylene group, a linear, branched or cyclic alkenylene group, an arylene group, Aralkylene groups are included. R2 to R9 are preferably hydrogen atoms, and in the case of hydrocarbon groups, it is more preferable that they are thialated.
The 2 to 4 groups bonded to R1 may be the same or different, but are preferably the same.

  Furthermore, as a more specific structure than Formula (1), what has a structure represented by following General formula (3) is more preferable.

(In the formula, R1 represents a linear or branched hydrocarbon group having 1 to 4 carbon atoms which may be thiated, a cyclic hydrocarbon group having 3 to 6 carbon atoms which may be thiated, 1, Represents a 4-dithian group, an arylene group, an aralkylene group, or a direct bond, R1 may be substituted or unsubstituted, and R2 to R9 may be a hydrogen atom or a substituted or unsubstituted straight chain that may be thiated. Represents a chain or branched hydrocarbon group having 1 to 4 carbon atoms or a cyclic hydrocarbon group having 3 to 6 carbon atoms, a, b, c and d each represents an integer of 0 or 1, and 2 ≦ a + b + c + d ≦ 4 Meet)

  Here, the substituted or unsubstituted C1-C4 hydrocarbon group represented by R1 includes a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkenyl group, an aryl group and an aralkyl group. Is included. R1 is preferably a methylene group, an ethylene group, or a propylene group.

The hydrogen atom represented by R2 to R9 or the substituted or unsubstituted hydrocarbon group having 1 to 4 carbon atoms includes a linear, branched or cyclic alkylene group, a linear, branched or cyclic alkenylene group, an arylene group, Aralkylene groups are included. R2 to R9 are preferably hydrogen atoms, and in the case of hydrocarbon groups, it is more preferable that they are thialated.
The 2 to 4 groups bonded to R1 may be the same or different, but are preferably the same.

  Here, among the compounds having the structure represented by the formula (1), specific examples of particularly preferable compounds include 1,4-bis (3-thietanyldithio) -2,3-dithiabutane, 1,1,1-tris. (3-thietanyldithio) methane, 1,1,1-tris (3-thietanyldithiomethylthio) methane, 1,1,2,2-tetrakis (3-thietanyldithio) ethane, 1,1,2,2-tetrakis ( 3-thietanyldithiomethylthio) ethane, 1,1,3,3-tetrakis (3-thietanyldithio) propane, 1,1,3,3-tetrakis (3-thietanyldithiomethylthio) propane, 2- [1,1 -Bis (3-thietanyldithio) methyl] -1,3-dithietane, 2- [1,1-bis (3-thietanyldithiomethylthio) methyl] -1,3-dithietane, etc. It can be exemplified, but not limited to these exemplified compounds.

  As a method for producing a thietane compound having 2 to 4 disulfide bonds and 2 to 4 thietanyl groups in the molecule of the present invention and having a molecular weight of 1000 or less, a compound having a disulfide bond and a mercapto group And a method utilizing a disulfide exchange reaction that occurs with a compound having the following. At this time, in some cases, the target product can be more neatly produced by using an inorganic base, an organic base, an inorganic acid, an organic acid, or the like as a catalyst.

  The reaction solvent used in carrying out this reaction may be any solvent without solvent, polar solvent alone, or any material that can dissolve a compound having a disulfide bond and a compound having a mercapto group. It is also possible to use a mixed solvent of a solvent and a nonpolar solvent. Specific examples of the polar solvent here include alcohols such as water, methanol and ethanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, esters such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate, Examples include ethers such as diethyl ether and tetrahydrofuran, and aprotic polar solvents such as dimethylformamide, dimethylimidazolidinone, and dimethyl sulfoxide, but are not limited to the exemplified compounds. Specific examples of nonpolar solvents include aromatic hydrocarbons such as benzene, toluene and xylene and their halogen substitution products, aliphatic hydrocarbons such as hexane and cyclohexane, and halogenation such as dichloromethane, chloroform and carbon tetrachloride. Although hydrocarbons etc. are mentioned, it is not necessarily limited to an exemplary compound.

  Examples of the catalyst that can be used here include, as inorganic bases, alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal heavy metals. Examples of the organic base include tertiary amine, secondary amine, primary amine, metal alkoxide, trialkylphosphine, triarylphosphine, quaternary ammonium salt, and quaternary phosphonium salt. It is done. Examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, and examples of organic acids include formic acid, acetic acid, propionic acid, and phthalic acid. Among these, compounds having basicity are preferable, but tertiary amines, secondary amines, primary amines, and phosphines are more preferable.

  In the present invention, it is preferable to use bis (3-thietanyl) disulfide as the compound having a disulfide bond. In the present invention, the compound having a mercapto group means a polythiol having two or more functions, and the polythiol is preferably a compound having a mercaptomethylthio group.

  Specific examples of preferred polythiols in the present invention 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-dimethyl Lucapto-1-propanol (3-mercaptopropionate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercapto Propyl 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 te Rakisu (3-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 A heterocyclic compound 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.

  Among these compounds, more preferable compounds are compounds having a mercaptomethylthio group, and specifically include bis (mercaptomethyl) sulfide, bis (mercaptomethyl) disulfide, bis (mercaptomethylthio) methane, 1,2- Aliphatic polythiol compounds containing sulfur atoms in addition to mercapto groups such as bis (mercaptomethylthio) ethane, 1,2,3-tris (mercaptomethylthio) propane, tetrakis (mercaptomethylthiomethyl) methane, 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-thia N, 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 -Dithian, 2,2-bis (mercaptomethylthio) -1,3-propanedithiol, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3,6-bis (mercaptomethylthio) -1,9 Dimercapto-2,5,8-trithianonane, 4,6-bis (mercaptomethylthio) -1,9-dimercapto-2,5,8- Lithianonane, 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) methane, 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-tetrathi Atridecane, 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-te Lakis (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-dithianylthio} -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}- -{2,2-bis (mercaptomethylthio) ethyl} -7,9-bis (mercaptomethylthio) -2,4,6,10-tetrathiaundecane, 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-dithietanyl)} 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-Dichi An, 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-dimercapto-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- {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-mercaptome Ruthio-1,3-dithiolane, 2- [bis {3,4-bis (mercaptomethylthio) -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-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-dithiolanyl) thio} -5- [1- {2- (1,3-dithietanyl)}-3-mercapto-2 -Compounds having a dithioacetal or dithioketal skeleton such as thiapropylthio] -1,3-dithiolane,

  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 ] A compound having an ortho trithioformate skeleton such as methane,

3,3′-di (mercaptomethylthio) -1,5-dimercapto-2,4-dithiapentane, 2,2′-di (mercaptomethylthio) -1,3-dithiacyclopentane, 2,7-di (mercapto) Orthotetrathiocarbonate such as methyl) -1,4,5,9-tetrathiaspiro [4,4] nonane, 3,9-dimercapto-1,5,7,11-tetrathiaspiro [5,5] undecane Examples thereof include compounds having an ester skeleton. These exemplified compounds may be used alone or in combination of two or more.

  In the case of the present invention, the disulfide exchange reaction proceeds as shown in the following formula (5), for example.

  Here, R is a linear or branched hydrocarbon group having 1 to 4 carbon atoms which may be thiated, a cyclic hydrocarbon group having 3 to 6 carbon atoms which may be thiated, 1, 4 -Represents a dithian group, an arylene group, or an aralkylene group. R may be substituted or unsubstituted.

  In this reaction, the reaction between the disulfide bond of the raw material and the mercapto group is theoretically an equimolar reaction, but in order to improve the production rate of the target product, the number of moles of the raw material bis (3-thietanyl) disulfide. Is preferably used in an equivalent amount or more than the number of moles of the mercapto group of the polythiol compound. It is more preferable to use 2 times mole or more. It is more preferable to use 3 times mole or more. Considering economical efficiency and purification load, 10 times mole or less is preferable.

  In order to give top priority to economic efficiency and purification load, and minimize the amount of bis (3-thietanyl) disulfide used, the polythiol compound is added dropwise, and the reaction system always contains excess bis (3-thietanyl) disulfide. The method of proceeding the reaction with is preferable.

  The reaction temperature cannot be generally limited depending on the performance of the catalyst used. However, when the temperature is too high, the ring-opening polymerization of the thietanyl group proceeds, which is not preferable. When the temperature is too low, the exchange reaction does not proceed. Therefore, it is preferably in the range of 0 ° C to 100 ° C, more preferably in the range of 10 ° C to 80 ° C.

  After the exchange reaction is completed, it is preferable to remove the compound having an excess disulfide bond and 3-mercaptothietane as a by-product in view of the final compound and the physical properties of the resin obtained by polymerization and curing.

  The method for removing the compound will be described in the description relating to the handling of the polymerizable composition as follows.

  Further, the removed 3-mercaptothietane is recovered through an operation such as neutralization and distillation, and bis (3-thietanyl) disulfide is synthesized again and then used for the next disulfide exchange reaction.

  Next, it describes about the polymeric composition containing the thietane compound which has a structure represented by Formula (1) of this invention. A constituent requirement of the polymerizable composition of the present invention is to contain a thietane compound having a structure represented by the formula (1), but the refractive index and Abbe number of the resin obtained by curing the polymerizable composition. Adjustment of optical properties such as 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. For the purpose of improving the resin and improving the handleability, such as adjusting the physical properties, adjusting the transmittance and transparency, adjusting the viscosity of the polymerizable composition, and other handling and handling methods of transportation, etc. It is good to apply techniques and operations generally used in synthesizing organic compounds such as cold preservation, filtration, and decompression treatment, and to add known compounds as stabilizers and resin modifiers. It may be preferable for the purpose of obtaining a 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, to improve the hue or to increase the purity, but in the formula (1) of the present invention. The method for purifying the polymerizable composition containing the thietane compound having the structure represented can be a known method such as distillation, recrystallization, column chromatography (silica gel method, activated carbon method, ion exchange resin method, etc.), extraction, etc. Any method may be used at any timing, as long as the transparency and hue of a resin obtained by curing a composition generally obtained by purification are improved. In the present invention, an excessive amount of raw materials and by-products are present in the composition, but it is preferable to purify by the above-described method.

  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 It is used when synthesizing a polymerizable composition, for example, a causative substance that lowers the physical properties of the resin or a substance that inhibits the transparency of the resin, by washing with a polar and / or non-polar solvent at a timing such as after taking out the resin. Or a method of removing or reducing the amount of a by-product compound. 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. In the present invention, for example, a compound having an alcoholic hydroxyl group is preferable, and methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, tert-butanol and the like are more preferable. In the present invention, the component to be removed may be a thiol compound, and can be easily removed to the aqueous layer side by washing with an alkaline aqueous solution. Here, specific examples of preferable alkalis constituting the aqueous alkali solution are preferably alkali metals or inorganic alkalis such as alkaline earth metal hydroxides, carbonates, hydrides, and particularly hydroxides. preferable. About the usage-amount of an alkali component, when the component removed is a thiol compound, for example, it is good to use more than the equivalent of a thiol compound, and it is good to use normally 1.5 times equivalent or more. The concentration differs depending on the compound to be handled, the compound to be removed, and the solvent to be used, and cannot be limited in general. However, it does not have to interfere with the stirring performed at the time of washing. Furthermore, if the above alkali cleaning and alcohol cleaning are used in combination, a further cleaning effect may be expected.

  The components to be 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. Generally, 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 and storage stability of the compound constituting the polymerizable composition to be handled, it is 20 ° C. in the case of the polymerizable composition containing the compound having the structure represented by the formula (1). It is good to store at the following low temperature, preferably 10 ° C. or less. However, when the melting point is high, handling at the time of use may be good if it is carried out at a temperature higher than the normal freezing point. 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 very 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 episulfide 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 allowable 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 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 properties and structure of the dissolved gas, and the type. Is preferable.

  Subsequently, the resin modifier will be described. Examples of the resin modifier include known thietane compounds, dithietane compounds, trithietane compounds, thiolane compounds, dithiolane compounds, trithiolane compounds, dithian compounds, trithian compounds, episulfide compounds and epoxy compounds, amine compounds, the present compounds, Thiol compounds that can be used as raw materials of the invention, hydroxy compounds including phenolic compounds, iso (thio) cyanate compounds, mercapto organic acids, organic acids and anhydrides, amino acids and mercaptoamines, (meth) acrylates And the like, cyclic organic compounds and inorganic compounds having a sulfur atom or a selenium atom, and simple sulfur 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. 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 preferable for improving the refractive index of the resin, and in particular, when a single sulfur is used, the operation is simple and the effect of improving the refractive index is particularly large. preferable. As a single sulfur addition amount, 3 to 30% by weight may be used with respect to the entire polymerizable composition. Considering the heat resistance and brittleness of the resulting resin, it is preferable to use 5 to 25% by weight.

Here, a compound that can be used as a resin modifier will be specifically described.
Specific examples of thietane compounds other than the thietane compound of the present invention that can be used as the resin modifier of the present invention include bis (3-thietanyl) sulfide, 1,4-bis (3-thietanyl) -1,3, 4-trithiabutane, 1,6-bis (3-thietanyl) -1,3,4,6, -tetrathiahexane, 1,6-bis (3-thietanyl) -1,3,5,6, -tetrathia Hexane, 1,1-bis (3-thietanylthio) methane, 1,2-bis (3-thietanylthio) ethane, 1,2-bis (3-thietanylthio) propane, 1,3-bis (3-thietanylthio) propane, 1,3-bis (3-thietanylthio) -2-methylpropane, 1,4-bis (3-thietanylthio) butane, 1,4-bis (3-thietanylthio) -2-methylbutane, 1,3-bis 3-thietanylthio) butane, 1,5-bis (3-thietanylthio) pentane, 1,5-bis (3-thietanylthio) -2-methylpentane, 1,5-bis (3-thietanylthio) -3-thiapentane, , 6-bis (3-thietanylthio) hexane, 1,6-bis (3-thietanylthio) -2-methylhexane, 3,8-bis (3-thietanylthio) -3,6-dithiaoctane, 1,2,3- Tris (3-thietanylthio) propane, 2,2-bis (3-thietanylthio) -1,3-bis (3-thietanylthiomethyl) propane, 2,2-bis (3-thietanylthiomethyl) -1- (3-thietanylthio) butane, 1,5-bis (3-thietanylthio) -2- (3-thietanylthiomethyl) -3-thiapentane, 1,5-bis (3-thie Nylthio) -2,4-bis (3-thietanylthiomethyl) -3-thiapentane, 1- (3-thietanylthio) -2,2-bis (3-thietanylthiomethyl) -4-thiahexane, 1,5 , 6-Tris (3-thietanylthio) -4- (3-thietanylthiomethyl) -3-thiahexane, 1,8-bis (3-thietanylthio) -4- (3-thietanylthiomethyl) -3,6 -Dithiaoctane, 1,8-bis (3-thietanylthio) -4,5-bis (3-thietanylthiomethyl) -3,6-dithiaoctane, 1,8-bis (3-thietanylthio) -4,4-bis (3-thietanylthiomethyl) -3,6-dithiaoctane, 1,8-bis (3-thietanylthio) -2,5-bis (3-thietanylthiomethyl) -3,6-dithiaoctane, 1,8- Screw (3-thietanylthio) -2,4,5-tris (3-thietanylthiomethyl) -3,6-dithiaoctane, 1,1,1-tris [[2- (3-thietanylthio) ethyl] thiomethyl] -2 -(3-thietanylthio) ethane, 1,1,2,2-tetrakis [[2- (3-thietanylthio) ethyl] thiomethyl] ethane, 1,11-bis (3-thietanylthio) -4,8-bis (3 -Thietanylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (3-thietanylthio) -4,7-bis (3-thietanylthiomethyl) -3,6,9-trithia Undecane, 1,11-bis (3-thietanylthio) -5,7-bis (3-thietanylthiomethyl) -3,6,9-trithiaundecane, 1,1,3,3-tetrakis (3-thietanylthio) Tilthio) propane, 1,1,2,2-tetrakis (3-thietanylthiomethylthio) ethane, 3- (3-thietanylthiomethyl) -1,5-di (3-thietanylthio) -2,4-dithiapentane Chain aliphatic 3-thietanylthio compounds such as bis (3-thietanyl) disulfide, bis (3-thietanyl) trisulfide, bis (3-thietanyl) tetrasulfide, and the like, and

1,3-bis (3-thietanylthio) cyclohexane, 1,4-bis (3-thietanylthio) cyclohexane, 1,3-bis (3-thietanylthiomethyl) cyclohexane, 1,4-bis (3-thietanylthio) Methyl) cyclohexane, 2,5-bis (3-thietanylthiomethyl) -1,4-dithiane, 4,6-bis (3-thietanylthiomethyl) -1,3-dithiane, 4,5-bis ( 3-thietanylthiomethyl) -1,3-dithiolane, 2,4-bis (3-thietanylthiomethyl) -1,3-dithietane, 2,5-bis [[2- (3-thietanylthio) ethyl] Thiomethyl] -1,4-dithiane, 2,5-bis (3-thietanylthiomethyl) -2,5-dimethyl-1,4-dithiane, 2-bis (3-thietanylthio) methyl-1,3-dithi Orchids and cyclic aliphatic 3-thietanylthio compounds, and,
1,2-bis (3-thietanylthio) benzene, 1,3-bis (3-thietanylthio) benzene, 1,4-bis (3-thietanylthio) benzene, 1,2-bis (3-thietanylthiomethyl) benzene 1,3-bis (3-thietanylthiomethyl) benzene, 1,4-bis (3-thietanylthiomethyl) benzene, bis [4- (3-thietanylthio) phenyl] methane, 2,2-bis [ 4- (3-thietanylthio) phenyl] propane, bis [4- (3-thietanylthio) phenyl] sulfide, bis [4- (3-thietanylthio) phenyl] sulfone, 4,4′-bis (3-thietanylthio) biphenyl, etc. Aromatic 3-thietanylthio compounds of 1,3-bis (3-thietanylthio) propan-1-one, Examples thereof include 3-bis (3-thietanylthio) -2-methylpropan-1-one, but are not limited to these exemplary compounds. Among the exemplified compounds, preferred compounds include bis (3-thietanyl) sulfide, 1,4-bis (3-thietanyl) -1,3,4-trithiabutane, 1,6-bis (3-thietanyl) -1, 3,4,6, -tetrathiahexane, 1,6-bis (3-thietanyl) -1,3,5,6, -tetrathiahexane, 1,1-bis (3-thietanylthio) methane and 1,2 -Bis (3-thietanylthio) ethane, 1,2,3-tris (3-thietanylthio) propane, 1,8-bis (3-thietanylthio) -4- (3-thietanylthiomethyl) -3,6-dithiaoctane 1,11-bis (3-thietanylthio) -4,8-bis (3-thietanylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (3-thietanylthio) -4,7 -Screw 3-thietanylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (3-thietanylthio) -5,7-bis (3-thietanylthiomethyl) -3,6,9-tri Thiaundecane, 2,5-bis (3-thietanylthiomethyl) -1,4-dithiane, 2,5-bis [[2- (3-thietanylthio) ethyl] thiomethyl] -1,4-dithiane, 2, 5-bis (3-thietanylthiomethyl) -2,5-dimethyl-1,4-dithiane, 4,5-bis (3-thietanylthiomethyl) -1,3-dithiolane, 2,4-bis ( 3-thietanylthiomethyl) -1,3-dithietane, 2-bis (3-thietanylthio) methyl-1,3-dithiolane, bis (3-thietanyl) disulfide, bis (3-thietanyl) trisulfide, bis (3 -Chieta And bis (3-thietanyl) sulfide, 1,4-bis (3-thietanyl) -1,3,4-trithiabutane, 1,6-bis (3-thietanyl). -1,3,4,6, -tetrathiahexane, 1,6-bis (3-thietanyl) -1,3,5,6, -tetrathiahexane, bis (3-thietanylthio) methane, bis (3- Thietanylthiomethyl) sulfide, 2-bis (3-thietanylthio) methyl-1,3-dithiolane, bis (3-thietanyl) disulfide, bis (3-thietanyl) trisulfide, bis (3-thietanyl) tetrasulfide. .

  Next, specific examples of the episulfide compound as the resin modifier of the present invention include bis (1,2-epithioethyl) sulfide, bis (epithioethylthio) methane, bis (epithioethylthio) benzene, bis [ Epithioethyl compounds such as 4- (epithioethylthio) phenyl] sulfide, bis [4- (epithioethylthio) phenyl] methane, bis (1,2-epithioethyl) disulfide, bis (2,3-epithiopropyl) Sulfide, bis (2,3-epithiopropylthio) methane, 1,2-bis (2,3-epithiopropylthio) ethane, 1,2-bis (2,3-epithiopropylthio) propane, , 3-bis (2,3-epithiopropylthio) 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-epithiopropyl) Thio) 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-epithiopropylthio) hexane, 1,6-bis (2,3-epithiopropylthio) -2-methylhexane, 3,8-bis (2,3-epithiopropylthio) -3,6-dithiaoctane, 1,2,3-tris (2,3-epithiopropylthio) propane, 2,2-bis (2,3 -Epithiopropylthio) -1,3-bis (2 3-epithiopropylthiomethyl) propane, 2,2-bis (2,3-epithiopropylthiomethyl) -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-epithiopropylthio) -2,2-bis (2,3-epithiopropylthiomethyl) -4-thiahexane, 1,5, 6-Tris (2,3-epithiopropylthio) -4- (2,3-epithiopropylthiomethyl) -3-thiahexane, 1,8-bis (2,3-epithiopropylthio) -4- (2,3-epithiopropylthiome Til) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropylthio) -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-epithiopropyl) Thio) -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-epithiopropylthio) ethyl] thiomethyl] -2- (2,3- Epithiopropylthio) ethane, 1,1,2,2- Trakis [[2- (2,3-epithiopropylthio) ethyl] thiomethyl] ethane, 1,11-bis (2,3-epithiopropylthio) -4,8-bis (2,3-epithiopropyl) Thiomethyl) -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, Chain aliphatic 2,3-epithiopropylthio compounds such as bis (2,3-epithiopropyl) disulfide, 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) Can be exemplified aromatic 2,3-epithiopropyl oxy compounds such as phenyl, it is not limited only to the exemplified compounds.

  Among the exemplified compounds, preferred compounds are bis (1,2-epithioethyl) sulfide, bis (2,3-epithiopropyl) sulfide, bis (2,3-epithiopropylthio) methane, bis (1,2 -Epithioethyl) disulfide and bis (2,3-epithiopropyl) disulfide, and more preferred compounds are 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. And the like Le cyclohexene 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-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-epoxy Propylthio) -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) pentane, 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-epoxypropylthiomethyl) -3-thiapentane, 1,5-bis (2 , -Epoxypropylthio) -2,4-bis (2,3-epoxypropylthiomethyl) -3-thiapentane, 1- (2,3-epoxypropylthio) -2,2-bis (2,3-epoxypropyl) Thiomethyl) -4-thiahexane, 1,5,6-tris (2,3-epoxypropylthio) -4- (2,3-epoxypropylthiomethyl) -3-thiahexane, 1,8-bis (2, 3-epoxypropylthio) -4- (2,3-epoxypropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epoxypropylthio) -4,5-bis (2,3 -Epoxypropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epoxypropylthio) -4,4-bis (2,3-epoxypropylthiomethyl) -3,6-dithia Octane, 1,8-bis (2,3-epoxypropylthio) -2,5-bis (2,3-epoxypropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epoxy Propylthio) -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- (2,3-epoxypropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (2,3-epoxypropylthio) -5,7-bis (2,3-epoxypropylthio) Chain aliphatic 2,3-epoxypropylthio compounds such as methyl) -3,6,9-trithiaundecane, bis (2,3-epoxypropyl) disulfide, and the like, 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-epoxypropyl thio compounds,

  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, Cycloepoxy 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) Can be exemplified aromatic 2,3-epoxypropyloxy compounds such as phenyl, it is not limited only 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- or 1,4-diaminomethylcyclohexane, 2- or 4-aminopiperidine, 2- or 4-aminomethylpiperidine, 2- or 4-aminoethylpiperidine, N-aminoethylmorpholine, N- Primary polyamine compounds such as aminopropylmorpholine,

  Diethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine, diisobutylamine, di-n-pentylamine, di-3-pentylamine, dihexylamine, dioctylamine, di (2-ethylhexyl) amine, methyl Hexylamine, diallylamine, N-methylallylamine, piperidine, pyrrolidine, diphenylamine, N-methylamine, N-ethylamine, dibenzylamine, N-methylbenzylamine, N-ethylbenzylamine, dicyclohexylamine, N-methylaniline, N -Monofunctional secondary amine compounds such as ethylaniline, dinaphthylamine, 1-methylpiperazine, morpholine,

  N, N′-dimethylethylenediamine, N, N′-dimethyl-1,2-diaminopropane, N, N′-dimethyl-1,3-diaminopropane, N, N′-dimethyl-1,2-diaminobutane, N, N′-dimethyl-1,3-diaminobutane, N, N′-dimethyl-1,4-diaminobutane, N, N′-dimethyl-1,5-diaminopentane, N, N′-dimethyl-1 , 6-Diaminohexane, N, N′-dimethyl-1,7-diaminoheptane, N, N′-diethylethylenediamine, N, N′-diethyl-1,2-diaminopropane, N, N′-diethyl-1 , 3-diaminopropane, N, N′-diethyl-1,2-diaminobutane, N, N′-diethyl-1,3-diaminobutane, N, N′-diethyl-1,4-diaminobutane, N, N ' Diethyl-1,5-diaminopentane, N, N′-diethyl-1,6-diaminohexane, N, N′-diethyl-1,7-diaminoheptane, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine 2,6-dimethylpiperazine, homopiperazine, 1,1-di- (4-piperidyl) methane, 1,2-di- (4-piperidyl) ethane, 1,3-di- (4-piperidyl) propane, Secondary polyamine compounds such as 1,4-di- (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 of these compounds 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 bi- or higher functional polythiol compound include polythiols that can be used when synthesizing the above-described thietane compound having a disulfide bond. Among these compounds, the optical properties of the obtained resin, particularly the Abbe number, are exemplified. In consideration, it is preferable to select an aliphatic polythiol compound rather than an aromatic one. 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. 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 thereof include a condensation reaction product of an organic polybasic acid such as an acid and the polyol, an addition reaction product 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'-tetramethylxylyl 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 and 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, 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, 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.

  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, 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 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 an episulfide compound having a structure represented by the formula (1) of the present invention can be usually cured by using a method for polymerizing a known episulfide compound, and is a cured resin. The type and amount of the curing catalyst and the like, and the type and ratio of the monomer differ depending on the structure of the compound constituting the polymerizable composition, and cannot be generally limited. Other than the above resin modifiers, 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-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 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.

  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.

  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 episulfide compound of the present invention or may be added after being dissolved or dispersed in another compound constituting the polymerizable composition, but after being dissolved or dispersed in another compound. The addition may give a preferable result. 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 a polymerizable composition containing an episulfide compound having a structure represented by the formula (1) of the present invention is cured and a resin is molded, other than the above, as in a known molding method, depending on the purpose Stabilizers, resin modifiers, chain extenders, crosslinking agents, light stabilizers typified by HALS, UV absorbers typified by benzotriazole, antioxidants typified by hindered phenols, anti-coloring Various substances such as an agent, a dye represented by an anthraquinone-based disperse dye, a filler, an external mold release agent represented by a silicone series or an internal mold release agent, 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 release effect and do not impair physical properties such as transparency of the resin, but preferably a surfactant. 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. These internal mold 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. It is used in the range of 0.001 to 10 wt% with respect to the weight, 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-mentioned 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. The refractive index of the optical material of the present invention is usually 1.70 or more, and is preferably 1.74 or more, more preferably 1.76 or more, particularly from the viewpoint of fashionability or the like of an eyeglass lens produced using the optical material. Preferably it is 1.77 or more.

  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.

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 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.
-Heat resistance: Tg in the TMA penetration method (50 g load, pin tip 0.5 mmφ) was regarded as heat resistance. Those having no inflection point when the TMA curve was analyzed were set to> 130 ° C. for convenience.
-Resin transparency: Observed visually under a high-pressure mercury lamp. Cloudy ones were marked with x, and ones with excellent transparency were marked with ◯.

[Example 1]
A reactor equipped with a stirrer and a thermometer was charged with 420 g of bis (3-thietanyl) disulfide and 500 g of toluene, 0.5 g of N, N-dicyclohexylmethylamine was added as a catalyst, and then bis (mercapto) was added from a dropping funnel. Methyl) sulfide (79 g) was added dropwise at 30 ° C. over 15 hours to allow the long pattern reaction to proceed, and after completion of the dropwise addition, aging was performed with stirring for 5 hours. After completion of the reaction, the toluene layer was washed twice with 500 g of 15% aqueous sodium hydroxide solution. Next, after distilling off toluene under reduced pressure, 500 g of isopropyl alcohol was further charged, stirred for 30 minutes, and allowed to stand to separate. The upper isopropyl alcohol layer was removed. After removing the lower layer obtained by repeating the same washing operation twice, the isopropyl alcohol dissolved by topping was removed. Subsequently, purification was performed by passing the residue obtained after topping through a silica gel column using hexane and chloroform as developing solvents. As a result of analysis to confirm the structure of the compound obtained by purification, it was 1,4-bis (3-thietanyldithio) -2,3-dithiabutane (hereinafter abbreviated as compound (a)).
Here, the identification data of the obtained compound is shown below.

[Example 2]
The reaction, washing, removal and purification were carried out in the same manner as in Example 1 except that 84 g of 1,1,1-tris (mercaptomethylthio) methane was used instead of 79 g of bis (mercaptomethyl) disulfide. As a result of analysis to confirm the structure of the compound obtained by purification, it was 1,1,1-tris (3-thietanyldithiomethylthio) methane (hereinafter abbreviated as compound (b)).
Here, the identification data of the obtained compound is shown below.

[Example 3]
The reaction, washing, removal and purification were carried out in the same manner as in Example 1 except that 86 g of 1,1,2,2-tetrakis (mercaptomethylthio) ethane was used instead of 79 g of bis (mercaptomethyl) disulfide. As a result of analysis to confirm the structure of the compound obtained by purification, it was 1,1,2,2-tetrakis (3-thietanyldithiomethylthio) ethane (hereinafter abbreviated as compound (c)). .
Here, the identification data of the obtained compound is shown below.

[Example 4]
The reaction, washing, removal and purification were carried out in the same manner as in Example 1 except that 89 g of 1,1,3,3-tetrakis (mercaptomethylthio) propane was used instead of 79 g of bis (mercaptomethyl) disulfide. As a result of analysis to confirm the structure of the compound obtained by purification, it was 1,1,3,3-tetrakis (3-thietanyldithiomethylthio) propane (hereinafter abbreviated as compound (d)). .
Here, the identification data of the obtained compound is shown below.

[Example 5]
In the same manner as in Example 1, except that 130 g of 2- [1,1-bis (mercaptomethylthio) methyl] -1,3-dithietane was used instead of 79 g of bis (mercaptomethyl) disulfide, Purification was performed. As a result of analysis to confirm the structure of the compound obtained by purification, 2- [1,1-bis (3-thietanyldithiomethylthio) methyl] -1,3-dithietane (hereinafter referred to as compound (e) Abbreviated).
Here, the identification data of the obtained compound is shown below.

[Example 6]
30 g of compound (a) and 0.03 g of Biosorb 583 (manufactured by Kyodo Yakuhin Co., Ltd.) were mixed and dissolved in a beaker at room temperature of 20 ° C., and then 0.15 g of BF3 / dibutyl ether complex as a curing catalyst in a nitrogen atmosphere. After mixing, the mixture was degassed for 0.4 hours under reduced pressure, and then poured into a mold comprising 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 = 1.79 and νe = 29. The results are summarized in Table 6.

[Example 7]
A resin was obtained in the same manner as in Example 6 except that 30 g of compound (b) was used instead of compound (a). The obtained resin eventually had excellent transparency and good appearance without distortion. When the optical properties of the obtained resin were measured, the refractive index was ne = 1.77 and νe = 30. The physical properties obtained are summarized in Table 7.

[Example 8]
A resin was obtained in the same manner as in Example 6 except that 30 g of compound (c) was used instead of compound (a). The obtained resin eventually had excellent transparency and good appearance without distortion. When the optical properties of the obtained resin were measured, the refractive index was ne = 1.78 and νe = 30. The obtained physical properties are summarized in Table 6.

[Example 9]
A resin was obtained in the same manner as in Example 6 except that 30 g of compound (d) was used instead of compound (a). The obtained resin eventually had excellent transparency and good appearance without distortion. When the optical properties of the obtained resin were measured, the refractive index was ne = 1.77 and νe = 30. The obtained physical properties are summarized in Table 6.

[Example 10]
A resin was obtained in the same manner as in Example 6 except that 30 g of compound (e) was used instead of compound (a). The obtained resin eventually had excellent transparency and good appearance without distortion. When the optical properties of the obtained resin were measured, the refractive index was ne = 1.78 and νe = 30. The obtained physical properties are summarized in Table 6.

[Examples 11 to 15]
Resin in the same manner as in Example 6 except that 30 g of each of compounds (a) to (e) was used and 3.0 g of 1,1,2,2-tetrakis (mercaptomethylthio) ethane was added as a resin modifier. Got. The obtained resin eventually had excellent transparency and good appearance without distortion. The obtained physical properties are summarized in Table 6.

[Example 16]
Resin in the same manner as in Example 6 except that 30 g of compound (d) was used and 3.0 g of 1,1,2,2-tetrakis (mercaptomethylthio) ethane and 3.0 g of sulfur were added as a resin modifier. Got. The obtained resin eventually had excellent transparency and good appearance without distortion. The obtained physical properties are summarized in Table 6.

[Comparative Example 1]
Bis (3-thietanyl) disulfide was synthesized as a thietane compound, and a resin was obtained in the same manner as in Example 6.

  When the optical properties and heat resistance of the obtained resin were measured, the refractive index was ne = 1.74 and νe = 33. Compared with Examples 7-12, the refractive index was greatly inferior.

Claims (10)

The thietane compound which has a structure represented by following formula (3).

(Wherein, a, b, c and d each represents an integer of 0 or 1, satisfying 2 ≦ a + b + c + d ≦ 4. R1 may be linear or branched thiated with 1 to 4 carbon atoms. Represents a hydrocarbon group, a cyclic hydrocarbon group having 3 to 6 carbon atoms which may be thiated, a 1,4-dithian group, an arylene group or an aralkylene group, and these groups may be substituted or unsubstituted In the case of a + b + c + d = 2, R1 may represent a direct bond, R2 to R9 may be a hydrogen atom, or a substituted or unsubstituted straight chain or branched chain having 1 to 4 carbon atoms which may be thiated. Represents a hydrocarbon group or a cyclic hydrocarbon group having 3 to 6 carbon atoms.) The thietane compound of Claim 1 which has a structure represented by following formula (4).

(In the formula, n represents an integer of 2 to 4. R10 is a linear or branched hydrocarbon group having 1 to 4 carbon atoms which may be thiated or a cyclic group having 3 to 6 carbon atoms. Represents an optionally substituted hydrocarbon group, 1,4-dithiane group, arylene group, or aralkylene group, and these groups may be substituted or unsubstituted, and when n = 2, R10 represents a direct bond. R11 and R12 are each a hydrogen atom, a substituted or unsubstituted linear or branched hydrocarbon group having 1 to 4 carbon atoms or a cyclic hydrocarbon group having 3 to 6 carbon atoms, which may be thiated. Represents.) The thietane compound is 1,4-bis (3-thietanyldithio) -2,3-dithiabutane, 1,1,1-tris (3-thietanyldithiomethylthio) methane, 1,1,2,2-tetrakis (3- Thietanyldithiomethylthio) ethane, 1,1,3,3-tetrakis (3-thietanyldithiomethylthio) propane, or 2- [1,1-bis (3-thietanyldithiomethylthio) methyl] -1,3 The thietane compound according to claim 1 or 2, which is either dithietane. A polymerizable composition comprising the thietane compound according to any one of claims 1 to 3. Furthermore, the polymeric composition of Claim 4 containing a single-piece | unit sulfur. A resin obtained by curing the polymerizable composition according to claim 4 or 5. An optical material comprising the resin according to claim 6. A method for producing a resin, comprising a step of cast polymerization of the polymerizable composition according to claim 4. The method for producing the thietane compound according to any one of claims 1 to 3, wherein bis (3-thietanyl) disulfide and a compound having a mercaptomethylthio group are used as raw materials. The method according to claim 9, wherein a compound having an alcoholic hydroxyl group and / or an alkaline aqueous solution is used as the washing solvent.