JP2007327060A - Thioepoxy-based polymerizable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable composition giving a resin composed of a thioepoxy-based compound and having decreased variations of refractive index, hue, optical distortion, etc., and provide a method for the production of the composition. <P>SOLUTION: The polymerizable composition contains a compound having one or more structures expressed by formula (1) (R<SB>1</SB>is a 1-10C hydrocarbon group; and R<SB>2</SB>, R<SB>3</SB>and R<SB>4</SB>are each a 1-10C hydrocarbon group or hydrogen atom) provided that the total amount of the thioepoxy compound A having at least one dithioepoxy structure and at least one thioepoxy structure and the thioepoxy compound B having at least one epoxy structure and at least one structure expressed by thioepoxy is ≤4 mass% based on the total mass of the polymerizable composition. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

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

In recent years, plastic lenses are rapidly 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, although higher refractive index and higher Abbe number have been demanded, on the other hand, the refractive index and Abbe number are contradictory physical properties such that the higher the refractive index, the lower the Abbe number. It is very difficult to improve both at the same time. In view of this, studies have been actively conducted to increase the refractive index while suppressing the decrease in the Abbe number.
Among these studies, the most typical proposal is a method using a thioepoxy compound (see, for example, Patent Document 2 and Patent Document 3).

JP-A-63-46213 WO-89 / 10575 publication Japanese Patent Laid-Open No. 9-110979

  According to these methods, a high refractive index can be realized while having a relatively high Abbe number. However, the resin obtained by these methods may not be stable in refractive index and hue due to quality fluctuations when the polymerizable composition as a raw material is produced industrially, and optical distortion is likely to occur. There is. If the refractive index is not stable, there is a problem that the power is not stable when the resin is obtained as a lens. If the hue is not stable, there is a problem that when the resin is used for the spectacle lens, lenses having different hues on the left and right are used. In a resin for optical use, optical distortion is treated as a defective product. Therefore, if the optical distortion is easily generated, the yield of the obtained resin is greatly deteriorated, which is industrially disadvantageous. Therefore, it was necessary to elucidate the cause of this refractive index blur, hue blur, and optical distortion blur.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have succeeded in obtaining knowledge about the behavior of the thioepoxy compound by paying attention to the by-product. That is, the thioepoxy compound A having at least one structure represented by the formula (2) and at least one structure represented by the formula (3) and at least one structure represented by the formula (4) are used. And thioepoxy compound B having at least one structure represented by formula (3) was found to cause the refractive index blur, hue blur, and optical distortion blur of the resulting resin. In addition, regarding the allowable amount, there is no problem if the total of the thioepoxy compound A and the thioepoxy compound B is 0 with respect to the total mass of the polymerizable composition, but if it is 4% by mass or less, the refractive index of the resin obtained and It was also found that the hue is stabilized and optical distortion becomes difficult.

  Furthermore, about the polymeric composition containing the compound which has one or more structures shown by Formula (1) of this invention, the sum total of the thioepoxy compound A and the thioepoxy compound B is 4 with respect to polymeric composition total mass. A method of industrially producing at less than mass% has been studied. As a result, it was found that the total amount of thioepoxy compound A and thioepoxy compound B in the resulting polymerizable composition can be reduced if purification is performed by column chromatography such as a silica gel column. From an industrial point of view, separation by chromatography is not preferable in terms of cost and efficiency. Therefore, further studies have been made with emphasis on industrially possible production methods. As a result, the amount of the thiating agent used when producing the compound having at least one structure represented by the formula (1) is limited, that is, the thiating agent used when producing a known polythioepoxy compound. The amount of the acid or anhydride thereof used is limited, that is, the equivalent of 0.9 to 1.3 equivalents relative to the epoxy group equivalent in the polyepoxy compound, that is, the acid or anhydride thereof, By a method of controlling the reaction temperature within the range of 0 ° C. to 50 ° C. or a combination thereof, a method for controlling the reaction temperature in the range of 0 ° C. to 50 ° C. It has been found that it can be industrially produced so that the total of the compound A and the thioepoxy compound B is 4% by mass or less with respect to the total mass of the polymerizable composition.

That is, the present invention
[1] Formula (1)

(Wherein R ₁ represents a hydrocarbon having 1 to 10 carbon atoms, R ₂ , R ₃ , and R ₄ each represents a hydrocarbon group or hydrogen atom having 1 to 10 carbon atoms) In the polymerizable composition containing the compound having the above, the thioepoxy compound A having at least one structure represented by the formula (2) and at least one structure represented by the formula (3), and the formula The total of the thioepoxy compound B having at least one structure represented by (4) and having at least one structure represented by formula (3) is 4% by mass with respect to the total mass of the polymerizable composition. A polymerizable composition characterized by the following.

[2] The thioepoxy compound A is a compound represented by the formula (5), the thioepoxy compound B is a compound represented by the formula (6), and a structure represented by the formula (1). The polymerizable composition as described in [1], wherein the compound having one or more is a compound represented by the formula (7).

(Y represents a substituted or unsubstituted linear, branched or cyclic divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted 1,4-dithian group, an arylene group or an aralkylene group. m represents an integer of 0 to 2, and n represents an integer of 0 to 4.)

(Wherein, R ₅ to R ₁₀ each represents a hydrocarbon group or hydrogen having 1 to 10 carbon atoms.
Y represents a substituted or unsubstituted linear, branched or cyclic divalent hydrocarbon group having 1 to 10 hydrocarbons, a substituted or unsubstituted 1,4-dithian group, an arylene group or an aralkylene group. m represents an integer of 0 to 2, and n represents an integer of 0 to 4. )

[3] The thioepoxy compound A is 2,3-epidithiopropyl (2,3-epithiopropyl) disulfide and / or 2,3-epidithiopropyl (2,3-epithiopropyl) sulfide, The thioepoxy compound B is 2,3-epoxypropyl (2,3-epithiopropyl) disulfide and / or 2,3-epoxypropyl (2,3-epithiopropyl) sulfide, and further represented by the formula (1) In any one of [1] to [2], the compound having one or more of the structures represented is bis (2,3-epithiopropyl) disulfide and / or bis (2,3-epithiopropyl) sulfide. The polymerizable composition as described.
[4] By using 0.9 to 1.3 equivalents of the thiating agent used in the production of the polythioepoxy compound from the polyepoxy compound with respect to the equivalent of the epoxy group in the polyepoxy compound, the formula (1) The manufacturing method of the polymeric composition which the sum total of the thioepoxy compound A and the thioepoxy compound B in it makes 4 mass% or less with respect to polymeric composition total mass.
[5] 0.9 to 1.3 equivalents of the thiating agent used in the production of the polythioepoxy compound from the polyepoxy compound is used relative to the equivalent of the epoxy group in the polyepoxy compound, and the reaction temperature is 0. The manufacturing method of the polymeric composition which the sum total of the thioepoxy compound A and the thioepoxy compound B in Formula (1) makes 4 mass% or less with respect to polymeric composition total mass by setting it as 50 degreeC from 50 degreeC.
[6] 0.9 to 1.3 equivalents of the thiating agent used in the production of the polythioepoxy compound from the polyepoxy compound with respect to the equivalent of the epoxy group in the polyepoxy compound, and an acid or anhydride thereof The thioepoxy compound A and the thioepoxy compound B in the formula (1) are used by using 0.2 equivalent or less of the product with respect to the equivalent of the epoxy group in the polyepoxy compound and setting the reaction temperature to 0 to 50 ° C. The manufacturing method of the polymeric composition which makes the sum total 4 mass% or less with respect to polymeric composition total mass.
[7] The thioepoxy compound A is a compound represented by the formula (5), the thioepoxy compound B is a compound represented by the formula (6), and a structure represented by the formula (1). [4] The production method according to any one of [6] to [6], wherein the compound having one or more is a compound represented by the formula (7).

(Y represents a substituted or unsubstituted linear, branched or cyclic divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted 1,4-dithian group, an arylene group or an aralkylene group. m represents an integer of 0 to 2, and n represents an integer of 0 to 4.)

(Wherein, R ₅ to R ₁₀ each represents a hydrocarbon group or hydrogen having 1 to 10 carbon atoms.
Y represents a substituted or unsubstituted linear, branched or cyclic divalent hydrocarbon group having 1 to 10 hydrocarbons, a substituted or unsubstituted 1,4-dithian group, an arylene group or an aralkylene group. m represents an integer of 0 to 2, and n represents an integer of 0 to 4. )
[8] The thioepoxy compound A is 2,3-epidithiopropyl (2,3-epithiopropyl) disulfide and / or 2,3-epidithiopropyl (2,3-epithiopropyl) sulfide, The thioepoxy compound B is 2,3-epoxypropyl (2,3-epithiopropyl) disulfide and / or 2,3-epoxypropyl (2,3-epithiopropyl) sulfide, and further represented by the formula (1) The production method according to [7], wherein the compound having one or more of the structures represented is bis (2,3-epithiopropyl) disulfide and / or bis (2,3-epithiopropyl) sulfide.
[9] The polymerizable composition according to any one of [1] to [3] and / or the polymerizable composition obtained by the method according to any one of [4] to [8]. A method for producing an optical material that is used to obtain an optical material.
[10] The manufacturing method according to [9], wherein the optical material is a lens.
[11] The production method according to [10], which is performed by a casting polymerization method.
[12] A lens obtained by the method according to [11].
It is about.

  The polymerizable composition containing a thioepoxy compound having at least one structure represented by the formula (1) according to the present invention has at least one structure represented by the formula (2) and has the formula (3) ) And a thioepoxy compound B having at least one structure represented by formula (3) and at least one structure represented by formula (3). The total amount of is 4% by mass or less with respect to the total mass of the polymerizable composition, but is preferably 2% by mass or less. If it is 1.5 mass% or less, it is more preferable. If a polymerizable composition is produced in this range, the refractive index and hue of the resulting resin will be stabilized, and optical distortion will be difficult.

  According to the present invention, a transparent cured resin with suppressed refractive index blur and optical distortion blur as an optical material in the ultra-high refractive index field can be obtained, which contributes to improving the yield of lenses, particularly in the field of eyeglass lenses.

In the formula (1), R ₁ represents a divalent hydrocarbon group having 1 to 10 carbon atoms, specifically, a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, phenylene, alkyl-substituted phenylene And an arylene group having 6 to 10 carbon atoms, such as naphthalene, or an aralkylene group having 7 to 10 carbon atoms composed of a combination of alkylene and arylene, an alkylene group having 1 to 10 carbon atoms is preferable. More preferred is methylene or ethylene. More preferred is methylene. R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and the monovalent hydrocarbon group having 1 to 10 carbon atoms may be linear, branched or Although a cyclic | annular C1-C10 alkyl group, a C6-C10 aryl group, and a C7-C10 aralkyl group are mentioned, a hydrogen atom or a C1-C10 alkylene group is preferable.
A hydrogen atom or a methyl group is more preferable. A hydrogen atom is more preferable.

  As the compound having one or more structures represented by the formula (1), a compound mainly represented by the following formula (7) is preferable.

(In the formula, R _{5 to} R ₁₀ each represent a hydrocarbon group having 1 to 10 carbon atoms or hydrogen. Y is a substituted or unsubstituted divalent fatty acid having 1 to 10 linear, branched or cyclic hydrocarbons. A hydrocarbon group, a substituted or unsubstituted 1,4-dithiane group, an arylene group, and an aralkylene group, m represents an integer of 0 to 2, and n represents an integer of 0 to 4).

Here, R _{5 to} R ₁₀ each have the same meaning as R _{2 to} R _4, and particularly preferably a hydrogen atom. Y represents a substituted or unsubstituted linear, branched or cyclic divalent aliphatic hydrocarbon group having 1 to 10 hydrocarbons, a substituted or unsubstituted 1,4-dithian group, an arylene group or an aralkylene group. The divalent aliphatic hydrocarbon group having 1 to 10 hydrocarbons is preferably a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, particularly a linear alkylene group. Examples of the arylene and aralkylene groups are the same as those described for R ₁ . Further, Y may have a substituent, as long as it does not adversely affect the physical properties (for example, transparency, uniformity, refractive index, heat resistance, etc.) of the resin produced using the compound. Although it does not restrict | limit in particular, you may have a reactive group. In particular, the structure represented by the formula (1), particularly a trifunctional or higher functional compound having a 2,3-epithiopropylthio group as a substituent, may be used, but a bifunctional compound is more preferable. Further, a compound where n = 0 and / or a compound where m = 0 and n = 1 is most preferable.

  The thioepoxy compound having at least one structure represented by the formula (1) in the molecule according to the present invention, for example, the polythioepoxy compound of the above formula (7) is derived from a polyepoxy compound having two or more functions. . These polyepoxy compounds can be easily obtained by known methods. For example, a polythiol compound having a straight-chain or branched alkyl sulfide structure, hydrogen sulfide, sodium hydrosulfide, or sodium sulfide and an epihalohydrin compound, preferably epichlorohydrin or epibromohydrin is reacted in the presence of an alkali, and is represented by the formula (8). An alkyl sulfide type epoxy compound is obtained.

（式中、Ｙ、ｍ、ｎは前記に同じ。）

(In the formula, Y, m and n are the same as above.)

  The polythioepoxy compound represented by the formula (9) is obtained by reacting the obtained epoxy compound with a thiocyanating agent such as thiocyanates, thioureas, triphenylphosphine sulfide and the like. Of the thiazing agents used here, thiocyanates and thioureas are preferred. In view of reaction results and cost, thiourea is more preferable.

（式中、Ｙ、ｍ、ｎは前記に同じ。）

(In the formula, Y, m and n are the same as above.)

  Specific examples of the polythiol compound used as a raw material here include 1,1-methanedithiol, 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, , 4-butanedithiol, 1,2,3-trimercaptopropane, tetrakis (mercaptomethyl) methane, 1,2-dimercaptocyclohexane, bis (2-mercaptoethyl) sulfide, 2,3-dimercapto-1-propanol, Ethylene glycol bis (3-mercaptopropionate), diethylene glycol bis (3-mercaptopropionate), diethylene glycol bis (2-mercaptoglycolate), pentaerythritol tetrakis (2-mercaptothioglycolate), pentaerythritol Rutetrakis (3-mercaptopropionate), trimethylolpropane tris (2-mercaptothioglycolate), trimethylolpropane tris3-mercaptopropionate), 1,1,1-trimethylmercaptoethane, 1,1,1 -Trimethylmercaptopropane, 2,5-dimercaptomethylthiophane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-bis {(2-mercaptoethyl) thiomethyl} -1,4-dithiane, 1,3-cyclohexanedithiol, 1,4-cyclohexanedithiol, 4,8-dimercaptomethyl-1,11-mercapto-3,6,9- Trithiaundecane, 4,7-dimercaptomethyl-1,11-me Mercapto-3,6,9-trithiaundecane, 5,7-mercaptomethyl 1,11-mercapto-3,6,9-trithiaundecane of aliphatic thiols and,

1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, 1,4- Bis (mercaptomethyl) benzene, 2,2′-dimercaptobiphenyl, 4,4′-dimercaptobiphenyl, bis (4-mercaptophenyl) methane, bis (4-mercaptophenyl) sulfide, bis (4-mercaptophenyl) Aromatic thiols such as sulfone, 2,2-bis (4-mercaptophenyl) propane, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,2,5-trimercaptobenzene Although it is mentioned, it is not limited only to these exemplary compounds.

  Specific examples of the polythioepoxy compound having a structure represented by the formula (5) obtained by thialation of the polyepoxy compound include bis (2,3-epithiopropyl) sulfide, bis (2,3 -Epithiopropyl) disulfide, bis (2,3-epithiopropylthio) methane, 1,2-bis (2,3-epithiopropylthio) ethane, 1,2-bis (2,3-epithiopropyl) Thio) propane, 1,3-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-epithiopropylthio) butane, 1,5- Screw (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-epithio) Propylthio) -4- (2,3-epithiopropylthiomethyl) -3-thiahexane, 1,8-bis (2,3-epithiopropylthio) -4- (2,3-epithiopropylthiomethyl) ) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropylthio) -4,5-bis (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8 -Bis (2,3-epithiopropy Ruthio) -4,4-bis (2,3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropylthio) -2,5-bis (2, 3-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (2,3-epithiopropylthio) -2,4,5-tris (2,3-epithiopropylthiomethyl)- 3,6-dithiaoctane, 1,1,1-tris [{2- (2,3-epithiopropylthio) ethyl} thiomethyl] -2- (2,3-epithiopropylthio) ethane, 1,1, 2,2-tetrakis [{2- (2,3-epithiopropylthio) ethyl} thiomethyl] ethane, 1,11-bis (2,3-epithiopropylthio) -4,8-bis (2,3 -Epithiopropylthiomethyl) -3,6,9- Lithiaundecane, 1,11-bis (2,3-epithiopropylthio) -4,7-bis (2,3-epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1,11- Chain aliphatic 2,3-epi such as bis (2,3-epithiopropylthio) -5,7-bis (2,3-epithiopropylthiomethyl) -3,6,9-trithiaundecane A thiopropylthio compound, 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 compounds and the like, but are not limited to these exemplified compounds. Among these exemplified compounds, bis (2,3-epithiopropyl) sulfide and bis (2,3-epithiopropyl) disulfide are preferable compounds, and bis (2,3-epithiopropyl) sulfide is a more preferable compound. It is.

  The total of the thioepoxy compound A and the thioepoxy compound B in the polymerizable composition containing the compound having one or more structures represented by the formula (1) according to the present invention is 4% by mass with respect to the total mass of the polymerizable composition. As a method for producing the following polymerizable composition, in a known method for producing a compound having at least one structure represented by the formula (1) using a thiating agent and an acid or an anhydride thereof, The most effective method is to limit the amount of the thiating agent and acid or anhydride used, and further to limit the temperature conditions.

  For example, when a polythioepoxy compound having a structure represented by the formula (9) is produced from a polyepoxy compound having a structure represented by the formula (8), the amount of a thiating agent and an acid or its anhydride used In consideration of the epoxy group equivalent of the polyepoxy compound, the reaction is limited and charged. In this case, depending on the structure and physical properties of the polyepoxy compound as a raw material, and cannot be unconditionally limited, the chelating agent is used with respect to the equivalent of the epoxy group in the polyepoxy compound having the structure represented by the formula (8). It is good to use 0.9 equivalent to 1.3 equivalent. At this time, the amount used is preferably 0.95 equivalents to 1.25 equivalents. 0.975 equivalent to 1.21 equivalent is more preferable.

  About an acid or its anhydride, it is good to use at 0.2 equivalent or less with respect to the equivalent of the epoxy group in the polyepoxy compound which has a structure represented by Formula (8). At this time, the amount used is preferably 0.15 equivalent or less. It is more preferable if it is 0.1 equivalent or less.

  The reaction temperature is preferably in the range of 0 ° C. to 50 ° C., preferably 5 ° C. to 45 ° C. More preferably, it is 10 to 40 ° C.

  In order to industrially control the reaction temperature as described above, it is preferable to drop one of the composition containing the polyepoxy compound and the composition containing the thiating agent into the other. In particular, it is more preferable to use a composition containing a chelating agent as a laying solution and drop a composition containing a polyepoxy compound dropwise. In this case, the composition containing the polyepoxy compound may contain the solvent, additive, moisture, etc. used in the synthesis of the polyepoxy compound, and industrially, the solvent remains contained. When dripped, it is preferable from a viewpoint of reaction efficiency, temperature control, and the quality of the thioepoxy compound obtained.

  As a reaction solvent used in the thialation, a polar solvent alone or a mixed solvent of a polar solvent and a nonpolar solvent is often used to obtain good results. 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 tetrahydrofuran, 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 thiating agent that can be used here include thiocyanates, thioureas, triphenylphosphine sulfide and the like as described above, and thiocyanates and thioureas are preferable. In view of reaction results and cost, thiourea is more preferable.

  In order to suppress refractive index fluctuation and optical distortion fluctuation in the polymerizable composition produced by the above method, the thioepoxy compound A whose content is defined is a compound represented by the following formula (5). Can be mentioned.

（Ｙ、ｍ、ｎは前記に同じ）

(Y, m and n are the same as above)

  Specific examples of the thioepoxy compound A include 2,3-epidithiopropyl (2,3-epithiopropyl) sulfide, 2,3-epidithiopropyl (2,3-epithiopropyl) disulfide, 2,3-epi. Dithiopropylthio (2,3-epithiopropyl) thiomethane, 1- (2,3-epidithiopropylthio) -2- (2,3-epithiopropyl) thioethane, 1- (2,3-epidithiopropyl) Thio) -2- (2,3-epithiopropyl) thiopropane, 1- (2,3-epidithiopropylthio) -3- (2,3-epithiopropyl) thiopropane, 1- (2,3-epi Dithiopropylthio) -3- (2,3-epithiopropyl) thio-2-methylpropane, 1- (2,3-epidithiopropylthio) -4- (2,3-epithiopropyl) Thiobutane, 1- (2,3-epidithiopropylthio) -4- (2,3-epithiopropyl) thio-2-methylbutane, 1- (2,3-epidithiopropylthio) -3- (2, 3-epithiopropyl) thiobutane, 1- (2,3-epidithiopropylthio) -5- (2,3-epithiopropyl) thiopentane, 1- (2,3-epidithiopropylthio) -5- ( 2,3-epithiopropyl) thio-2-methylpentane, 1- (2,3-epidithiopropylthio) -5- (2,3-epithiopropyl) thio-3-thiapentane, 1- (2, 3-epidithiopropylthio) -6- (2,3-epithiopropyl) thiohexane, 1- (2,3-epidithiopropylthio) -6- (2,3-epithiopropyl) thio-2-methyl Hexane, 1- (2 3-epidithiopropylthio) -8- (2,3-epithiopropyl) thio-3,6-dithiaoctane and the like structure represented by the above formula (2) (2,3-epidithio) (2,3-epithiopropyl) thio compound having a propylthio group), and

1- (2,3-epidithiopropylthio) -3- (2,3-epithiopropyl) thiocyclohexane, 1- (2,3-epidithiopropylthio) -4- (2,3-epithiopropyl) ) Thiocyclohexane, 1- (2,3-epidithiopropylthiomethyl) -3- (2,3-epithiopropyl) thiomethylcyclohexane, 1- (2,3-epidithiopropylthiomethyl) -4- ( 2,3-epithiopropyl) thiomethylcyclohexane, 2- (2,3-epidithiopropylthiomethyl) -5- (2,3-epithiopropyl) thiomethyl-1,4-dithiane, 2-{(2 -(2,3-epidithiopropylthioethyl) thio) ethyl} -5- {2- (2,3-epithiopropyl) thioethyl} thiomethyl-1,4-dithiane, 2- (2,3-epi Cycloaliphatic structures such as thiopropylthiomethyl) -5- (2,3-epithiopropyl) thiomethyl-2,5-dimethyl-1,4-dithiane (2,3) (2,3-epithiopropyl) thio compound having -epidithiopropylthio group), and

1- (2,3-epidithiopropylthio) -2- (2,3-epithiopropyl) thiobenzene, 1- (2,3-epidithiopropylthio-) 3- (2,3-epithiopropyl) Thiobenzene, 1- (2,3-epidithiopropylthio) -4- (2,3-epithiopropyl) thiobenzene, 1- (2,3-epidithiopropylthiomethyl) -2- (2,3-epi Thiopropyl) thiomethylbenzene, 1- (2,3-epidithiopropylthiomethyl) -3- (2,3-epithiopropyl) thiomethylbenzene, 1- (2,3-epidithiopropylthiomethyl)- 4- (2,3-epithiopropyl) thiomethylbenzene, {4- (2,3-epithiopropylthio) phenyl-4 ′-(2,3-epidithiopropylthio) phenyl} methane, 2,2 -{ 4- (2,3-epithiopropyl) thiophenyl-4 ′-(2,3-epidithiopropylthio) phenyl} propane, {4- (2,3-epithiopropyl) thiophenyl-4 ′-(2, 3-epidithiopropylthio) phenyl} sulfide, {4- (2,3-epithiopropylthio) phenyl-4 ′-(2,3-epidithiopropylthio) phenyl} sulfone, 4- (2,3- Epithiopropylthio) -4 '-(2,3-epidithiopropylthio) biphenyl, 4- (2,3-epithiopropylthio) -4'-(2,3-epidithiopropylthio) phenyl sulfide, etc. An aromatic (2,3-epithiopropyl) thio compound having a structure (2,3-epidithiopropylthio group) represented by the above formula (2) can be exemplified, but only exemplary compounds can be exemplified. Not intended to be constant.

Moreover, as thioepoxy compound B, the compound represented by following formula (6) is mentioned.

（Ｙ、ｍ、ｎは前記に同じ）

(Y, m and n are the same as above)

  Specific examples of the thioepoxy compound B include 2,3-epoxypropyl (2,3-epithiopropyl) sulfide, 2,3-epoxypropyl (2,3-epithiopropyl) disulfide, and 2,3-epoxypropylthio. (2,3-epithiopropyl) thiomethane, 1- (2,3-epoxypropylthio) -2- (2,3-epithiopropyl) thioethane, 1- (2,3-epoxypropylthio) -2- (2,3-epithiopropyl) thiopropane, 1- (2,3-epoxypropylthio) -3- (2,3-epithiopropyl) thiopropane, 1- (2,3-epoxypropylthio) -3- (2,3-epithiopropyl) thio-2-methylpropane, 1- (2,3-epoxypropylthio) -4- (2,3-epithiopropyl) thiobutane, (2,3-epoxypropylthio) -4- (2,3-epithiopropyl) thio-2-methylbutane, 1- (2,3-epoxypropylthio) -3- (2,3-epithiopropyl) Thiobutane, 1- (2,3-epoxypropylthio) -5- (2,3-epithiopropyl) thiopentane, 1- (2,3-epoxypropylthio) -5- (2,3-epithiopropyl) Thio-2-methylpentane, 1- (2,3-epoxypropylthio) -5- (2,3-epithiopropyl) thio-3-thiapentane, 1- (2,3-epoxypropylthio) -6 (2,3-epithiopropyl) thiohexane, 1- (2,3-epoxypropylthio) -6- (2,3-epithiopropyl) thio-2-methylhexane, 1- (2,3-epoxypropyl) Thio)- -Having a structure (2,3-epoxypropylthio group) represented by the above-mentioned formula (4) of a chain aliphatic group such as (2,3-epithiopropyl) thio-3,6-dithiaoctane (2,3 -Epithiopropyl) thio compounds, and

1- (2,3-epoxypropylthio) -3- (2,3-epithiopropyl) thiocyclohexane, 1- (2,3-epoxypropylthio) -4- (2,3-epithiopropyl) thio Cyclohexane, 1- (2,3-epoxypropylthiomethyl) -3- (2,3-epithiopropyl) thiomethylcyclohexane, 1- (2,3-epoxypropylthiomethyl) -4- (2,3- Epithiopropyl) thiomethylcyclohexane, 2- (2,3-epoxypropylthiomethyl) -5- (2,3-epithiopropyl) thiomethyl-1,4-dithiane, 2-{(2- (2,3 -Epoxypropylthioethyl) thio) ethyl} -5- {2- (2,3-epithiopropyl) thioethyl} thiomethyl-1,4-dithiane, 2- (2,3-epoxypropyl) A structure (2,3-epoxypropyl) represented by the above-mentioned formula (4) of cycloaliphatic such as (Omethyl) -5- (2,3-epithiopropyl) thiomethyl-2,5-dimethyl-1,4-dithiane (2,3-epithiopropyl) thio compound having a thio group, and

1- (2,3-epoxypropylthio) -2- (2,3-epithiopropyl) thiobenzene, 1- (2,3-epoxypropylthio-) 3- (2,3-epithiopropyl) thiobenzene, 1- (2,3-epoxypropylthio) -4- (2,3-epithiopropyl) thiobenzene, 1- (2,3-epoxypropylthiomethyl) -2- (2,3-epithiopropyl) thio Methylbenzene, 1- (2,3-epoxypropylthiomethyl) -3- (2,3-epithiopropyl) thiomethylbenzene, 1- (2,3-epoxypropylthiomethyl) -4- (2,3 -Epithiopropyl) thiomethylbenzene, {4- (2,3-epithiopropylthio) phenyl-4 '-(2,3-epoxypropylthio) phenyl} methane, 2,2- {4- (2, 3- Epithiopropyl) thiophenyl-4 ′-(2,3-epoxypropylthio) phenyl} propane, {4- (2,3-epithiopropyl) thiophenyl-4 ′-(2,3-epoxypropylthio) phenyl} Sulfide, {4- (2,3-epithiopropylthio) phenyl-4 ′-(2,3-epoxypropylthio) phenyl} sulfone, 4- (2,3-epithiopropylthio) -4 ′-( 2,3-epoxypropylthio) biphenyl, 4- (2,3-epithiopropylthio) -4 ′-(2,3-epoxypropylthio) phenyl sulfide and other structures represented by the above formula (4) ( An aromatic (2,3-epithiopropyl) thio compound having a 2,3-epoxypropylthio group) can be exemplified, but is not limited to the exemplified compounds.

  In the polymerizable composition according to the present invention, the total of the thioepoxy compound A and the thioepoxy compound B in the polymerizable composition containing a compound having one or more structures represented by the formula (1) is a polymerizable composition. It is a polymerizable composition that is 4% by mass or less based on the total mass of the product. This polymerizable composition includes polysulfide oligomers such as dimers, trimers, and tetramers of the exemplified compounds, polymerization inhibitors, and the like. Inorganic acids and organic acids added as organic solvents, organic compounds such as solvents and other by-products, and inorganic compounds may also be included within a range not causing problems.

  The polymerizable composition according to the present invention can be applied not only to a high refractive index resin but also to a medium refractive index resin, mainly for adjusting various physical properties such as impact resistance and specific gravity of the obtained resin, A resin modifier can be added for the purpose of improving the resin, for example, to adjust the viscosity and other handling properties.

  Examples of the resin modifier include thioepoxy compounds other than those contained in the polymerizable composition according to the present invention, thiol compounds, iso (thio) cyanates, mercapto organic acids, organic acids and anhydrides, amino acids and mercaptoamines. And olefins including amines, (meth) acrylates and the like.

  Specific examples of the thiol compound as the resin modifier include methyl mercaptan, ethyl mercaptan, 1,1-methanedithiol, 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2 -Propanedithiol, 1,4-butanedithiol, 1,2,3-trimercaptopropane, tetrakis (mercaptomethyl) methane, 1,2-dimercaptocyclohexane, bis (2-mercaptoethyl) sulfide, 2,3-dimercapto -1-propanol, ethylene glycol bis (3-mercaptopropionate), diethylene glycol bis (3-mercaptopropionate), diethylene glycol bis (2-mercaptoglycolate), pentaerythritol tetrakis (2-mercaptothioglyco) ), Pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (2-mercaptothioglycolate), trimethylolpropane tris 3-mercaptopropionate), 1,1,1-trimethylmercaptoethane 1,1,1-trimethylmercaptopropane, 2,5-dimercaptomethylthiophane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,5-dimercaptomethyl-1,4-dithiane 2,5-bis {(2-mercaptoethyl) thiomethyl} -1,4-dithiane, 1,3-cyclohexanedithiol, 1,4-cyclohexanedithiol, 4,8-dimercaptomethyl-1,11-mercapto- 3,6,9-trithiaundecane, 4,7-dimer Putomechiru 1,11 mercapto-3,6,9-trithiaundecane, 5,7-mercaptomethyl 1,11-mercapto-3,6,9-trithiaundecane of aliphatic thiols and,

Benzylthiol, thiophenol, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) Benzene, 1,4-bis (mercaptomethyl) benzene, 2,2′-dimercaptobiphenyl, 4,4′-dimercaptobiphenyl, bis (4-mercaptophenyl) methane, bis (4-mercaptophenyl) sulfide, bis (4-mercaptophenyl) sulfone, 2,2-bis (4-mercaptophenyl) propane, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,2,5-trimercaptobenzene An aromatic thiol such as, but not limited to the exemplary compounds.

  Specific examples of the iso (thio) cyanate compounds as the resin modifier of the present invention include methyl isocyanate, ethyl isocyanate, n-propyl isocyanate, isopropyl isocyanate, n-butyl isocyanate, sec-butyl isocyanate. Nert, tert-butyl isocyanate, pentyl isocyanate, hexyl isocyanate, heptyl isocyanate, octyl isocyanate, decyl isocyanate, lauryl isocyanate, myristyl isocyanate, octadecyl isocyanate, 3-pentyl isocyanate, 2-ethylhexyl isocyanate Narate, 2,3-dimethylcyclohexyl isocyanate, 2-methoxyphenyl isocyanate, 4-methoxyphenyl isocyanate, α-methylbenzyl isocyanate DOO, phenylethyl isocyanate, phenyl isocyanate, o-, m-, or p- tolyl isocyanate, cyclohexyl isocyanate, benzyl isocyanate, monofunctional isocyanate compounds such as isocyanate methyl bicycloheptane,

Hexamethylene diisocyanate, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4 , 4-trimethylhexamethylene diisocyanate, 1,6,11-undecatriisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, bis (isocyanato Ethyl) carbonate, bis (isocyanatoethyl) ether, lysine diisocyanate methyl ester, lysine triisocyanate, xylylene diisocyanate, bis (isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, α, α, α ', Α'-tetramethylxylylene Diisocyanate, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl) diphenyl ether, bis (isocyanatoethyl) phthalate, mesityrylene triisocyanate, 2,6-di (isocyanate) Aliphatic polyisocyanate compounds such as natomethyl) furan,

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

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

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

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

Diphenyl disulfide-4,4-diisocyanate, 2,2-dimethyldiphenyl disulfide-5,5-diisocyanate, 3,3-dimethyldiphenyl disulfide-5,5-diisocyanate, 3,3-dimethyldiphenyl disulfide 6,6-diisocyanate, 4,4-dimethyldiphenyl disulfide-5,5-diisocyanate, 3,3-dimethoxydiphenyl disulfide-4,4-diisocyanate, 4,4-dimethoxydiphenyl disulfide-3 Aromatic disulfide isocyanate compounds such as 1,3-diisocyanate,

Sulfur-containing heterocyclic compounds such as 2,5-diisocyanatothiophene, 2,5-bis (isocyanatomethyl) thiophene,

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

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

Aliphatic polyisothiocyanate compounds such as 1,6-diisothiocyanatohexane and p-phenylene isopropylidene diisothiocyanate, cycloaliphatic diisothiocyanate, and alicyclic polyisothiocyanates such as diisothiocyanatomethylbicycloheptane Narate compounds,

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 Sochioshianato,

Furthermore, carbonyl isothiocyanes such as 1,3-benzenedicarbonyldiisothiocyanate, 1,4-benzenedicarbonyldiisothiocyanate, (2,2-pyridine) -4,4-dicarbonyldiisothiocyanate, etc. Examples thereof include, but are not limited to, exemplified compounds.

Specific examples of the isothiocyanate compound containing one or more sulfur atoms in addition to the isothiocyanate group include thiobis (3-isothiocyanatopropane), thiobis (2-isothiocyanatoethane), dithiobis ( Sulfur-containing aliphatic isothiocyanate compounds such as 2-isothiocyanatoethane), 1-isothiocyanato-4-[(2-isothiocyanato) sulfonyl] benzene, thiobis (4-isothiocyanatobenzene), sulfonylbis (4-isothi Ouocyanatobenzene), sulfur-containing aromatic isothiocyanate compounds such as dithiobis (4-isothiocyanatobenzene), 2,5-diisothiocyanatothiophene, 2,5-diisothiocyanato-1,4-dithiane, etc. However, it is not limited to the exemplified compounds.

  Furthermore, halogen-substituted products such as chlorine-substituted products and bromine-substituted products, alkyl-substituted products, alkoxy-substituted products, nitro-substituted products and prepolymer-modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, and burette-modified products. Bodies, dimerization or trimerization reaction products and the like can also be used.

Furthermore, the isothiocyanate compound which has an isocyanate 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,

Furthermore, examples include compounds containing a sulfur atom in addition to isothiocyanate groups such as 4-isocyanato-4′-isothiocyanatodiphenyl sulfide and 2-isocyanato-2′-isothiocyanatodiethyl disulfide. It is not limited to.
Furthermore, halogen-substituted products such as chlorine-substituted products and bromine-substituted products, alkyl-substituted products, alkoxy-substituted products, nitro-substituted products and prepolymer-modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, and burette-modified products. Bodies, dimerization or trimerization reaction products, and the like can also be used.

  Specific examples of the mercapto organic acid include thioglycolic acid, 3-mercaptopropionic acid, thioacetic acid, thiolactic acid, thiomalic acid, thiosalicylic acid, and the like. Examples of the organic acid and its anhydride include the polymerization inhibitors described above. Besides thiodiglycolic acid, thiodipropionic acid, dithiodipropionic acid, phthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnorbornenoic anhydride, methylnorbornanoic acid Examples include anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like, but are not limited to the exemplified compounds.

  Specific examples of the amine compounds include ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, ter-butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, laurylamine, myristylamine. , 3-pentylamine, 2-ethylhexylamine, 1,2-dimethylhexylamine, allylamine, aminomethylbicycloheptane, cyclopentylamine, cyclohexylamine, 2,3-dimethylcyclohexylamine, aminomethylcyclohexane, aniline, benzylamine, phenethylamine 2-, 3-, or 4-methylbenzylamine, o-, m-, or p-methylaniline, o-, m-, or p-ethylaniline, amino Morpholine, naphthylamine, furfurylamine, α-aminodiphenylmethane, toluidine, aminopyridine, aminophenol, aminoethanol, 1-aminopropanol, 2-aminopropanol, aminobutanol, aminopentanol, aminohexanol, methoxyethylamine, 2- (2 -Aminoethoxy) Monofunctional 1 such as ethanol, 3-ethoxypropylamine, 3-propoxypropylamine, 3-butoxypropylamine, 3-isopropoxypropylamine, 3-isobutoxypropylamine, 2,2-diethoxyethylamine Secondary amine compounds,

Ethylenediamine, 1,2-, or 1,3-diaminopropane, 1,2-, 1,3-, or 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7 -Diaminoheptane, 1,8-diaminooctane, 1,10-diaminodecane, 1,2-, 1,3-, or 1,4-diaminocyclohexane, o-, m- or p-diaminobenzene, 3,4 -Or 4,4'-diaminobenzophenone, 3,4- or 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-, or 4,4 '-Diaminodiphenylsulfone, 2,7-diaminofluorene, 1,5-, 1,8-, or 2,3-diaminonaphthalene, 2,3 2,6- or 3,4-diaminopyridine, 2,4- or 2,6-diaminotoluene, m- or p-xylylenediamine, isophoronediamine, diaminomethylbicycloheptane, 1,3-, Alternatively, 1,4-diaminomethylcyclohexane, 2-, or 4-aminopiperidine, 2-, or 4-aminomethylpiperidine, 2-, or 4-aminoethylpiperidine, N-aminoethylmorpholine, N-aminopropylmorpholine, etc. A primary polyamine compound, and

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

N, N′-dimethylethylenediamine, N, N′-dimethyl-1,2-diaminopropane, N, N′-dimethyl-1,3-diaminopropane, N, N′-dimethyl-1,2-diaminobutane, N, N′-dimethyl-1,3-diaminobutane, N, N′-dimethyl-1,4-diaminobutane, N, N′-dimethyl-1,5-diaminopentane, N, N′-dimethyl-1 , 6-Diaminohexane, N, N′-dimethyl-1,7-diaminoheptane, N, N′-diethylethylenediamine, N, N′-diethyl-1,2-diaminopropane, N, N′-diethyl-1 , 3-diaminopropane, N, N′-diethyl-1,2-diaminobutane, N, N′-diethyl-1,3-diaminobutane, N, N′-diethyl-1,4-diaminobutane, N, N'-diethyl-1,5-di Aminopentane, N, N′-diethyl-1,6-diaminohexane, N, N′-diethyl-1,7-diaminoheptane, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 2,6-dimethyl Piperazine, homopiperazine, 1,1-di- (4-piperidyl) methane, 1,2-di- (4-piperidyl) ethane, 1,3-di- (4-piperidyl) propane, 1,4-di- Secondary polyamine compounds such as (4-piperidyl) butane and tetramethylguanidine can be exemplified, but are not limited to the exemplified compounds.

  Specific examples of the olefin compounds include benzyl acrylate, benzyl methacrylate, butoxyethyl acrylate, butoxymethyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxymethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, phenoxyethyl. Acrylate, phenoxyethyl methacrylate, phenyl methacrylate, 3-phenoxy-2-hydroxypropyl acrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate Relate, 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-acryloxydiethoxy) Phenyl) propane, 2,2-bis (4-methacryloxydiethoxyphenyl) propane, bisphenol F diacri Bisphenol F dimethacrylate, 1,1-bis (4-acryloxyethoxyphenyl) methane, 1,1-bis (4-methacryloxyethoxyphenyl) methane, 1,1-bis (4-acryloxydiethoxy) Phenyl) methane, 1,1-bis (4-methacryloxydiethoxyphenyl) methane, dimethyloltricyclodecane diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, glycerol diacrylate, glycerol dimethacrylate, pentaerythritol Triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, methylthioacrylate, methylthiomethacrylate, phenylthioacrylate, benzylthiomethacrylate (Meth) acrylate compounds such as carbonate, xylylene dithiol diacrylate, xylylene dithiol dimethacrylate, mercaptoethyl sulfide diacrylate, mercaptoethyl sulfide dimethacrylate, allyl glycidyl ether, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl carbonate And allyl compounds such as diethylene glycol bisallyl carbonate, vinyl compounds such as styrene, chlorostyrene, methylstyrene, bromostyrene, dibromostyrene, divinylbenzene, 3,9-divinylspirobi (m-dioxane), and diisopropenylbenzene. However, it is not limited only to the exemplified compounds.

  Any of the above resin modifiers may be used alone or in combination of two or more.

  As the curing catalyst used in the present invention, tertiary amines, phosphines, quaternary ammonium salts, quaternary phosphonium 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-diethyl. Ethanolamine, N, N-dibutylethanolamine, N, N-dimethylbenzylamine, diethylbenzylamine, N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N-methyldicyclohexylamine, N-methylmorpholine, N-isopropylmorpholine, pyridine, N, N-dimethylaniline, β-picoline, N, N′-dimethylpiperazine, N-methylpiperidine, 2,2′-bipyridyl, hexamethylenetetramine, 1,8-diazabicyclo (5, 4 , 0) -7-undecene, tertiary amines such as trimethylphosphine, triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tribenzylphosphine, 1,2-bis ( Phosphines such as diphenylphosphino) ethane, 1,2-bis (dimethylphosphino) ethane, quaternary ammonium salts such as tetramethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetramethylphosphonium bromide, tetrabutyl Quaternary phosphonium salts such as phosphonium chloride, tetrabutylphosphonium bromide, dimethyltin dichloride, dibutyltin dichloride, dibutyltin dilaurate, tetrachlorotin Lewis acids such as dibutyltin oxide, diacetoxytetrabutyldistanoxane, zinc chloride, acetylacetone zinc, aluminum chloride, aluminum fluoride, triphenylaluminum, tetrachlorotitanium, calcium acetate, 2,2′-azobis (2-cyclo Propylpropionitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), t-butylperoxy-2- Radical polymerization catalysts such as ethylhexanoate, n-butyl-4,4′-bis (t-butylperoxy) valerate, t-butylperoxybenzoate, diphenyliodonium hexafluorophosphoric acid, diphenyliodonium hexafluoroarsenic acid, diphenyliodonium Hexafluoroantimony, trif Nils Gandolfo iodonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, although cationic polymerization catalyst such as triphenylsulfonium hexafluoroarsenate and the like, are not limited only to these exemplified compounds. Among these exemplified compounds, preferred are tertiary amine compounds and phosphine compounds, quaternary ammonium salts, and quaternary phosphonium salts.

  The above curing catalysts may be used alone or in combination of two or more.

  When the addition amount of the curing catalyst is 0.001 to 1% by mass with respect to the total mass of the polymerizable composition containing the thioepoxy compound, pot life, transparency of the resulting resin, optical physical properties, or weather resistance It is preferable with respect to sex. More preferably, it is used in the range of 0.01 to 5 mass%.

  A typical polymerization method for obtaining the resin (for example, plastic lens) of the present invention includes cast polymerization. That is, a polymerizable composition containing a thioepoxy compound containing a curing catalyst is injected between molding molds held by a gasket or a tape. At this time, there is no problem even if processing such as defoaming is performed as necessary.

  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 type and amount of the curing catalyst or the like for obtaining the resin of the present invention, and the type and ratio of the monomer vary depending on the composition of the polymerizable composition to be polymerized, and thus cannot be limited in general.

  The conditions for the heat polymerization of the polymerizable composition of the present invention injected into the molding mold cannot be limited because the conditions vary greatly depending on the type of thioepoxy compound, the type of curing catalyst, the shape of the mold, etc., but are approximately -50 to 200 ° C. It is carried out at a temperature for 1 to 100 hours.

  In some cases, if the temperature is maintained or gradually raised in a temperature range of 10 ° C. to 150 ° C. and polymerized in 1 to 80 hours, a preferable result may be obtained.

  Furthermore, the polymerizable composition of the present invention can shorten the polymerization time by irradiation with energy rays such as ultraviolet rays and electron beams. In this case, a curing catalyst such as a radical polymerization catalyst or a cationic polymerization catalyst may be required.

  In the resin molding of the present invention, a chain extender, a crosslinking agent, a light stabilizer, an ultraviolet absorber, an antioxidant, an anti-coloring agent, a dye, and a filler, as in a known molding method, depending on the purpose. Various substances such as an external or internal mold release agent and an adhesion improver may be added.

  In addition, the extracted resin may be subjected to a treatment such as annealing as necessary.

    The resin obtained by curing the polymerizable composition of the present invention is a resin that has no hue and refractive index fluctuation and is very excellent in transparency without optical distortion. This resin can be obtained as molded products of various forms by changing the mold during casting polymerization, and requires an optical element such as a spectacle lens, a camera lens, and a light emitting diode (LED), which requires a stable refractive index. It can be used for various uses as a material and transparent resin. In particular, it is suitable as an optical material such as a spectacle lens and a camera lens.

  Furthermore, in the lens using the resin of the present invention, if necessary, in order to improve antireflection, imparting high hardness, improving wear resistance, improving chemical resistance, imparting antifogging, imparting fashion, etc. Physical or chemical treatments such as surface polishing, antistatic treatment, hard coat treatment, non-reflective coat treatment, and dyeing treatment can be performed.

Hereinafter, the present invention will be specifically described by way of examples. In addition, among the performance tests of the obtained resin, refractive index and optical distortion were evaluated by the following test methods.
Refractive index (ne): Measured at 20 ° C. using a Pulfrich refractometer.
Hue: The structure represented by the formula (2) with respect to the total mass of the polymerizable composition containing a compound having a YI value of the resin measured by a color difference meter having one or more structures represented by the formula (1) A thioepoxy compound having at least one in the molecule and at least one structure represented by formula (3) in the molecule, and at least one structure represented by formula (4) in the molecule. And a value (described in Examples 1 and 4) when a polymerizable composition having a total amount of 0 of the thioepoxy compound having at least one structure represented by the formula (3) in the molecule is cured. If there is a difference of ± 1 or more, ×. When it was less than that, it was marked as ◯.
Optical distortion: Observed visually under a high-pressure mercury lamp. Those with optical distortion were marked with ×, and those without distortion were marked with ◯.

In the examples, bis (2,3-epithiopropyl) disulfide (referred to as compound (a)) and bis (2,3-epithiopropyl) are used as thioepoxy compounds having one or more structures represented by the formula (1). The sulfide (referred to as compound (b)) and by-product impurities have at least one structure represented by formula (2) in the molecule and the structure represented by formula (3) in the molecule. 2,3-epidithiopropyl (2,3-epithiopropyl) disulfide (referred to as compound (c)) and 2,3-epidithiopropyl (2,3-epithiopropyl) as at least one thioepoxy compound Using sulfide (referred to as compound (d)), it has at least one structure represented by formula (4) in the molecule and at least one structure represented by formula (3) in the molecule. Thio 2,3-epoxypropyl (2,3-epithiopropyl) disulfide (referred to as compound (e)) and 2,3-epoxypropyl (2,3-epithiopropyl) sulfide (compound (f) and In particular, the purity analysis and the polymerization of the polymerizable composition were conducted to evaluate each.
Further, compound (c), compound (d), compound (e) and compound (f) were synthesized and isolated as follows, their structures were determined in advance, and analysis factors were also determined.

Synthesis example 1
Synthesis of Compound (c) 1000 ml of methanol and 3.5 g of calcium hydroxide were charged into a reactor equipped with a stirrer and a thermometer, and 450 g of hydrogen sulfide gas was blown in for 6 hours while dropping 555 g of epichlorohydrin. At this time, the liquid temperature in the reactor was always kept at 0 ° C to 5 ° C. After completion of the reaction, hydrogen sulfide was degassed, and then methanol was distilled off to obtain 760 g of crude 1-chloro-3-mercapto-2-propanol. The resulting compound was simply distilled to a purity of 99%. Next, iodine solids were dividedly charged into 250 g of distilled product, water, methanol and 180 g of sodium bicarbonate. Subsequently, toluene and 350 g of 25% caustic soda were charged and aged for 3 hours. After the aging organic layer was washed twice with water, 130 g of thiourea, 5 g of acetic acid and methanol were mixed and stirred at 25 ° C. for 16 hours. After completion of aging, the toluene layer was washed with brine to obtain a toluene layer containing compound (a). The toluene layer thus obtained was mixed with 130 g of thiourea and 5 g of acetic acid and stirred at 25 ° C. for 6 hours. After completion of aging, the toluene layer was washed with brine to obtain a toluene layer containing compound (c). The toluene layer was concentrated and purified with a silica gel column using chloroform and hexane as developing solvents.
As a result of purification, 32 g of the purified compound (c) was obtained.

  The identification data of the obtained compound (c) are shown below.

Synthesis example 2
Synthesis of Compound (d) In a reactor equipped with a stirrer and a thermometer, a mixture of 250 g of 1-chloro-3-mercapto-2-propanol and 2.5 g of calcium hydroxide was kept at 40 ° C. while maintaining the internal temperature. Epichlorohydrin 190g was dripped. Subsequently, toluene and 350 g of 25% caustic soda were charged and aged for 3 hours. After the aging organic layer was washed twice with water, 120 g of thiourea, 5 g of acetic acid and methanol were mixed and stirred at 25 ° C. for 10 hours. After completion of aging, the toluene layer was washed with brine to obtain a toluene layer containing compound (b). The obtained toluene layer was mixed with 120 g of thiourea and 5 g of acetic acid and stirred at 25 ° C. for 6 hours. After completion of aging, the toluene layer was washed with brine to obtain a toluene layer containing compound (d). The toluene layer was concentrated and purified with a silica gel column using chloroform and hexane as developing solvents. As a result of purification, 28 g of the purified compound (d) was obtained.

  The identification data of the obtained compound (d) are shown below.

Synthesis example 3
Synthesis of Compound (e) 1000 ml of methanol and 3.5 g of calcium hydroxide were charged into a reactor equipped with a stirrer and a thermometer, and 450 g of hydrogen sulfide gas was blown in for 6 hours while dropping 555 g of epichlorohydrin. At this time, the liquid temperature in the reactor was always kept at 0 ° C to 5 ° C. After completion of the reaction, hydrogen sulfide was degassed, and then methanol was distilled off to obtain 760 g of crude 1-chloro-3-mercapto-2-propanol. The resulting compound was simply distilled to a purity of 99%. Next, iodine solids were dividedly charged into 250 g of distilled product, water, methanol and 180 g of sodium bicarbonate. Subsequently, toluene and 350 g of 25% caustic soda were charged and aged for 3 hours. After the aging organic layer was washed twice with water, 70 g of thiourea, 5 g of acetic acid and methanol were mixed and stirred at 25 ° C. for 8 hours. After completion of aging, the toluene layer was washed with brine to obtain a toluene layer containing compound (e). The toluene layer was concentrated and purified with a silica gel column using chloroform and hexane as developing solvents. As a result of purification, 25 g of purified compound (e) was obtained.

  The identification data of the obtained compound (e) are shown below.

Synthesis example 4
Synthesis of Compound (f) In a reactor equipped with a stirrer and a thermometer, a mixture of 250 g of 3-chloro-1-mercapto-2-propanol and 2.5 g of calcium hydroxide was kept at 40 ° C. while maintaining the internal temperature. Epichlorohydrin 190g was dripped. Subsequently, toluene and 350 g of 25% caustic soda were charged and aged for 3 hours. After the aging organic layer was washed twice with water, 70 g of thiourea, 5 g of acetic acid and methanol were mixed and stirred at 25 ° C. for 6 hours. After completion of aging, the toluene layer was washed with brine to obtain a toluene layer containing compound (f). The toluene layer was concentrated and purified with a silica gel column using chloroform and hexane as developing solvents. As a result of purification, 24 g of the purified product of compound (f) was obtained.

  The identification data of the obtained compound (f) are shown below.

Example 1
Acetic acid as a catalyst in a solvent of 200 g of toluene and 100 g of methanol using 152 g (1.05 equivalents) of thiourea as a thiating agent for 178 g (purity 95%) of bis (2,3-epoxypropyl) disulfide The reaction was performed at 15 ° C. using 2.5 g (0.022 equivalent). After completion of the reaction, brine was charged and the organic layer was washed three times, and then the organic layer was taken out and concentrated. The obtained residue was dissolved in cyclohexane, and the supernatant was passed through a silica gel column and concentrated. The residue obtained after the concentration was a polymerizable composition in which, in addition to the compound (a), the total of the compound (c) and the compound (e) was 0.8% by mass. As a result of chromatographic purification of this polymerizable composition on a silica gel column using chloroform and hexane as developing solvents, the total of the compound (c) and the compound (e) in the obtained polymerizable composition was 0% by mass. there were. 100 g obtained by this chromatographic purification was mixed with 0.1 g of N, N-dimethylcyclohexylamine as a curing catalyst and then mixed and degassed for 0.1 hour under reduced pressure, and then a mold comprising a glass mold and a gasket. Injected into mold. 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 physical properties of the obtained resin are shown in Table 1. The obtained resin was YI = 5.4 and was good without optical distortion.

Example 2
The synthesis was performed in the same manner as in Example 1 using 1.05 equivalent of thiourea as a thiating agent for the epoxy group of bis (2,3-epoxypropyl) disulfide. The obtained polymerizable composition was a polymerizable composition in which the total of the compound (c) and the compound (e) was 0.8% by mass in addition to the compound (a). Without chromatographic purification of 100 g of this polymerizable composition, 0.1 g of N, N-dimethylcyclohexylamine was added as a curing catalyst and the mixture was degassed for 0.1 hour under reduced pressure, and then a glass mold and gasket It poured into the mold which consists of. 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 physical properties of the obtained resin are shown in Table 1. The obtained resin was good without optical distortion.

Example 3
The same operation as in Example 2 was performed 10 times to examine the yield. The total of the compound (c) and the compound (e) in the polymerizable composition obtained by the reaction was stable at 1% by mass or less. The resins obtained by polymerization were all the same as in Example 1 with respect to refractive index and hue, and were good without optical distortion.

Example 4
A polymerizable composition was taken out by reacting in the same manner as in Example 1 except that 1.15 equivalent of thiourea was used with respect to the epoxy group. The obtained polymerizable composition was a polymerizable composition containing 0.7% by mass of the total of the compound (c) and the compound (e) in addition to the compound (a). 100 g of this polymerizable composition was added with 0.1 g of N, N-dimethylcyclohexylamine as a curing catalyst and mixed, and then degassed for 0.1 hour under reduced pressure, and then a mold mold comprising a glass mold and a gasket. Injected into. 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 physical properties of the obtained resin are shown in Table 1. The obtained resin was good without optical distortion.

Example 5
The same operation as in Example 4 was performed 10 times to examine the yield. The total of the compound (c) and the compound (e) in the polymerizable composition obtained by the reaction was stable at 1% by mass or less. The resins obtained by polymerization were all the same as in Example 1 with respect to refractive index and hue, and were good without optical distortion.

Example 6
Using bis (2,3-epoxypropyl) sulfide as the epoxy compound, the reaction and purification by column chromatography were performed in the same manner as in Example 1. The total of the compound (d) and the compound (f) in the polymerizable composition obtained after purification was 0% by mass.
100 g of this polymerizable composition was added with 0.1 g of N, N-dimethylcyclohexylamine as a curing catalyst and mixed, and then degassed for 0.1 hour under reduced pressure, and then a mold mold comprising a glass mold and a gasket. Injected into. 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 physical properties of the obtained resin are shown in Table 1. The obtained resin was YI = 4.2 and good without optical distortion.

Example 7
The reaction was conducted in the same manner as in Example 6 except that 1.15 equivalents of the thiating agent was used with respect to the epoxy group and the reaction temperature was 25 ° C. The obtained polymerizable composition was a polymerizable composition containing 0.9% by mass of the total of the compound (d) and the compound (f) in addition to the compound (b). 100 g of this polymerizable composition was added with 0.1 g of N, N-dimethylcyclohexylamine as a curing catalyst and mixed, and then degassed for 0.1 hour under reduced pressure, and then a mold mold comprising a glass mold and a gasket. Injected into.
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 physical properties of the obtained resin are shown in Table 1. The obtained resin was good without optical distortion.

Example 8
The same operation as in Example 7 was performed 10 times, and the yield was examined. The total of the compound (d) and the compound (f) in the polymerizable composition obtained by the reaction was stable at 1.5% by mass or less. The resins obtained by polymerization were all the same as in Example 6 in terms of refractive index and hue, and were good without optical distortion.

Example 9
The reaction was conducted in the same manner as in Example 6 except that 1.20 equivalents of the thiating agent was used relative to the epoxy group. The obtained polymerizable composition was a polymerizable composition containing 1.2% by mass of the total of the compound (d) and the compound (f) in addition to the compound (b). 100 g of this polymerizable composition was added with 0.1 g of N, N-dimethylcyclohexylamine as a curing catalyst and mixed, and then degassed for 0.1 hour under reduced pressure, and then a mold mold comprising a glass mold and a gasket. Injected into. 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 physical properties of the obtained resin are shown in Table 1. The obtained resin was good without optical distortion.

Example 10
The same operation as in Example 9 was performed 10 times to examine the yield. The total of the compound (d) and the compound (f) in the polymerizable composition obtained by the reaction was stable at 1.5% by mass or less. The resins obtained by polymerization were all the same as in Example 6 in terms of refractive index and hue, and were good without optical distortion.

Example 11
The reaction was performed in the same manner as in Example 4 except that 1.28 equivalents of the thiating agent was used with respect to the epoxy group and the reaction temperature was set to 35 ° C. The obtained polymerizable composition was a polymerizable composition containing 1.4% by mass of the total of the compound (d) and the compound (f) in addition to the compound (b). 100 g of this polymerizable composition was added with 0.1 g of N, N-dimethylcyclohexylamine as a curing catalyst and mixed, and then degassed for 0.1 hour under reduced pressure, and then a mold mold comprising a glass mold and a gasket. Injected into. 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 physical properties of the obtained resin are shown in Table 1. The obtained resin was good without optical distortion.

Example 12
The same operation as in Example 11 was performed 10 times to examine the yield. The total of the compound (d) and the compound (f) in the polymerizable composition obtained by the reaction was stable at 1.5% by mass or less. The resins obtained by polymerization were all the same as in Example 6 in terms of refractive index and hue, and were good without optical distortion.

Example 13
1.28 equivalents of a thiating agent is used with respect to the epoxy group, the reaction temperature is set to 35 ° C., and the composition containing the polyepoxy compound is added dropwise to the composition containing the thiating agent, as in Example 6. Reaction was performed. The obtained polymerizable composition was a polymerizable composition containing 1.2% by mass of the total of the compound (d) and the compound (f) in addition to the compound (b). 100 g of this polymerizable composition was added with 0.1 g of N, N-dimethylcyclohexylamine as a curing catalyst and mixed, and then degassed for 0.1 hour under reduced pressure, and then a mold mold comprising a glass mold and a gasket. Injected into. 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 physical properties of the obtained resin are shown in Table 1. The obtained resin was good without optical distortion.

Example 14
The same operation as in Example 13 was performed 10 times to examine the yield. The total of the compound (d) and the compound (f) in the polymerizable composition obtained by the reaction was stable at 1.5% by mass or less. The resins obtained by polymerization were all the same as in Example 6 in terms of refractive index and hue, and were good without optical distortion.

Comparative Example 1
The reaction was performed in the same manner as in Example 1 except that 3.5 equivalents of a thiating agent was used with respect to the epoxy group. The obtained polymerizable composition was a polymerizable composition containing 4.2% by mass of the total of the compound (c) and the compound (e) in addition to the compound (a). This polymerizable composition was clearly yellow with visual observation. After adding 0.1 g of N, N-dimethylcyclohexylamine as a curing catalyst to 100 g of this polymerizable composition and mixing, the mixture was degassed for 0.1 hour under reduced pressure, and then formed into a mold comprising a glass mold and a gasket. Injected. 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 physical properties of the obtained resin are shown in Table 1. The obtained resin had high YI, optical distortion, and a difference in refractive index as compared with Example 1.

Comparative Example 2
The same operation as in Comparative Example 2 was performed 10 times, and the yield was examined. The total of the compound (c) and the compound (e) in the polymerizable composition obtained by the reaction was 4% by mass or more. All the resins obtained by polymerization are higher in YI than in Example 1 in terms of refractive index and hue, have a difference in refractive index, and further, those having optical distortion are 8 times out of 10 times, yield. A decline was also confirmed.

Comparative Example 3
The reaction was performed in the same manner as in Example 6 except that 0.8 equivalent of the thiating agent was used with respect to the epoxy group. The obtained polymerizable composition was a polymerizable composition containing 5.6% by mass of the total of the compound (d) and the compound (f) in addition to the compound (b). After adding 0.1 g of N, N-dimethylcyclohexylamine as a curing catalyst to 100 g of this polymerizable composition and mixing, the mixture was degassed for 0.1 hour under reduced pressure, and then formed into a mold comprising a glass mold and a gasket. Injected. 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 physical properties of the obtained resin are shown in Table 1. The obtained resin had a high YI, optical distortion, and a difference in refractive index as compared with Example 6.

Comparative Example 4
The same operation as in Comparative Example 3 was performed 10 times, and the yield was examined. The total of the compound (d) and the compound (f) in the polymerizable composition obtained by the reaction was 4% by mass or more. The resins obtained by polymerization all have a higher YI and a difference in refractive index than those of Example 1 in terms of refractive index and hue, and further, optical distortion is observed in all 10 times, resulting in a decrease in yield. confirmed.

Comparative Example 5
The reaction was performed in the same manner as in Example 4 except that 3.5 equivalents of the thiating agent was used with respect to the epoxy group and the reaction temperature was 60 ° C. The obtained polymerizable composition was a polymerizable composition containing, in addition to the compound (b), 5.2% by mass of the total of the compound (d) and the compound (f). After adding 0.1 g of N, N-dimethylcyclohexylamine as a curing catalyst to 100 g of this polymerizable composition and mixing, the mixture was degassed for 0.1 hour under reduced pressure, and then formed into a mold comprising a glass mold and a gasket. Injected. 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 physical properties of the obtained resin are shown in Table 1. The obtained resin had high YI, optical distortion, and a difference in refractive index as compared with Example 4.

Comparative Example 6
The same operation as in Comparative Example 5 was performed 10 times, and the yield was examined. The total of the compound (d) and the compound (f) in the polymerizable composition obtained by the reaction was 4% by mass or more. The resins obtained by polymerization all have a high YI and a difference in refractive index as compared with Example 6 in terms of refractive index and hue, and furthermore, those having optical distortion are 8 times out of 10 times, yield. A decline was also confirmed.

Claims (12)

Formula (1)

(Wherein R ₁ represents a hydrocarbon having 1 to 10 carbon atoms, R ₂ , R ₃ , and R ₄ each represents a hydrocarbon group or hydrogen atom having 1 to 10 carbon atoms) In the polymerizable composition containing the compound having the above, the thioepoxy compound A having at least one structure represented by the formula (2) and at least one structure represented by the formula (3), and the formula The total of the thioepoxy compound B having at least one structure represented by (4) and having at least one structure represented by formula (3) is 4% by mass with respect to the total mass of the polymerizable composition. A polymerizable composition characterized by the following.

The thioepoxy compound A is a compound represented by the formula (5), the thioepoxy compound B is a compound represented by the formula (6), and further has one structure represented by the formula (1). The polymerizable composition according to claim 1, wherein the compound having the above is a compound represented by Formula (7).

(Y represents a substituted or unsubstituted linear, branched or cyclic divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted 1,4-dithian group, an arylene group or an aralkylene group. m represents an integer of 0 to 2, and n represents an integer of 0 to 4.)

(Wherein, R ₅ to R ₁₀ each represents a hydrocarbon group or hydrogen having 1 to 10 carbon atoms.
Y represents a substituted or unsubstituted linear, branched or cyclic divalent hydrocarbon group having 1 to 10 hydrocarbons, a substituted or unsubstituted 1,4-dithian group, an arylene group or an aralkylene group. m represents an integer of 0 to 2, and n represents an integer of 0 to 4. )   The thioepoxy compound A is 2,3-epidithiopropyl (2,3-epithiopropyl) disulfide and / or 2,3-epidithiopropyl (2,3-epithiopropyl) sulfide, and the thioepoxy compound B Is 2,3-epoxypropyl (2,3-epithiopropyl) disulfide and / or 2,3-epoxypropyl (2,3-epithiopropyl) sulfide, and is further represented by the formula (1) The polymerizable composition according to claim 1, wherein the compound having one or more structures is bis (2,3-epithiopropyl) disulfide and / or bis (2,3-epithiopropyl) sulfide. object.   The thioepoxy in the formula (1) is used by using 0.9 to 1.3 equivalents of the thiating agent used in the production of the polythioepoxy compound from the polyepoxy compound with respect to the equivalent of the epoxy group in the polyepoxy compound. The manufacturing method of the polymeric composition which the sum total of the compound A and the thioepoxy compound B makes 4 mass% or less with respect to polymeric composition total mass.   The thiating agent used in the production of the polythioepoxy compound from the polyepoxy compound is used in an amount of 0.9 to 1.3 equivalents relative to the equivalent of the epoxy group in the polyepoxy compound, and the reaction temperature is 0 ° C. to 50 ° C. The manufacturing method of the polymeric composition which the sum total of the thioepoxy compound A and the thioepoxy compound B in Formula (1) makes 4 mass% or less with respect to polymeric composition total mass by setting it as ° C.   The thiating agent used in the production of the polythioepoxy compound from the polyepoxy compound is used in an amount of 0.9 to 1.3 equivalents relative to the equivalent of the epoxy group in the polyepoxy compound, and the acid or anhydride thereof is used. The total of the thioepoxy compound A and the thioepoxy compound B in the formula (1) is obtained by using 0.2 equivalent or less with respect to the equivalent of the epoxy group in the polyepoxy compound and setting the reaction temperature to 0 ° C. to 50 ° C. The manufacturing method of the polymeric composition made into 4 mass% or less with respect to polymeric composition total mass. The thioepoxy compound A is a compound represented by the formula (5), the thioepoxy compound B is a compound represented by the formula (6), and further has one structure represented by the formula (1). The production method according to any one of claims 4 to 6, wherein the compound having the above is a compound represented by the formula (7).

(Y represents a substituted or unsubstituted linear, branched or cyclic divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted 1,4-dithian group, an arylene group or an aralkylene group. m represents an integer of 0 to 2, and n represents an integer of 0 to 4.)

(Wherein, R ₅ to R ₁₀ each represents a hydrocarbon group or hydrogen having 1 to 10 carbon atoms.
Y represents a substituted or unsubstituted linear, branched or cyclic divalent hydrocarbon group having 1 to 10 hydrocarbons, a substituted or unsubstituted 1,4-dithian group, an arylene group or an aralkylene group. m represents an integer of 0 to 2, and n represents an integer of 0 to 4. )   The thioepoxy compound A is 2,3-epidithiopropyl (2,3-epithiopropyl) disulfide and / or 2,3-epidithiopropyl (2,3-epithiopropyl) sulfide, and the thioepoxy compound B Is 2,3-epoxypropyl (2,3-epithiopropyl) disulfide and / or 2,3-epoxypropyl (2,3-epithiopropyl) sulfide, and is further represented by the formula (1) The production method according to claim 7, wherein the compound having one or more structures is bis (2,3-epithiopropyl) disulfide and / or bis (2,3-epithiopropyl) sulfide.   An optical material is obtained using the polymerizable composition according to any one of claims 1 to 3 and / or the polymerizable composition obtained by the method according to any one of claims 4 to 8. Manufacturing method of optical material.   The manufacturing method according to claim 9, wherein the optical material is a lens.   The production method according to claim 10, which is carried out by a casting polymerization method.   A lens obtained by the method according to claim 11.