JP4799471B2 - Lens manufacturing method - Google Patents

Description

  The present invention relates to a resin used for an optical material such as a plastic lens, a prism, an optical fiber, an information recording base, a filter, and a light emitting diode, and in particular, a method for producing a lens suitably used as a plastic lens resin for glasses. About.

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

  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 an episulfide 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 hue due to quality fluctuation when the polymerizable composition as a raw material is produced industrially, and optical distortion is likely to occur. There is a case. 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 hue blur and optical distortion blur.

  In view of such a situation, as a result of intensive studies to solve the above problems, the present inventors have succeeded in obtaining knowledge about the behavior by paying attention to a compound by-produced during the production of an episulfide compound. That is, among the by-products and impurities present in the episulfide compound, it is found that a compound having a halogeno group in particular has a great influence on the polymerization rate, resin hue, heat resistance, and weather resistance, and the amount thereof changes. It has been found that it causes quality fluctuation of the polymerizable composition. Furthermore, in the polymerizable composition containing an episulfide compound having one or more structures represented by the formula (1), the ratio of the compound having a halogeno group present in the polymerizable composition to the episulfide compound [(halogeno group By making the halogeno group in the compound having) / (episulfide group in the episulfide compound)] (functional group molar ratio) 0.0009 or less, the hue blur of the resulting resin is stabilized, and optical distortion is difficult to occur. In addition, it has also been found that heat resistance and weather resistance can be stabilized.

  Furthermore, in the polymerizable composition containing an episulfide compound having one or more structures represented by the formula (1) of the present invention, the ratio of the compound having a halogeno group present in the polymerizable composition to the episulfide compound [ A method for industrial production of (halogeno group in a compound having a halogeno group) / (episulfide group in an episulfide compound)] (functional group molar ratio) of 0.0009 or less has been studied. Although it was found that it was possible to reduce the ratio of the compound having a halogeno group present in the polymerizable composition to the episulfide compound if purification was performed by column chromatography such as a silica gel column, it was a laboratory method only. 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, when producing an episulfide compound from a halohydrin compound via an epoxy compound, the ratio of the alkali used to the halohydrin compound when producing the epoxy compound (alkali / halohydrin group (molar ratio) in the halohydrin compound) , Ie, a method of setting 1.01 to 1.45, a method of specifying a reaction temperature, ie, a method of setting to 10 ° C. to 40 ° C., and a method of specifying a reaction time, ie, alkali The ratio of the compound having a halogeno group present in the polymerizable composition to the episulfide compound [(halogeno group) by a method in which the total of the charging time and the aging time of the reaction is 4 to 10 hours, respectively, or in combination. Halogeno group in a compound having) / (episulfide group in an episulfide compound)] Leading to found the present invention that the industrial production possible group molar ratio) at 0.0009 or less.

That is, the present invention
(A): Formula (1) below

(Wherein R1 is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R2, R3, and R4 are each a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom.) In the polymerizable composition containing the episulfide compound having the above, the ratio of the compound having a halogeno group present in the polymerizable composition to be used to the episulfide compound [(halogeno group in the compound having a halogeno group) / (in the episulfide compound (Episulfide group)] (functional group molar ratio) is 0.0009 or less.

(B): Polymerizable composition as described in (A) whose episulfide compound is a compound represented by following formula (2).

(In the formula, R5 to R10 each represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. Y represents a substituent or an unsubstituted linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms, (Represents a substituted or unsubstituted 1,4-dithiane group or arylene group, m represents an integer of 0 to 2, and n represents an integer of 0 to 4).

  (C): The polymerizable composition according to any one of (A) to (B), wherein the episulfide compound is a compound represented by the following formula (3).

(Wherein R11 to R16 each represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom.)

  (D): The polymerizable composition according to any one of (A) to (C), wherein the compound having a halogeno group present in the polymerizable composition is a halohydrin compound having a hydroxyl group at the same time.

  (E): Formula (1) from a halohydrin compound via an epoxy compound

(Wherein R1 is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R2, R3, and R4 are each a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom.) The ratio of the alkali used to the halohydrin compound (alkali / halohydrin group (molar ratio) in the halohydrin compound) used when producing the epoxy compound when producing the polymerizable composition containing the episulfide compound as described above is 1. The manufacturing method characterized by setting it as 01-1.45.

  (F): Formula (1) from halohydrin compound via epoxy compound

(Wherein R1 is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R2, R3, and R4 are each a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom.) When producing a polymerizable composition containing the above-described episulfide compound, the ratio of the alkali to the halohydrin compound used in producing the epoxy compound (alkali / halohydrin group (molar ratio) in the halohydrin compound) is 1.01. To 1.45, and the reaction temperature is 10 ° C to 40 ° C.

(G): Formula (1) from a halohydrin compound via an epoxy compound

(Wherein R1 is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R2, R3, and R4 are each a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom.) The ratio of the alkali used to the halohydrin compound (alkali / halohydrin group (molar ratio) in the halohydrin compound) used when producing the epoxy compound when producing the polymerizable composition containing the episulfide compound as described above is 1. 01 to 1.45, the reaction temperature is set to 10 ° C. to 40 ° C., and the total of the alkali charging time and the reaction aging time is set to 4 to 10 hours.

  (H): The production method according to any one of (E) to (G), wherein the episulfide compound is a compound represented by the following formula (2).

(In the formula, R5 to R10 each represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. Y represents a substituent or an unsubstituted linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms, (Represents a substituted or unsubstituted 1,4-dithiane group or arylene group, m represents an integer of 0 to 2, and n represents an integer of 0 to 4).

(I): The polymerizable composition according to any one of (E) to (G), wherein the episulfide compound is a compound represented by the following formula (3).

(Wherein R11 to R16 each represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom.)

  (J): A method for producing a resin, wherein the polymerizable composition according to any one of (A) to (D) is heat-cured to obtain a resin.

  (K): A method for producing a resin, wherein the polymerizable composition obtained by the method according to any one of (E) to (I) is heat-cured to obtain a resin.

  (L): The production method according to (J) to (K), wherein the resin is an optical material.

  (M): The production method according to any one of (J) to (L), which is performed by a cast polymerization method.

(N): A lens obtained by the method described in (M).
It is about.

  According to the present invention, a ratio of a compound having a halogeno group present in a polymerizable composition containing an episulfide compound to an episulfide compound [(halogeno group in a compound having a halogeno group) / (episulfide group in an episulfide compound)] ( When the functional group molar ratio is 0.0009 or less, it is possible to obtain a resin having good hue and excellent heat resistance, weather resistance, and yield. The obtained resin contributes to the thinness and fashionability of the lens, particularly in the field of eyeglass lenses.

  The present invention is described in detail below.

  Ratio of compound having halogeno group present in polymerizable composition containing episulfide compound in the present invention to episulfide compound [(halogeno group in compound having halogeno group) / (episulfide group in episulfide compound)] (functional (Base molar ratio) 0.0009 or less, for example, for the determination of halogeno groups, the determination of halogen elements by elemental analysis, gas chromatography with a mass spectrometer as a detector and high-performance liquid chromatography The episulfide group is a value calculated from the results obtained by quantifying the episulfide group by the above-described method or infrared absorption spectrum method.

  In the formula (1) representing the episulfide compound constituting the polymerizable composition in the present invention, R1 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, specifically, linear, branched or cyclic. Examples include an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms such as phenylene, alkyl-substituted phenylene, and naphthalene, or an aralkylene group having 7 to 10 carbon atoms formed by a combination of alkylene and arylene. 1-10 alkylene groups are preferred. More preferred is methylene or ethylene. More preferred is methylene. R2, R3 and R4 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 a linear, branched or cyclic carbon. Although a 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 (2) is preferable.

(In the formula, R5 to R10 each represent a hydrocarbon group having 1 to 10 carbon atoms or hydrogen. Y represents a substituted or unsubstituted linear, branched or cyclic hydrocarbon group having 1 to 10 divalent aliphatic carbonization. A hydrogen 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, R5 to R10 each have the same meaning as R2 to R4, 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 R1. 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, it may be a trifunctional or higher functional compound having a structure represented by the formula (1), in particular, a β-epithiopropylthio group as a substituent, but a bifunctional compound is preferred. Further, a compound where n = 0 and / or a compound where m = 0 and n = 1 is most preferable.

  Specific examples of the episulfide compound constituting the polymerizable composition of the present invention include bis (β-epithiopropyl) sulfide, bis (β-epithiopropyl) disulfide, bis (β-epithiopropylthio) methane, , 2-bis (β-epithiopropylthio) ethane, 1,2-bis (β-epithiopropylthio) propane, 1,3-bis (β-epithiopropylthio) propane, 1,3-bis ( β-epithiopropylthio) -2-methylpropane, 1,4-bis (β-epithiopropylthio) butane, 1,4-bis (βepithiopropylthio) -2-methylbutane, 1,3-bis (Β-epithiopropylthio) butane, 1,5-bis (β-epithiopropylthio) pentane, 1,5-bis (β-epithiopropylthio) -2-methylpentane, 1,5- (Β-epithiopropylthio) -3-thiapentane, 1,6-bis (β-epithiopropylthio) hexane, 1,6-bis (β-epithiopropylthio) -2-methylhexane, 3, 8-bis (β-epithiopropylthio) -3,6-trithiaoctane, 1,2,3-tris (β-epithiopropylthio) propane, 2,2-bis (β-epithiopropylthio) -1,3-bis (β-epithiopropylthiomethyl) propane, 2,2-bis (β-epithiopropylthiomethyl) -1- (β-epithiopropylthio) butane, 1,5-bis ( β-epithiopropylthio) -2- (β-epithiopropylthiomethyl) -3-thiapentane, 1,5-bis (β-epithiopropylthio) -2,4-bis (β-epithiopropylthio) Methyl) -3-thiapen Tan, 1- (β-epithiopropylthio) -2,2-bis (β-epithiopropylthiomethyl) -4-thiahexane, 1,5, hexane, 1,8-bis (β-epithiopropylthio) ) -4- (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -4,5-bis (β-epithiopropylthiomethyl) -3 , 6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -4,4-bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithio) Propylthio) -2,5-bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -2,4,5-tris (β-epi Thiopropylthiomethyl) -3,6 Dithiaoctane, 1,1,1-tris [{2- (β-epithiopropylthio) ethyl} thiomethyl] -2- (β-epithiopropylthio) ethane, 1,1,2,2-tetrakis [{2 -(Β-epithiopropylthio) ethyl} thiomethyl] ethane, 1,11-bis (β-epithiopropylthio) -4,8-bis (β-epithiopropylthiomethyl) -3,6,9- Trithiaundecane, 1,11-bis (β-epithiopropylthio) -4,7-bis (β-epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (β A chain aliphatic β-epithiopropylthio compound such as -epithiopropylthio) -5,7-bis (β-epithiopropylthiomethyl) -3,6,9-trithiaundecane, and

  1,3-bis (β-epithiopropylthio) cyclohexane, 1,4-bis (β-epithiopropylthio) cyclohexane, 1,3-bis (β-epithiopropylthiomethyl) cyclohexane, 1,4- Bis (β-epithiopropylthiomethyl) cyclohexane, 2,5-bis (β-epithiopropylthiomethyl) -1,4-dithiane, 2,5-bis [{2- (β-epithiopropylthio) Cycloaliphatic β-epithiopropylthio compounds such as ethyl} thiomethyl] -1,4-dithiane, and

  1,3-bis (β-epithiopropylthio) benzene, 1,4-bis (β-epithiopropylthio) benzene, 1,3-bis (β-epithiopropylthiomethyl) benzene, 1,4- Bis (β-epithiopropylthiomethyl) benzene, bis {4- (β-epithiopropylthio) phenyl} methane, 2,2-bis {4- (β-epithiopropylthio) phenyl} propane, bis { Aromatic β such as 4- (β-epithiopropylthio) phenyl} sulfide, bis {4- (β-epithiopropylthio) phenyl} sulfone, 4,4′-bis (β-epithiopropylthio) biphenyl -Other reactions such as epithiopropylthio compounds, mercapto group-containing epithio compounds such as 3-mercaptopropylene sulfide, 4-mercaptobutene sulfide, etc. Monofunctional β-epithiopropylthio compounds having a functional group can be exemplified, but are not limited to these exemplified compounds. These compounds may be used alone or in combination of two or more.

  The polymerizable composition of the present invention comprises a ratio of a compound having a halogeno group present in the polymerizable composition to an episulfide compound [(halogeno group in a compound having a halogeno group) / (episulfide group in an episulfide compound)]. (Functional group molar ratio) is 0.0009 or less, not only a mixture of the above-mentioned episulfide compounds, but also other polysulfide oligomers such as dimers, trimers and tetramers of these compounds, and synthesis of episulfide compounds Episulfide compounds having a mercapto group that are generated when epihalohydrin is deficient at the time of, and further, organic compounds such as inorganic acids and organic acids, solvents, unreacted raw materials and other by-products and impurities used during episulfide synthesis, An inorganic compound may be included as long as it does not cause a problem.

  In the polymerizable composition containing the episulfide compound in the present invention, the ratio of the compound having a halogeno group to the episulfide compound, that is, (halogeno group in the compound having a halogeno group) / (episulfide group in the episulfide compound); The functional group molar ratio needs to be 0.0009 or less. By using a polymerizable composition that satisfies these conditions, it becomes possible to obtain a resin having a stable polymerizability, good hue, excellent heat resistance, and good weather resistance with a good industrial yield. In order to further improve the yield, the functional group molar ratio is preferably 0.0005 or less, and more preferably 0.0003 or less.

  The compound having a halogeno group in the present invention is a halogen-based solvent used in the reaction, a raw material or reaction catalyst in the production of an episulfide compound, a reaction stabilizer, an additive, an obtained intermediate, a by-product compound, Impurities in production raw materials and reaction solvents.

  Specific examples of the compound having a halogeno group that defines the abundance in the present invention include 2-chlorobiphenyl, 3-chlorobiphenyl, 4-chlorobiphenyl, 2,2′-dichlorobiphenyl, 2,4-dichlorobiphenyl, 2 , 5'-dichlorobiphenyl, 2,6'-dichlorobiphenyl, 4,4'-dichlorobiphenyl, trichlorobiphenyl, tetrachlorobiphenyl, 5-chloro-2'-deoxyuridine, 1-acetyl-5-chloroindoline, 2 -Sodium chloroethanesulfonate, 2-chloropyridine, 2-chlorothiazole, chlorobenzene, dichlorobenzene, trichlorobenzene, bromobenzene, dibromobenzene, benzyl chloride, benzyl bromide, 2-chloropropene, 5-amino-2-chlorotoluene, Bi (2-bromoethyl) ether, 2-chloro-2′-acetonaphthone, 9-chloroanthracene, 2-chlorobenzaldehyde, p-chlorobenzenesulfonyl chloride, p-chlorobenzenethiol, m-chlorobenzoic acid, 4-chlorobenzonitrile, 2 -Chlorobenzotrifluoride, 3-chlorobenzotrifluoride, o-chlorobenzyl alcohol, p-chlorobenzyl alcohol, 2-chloro-2-butene, 4-chloro-1-butene, 4-chlorobutyronitrile, γ- Chlorobutyroyl chloride, chlorocycloheptane, chlorocyclopropane, dichlorotoluene, 4-chloro-2,6-dimethylaniline, 1-chloro-2,4-dimethylbenzene, p-chlorodiphenyl ether, 2-chloroethanesulfone Sodium salt, p -Chloroethylbenzene, chloroethylene, 2-chloroethyl ethyl ether, 2-chlorofluorene, 2-chlorofluorobenzene, 5-chloro-2-hydroxybenzaldehyde, 5-chloro-4-hydroxy-3-methoxybenzaldehyde, 2-chloro Mesitylene, α-chloro-o-methoxyacetophenone, 4-chloro-2-methylaniline, chloromethylcyclohexane, 4-chloro-1,2-methylenedioxybenzene, chloromethylmagnesium, (chloromethyl) pentafluorobenzene, N -(Chloromethyl) phthalimide, chloropentafluorobenzene, 1-chloro-4-pentene, m-chlorophenylacetic acid, p-chlorophenylacetic acid, 2- (4-chlorophenyl) ethanol, 3-chloropropionitrile, α-c Lolopropiophenone, m-chlorostyrene, chlorosuccinic acid, dichlorosuccinic acid, dibromosuccinic acid, 2-chlorothiazole, 5-chloro-m-xylene, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, dichloroacetonitrile, 1,3- Dichloro-2-propanone, 1,4-dichloro-2,3-butanedione, 1,7-dichloroheptane, 1,8-dichlorooctane, 2,3-dichloropropane, 3,5-dichloropyridine, 2,3- Dichlorothiophene, 2,5-dichlorotoluene, epichlorohydrin, epibromohydrin, 3-chloro-1-propanol, 2- (2-chloroethoxy) ethanol, chloromethyloxirane, 2-chloroethanol, 2,3-dichloro- 1-propanol, 1,3-dichloro-2-propano 3-chloro-1,2-propanediol, 1,2-epoxy-7-chloro-6-hydroxy-3,4-dithiaheptane, 1,2-epoxy-8-chloro-7-hydroxy-4,5- Dithiaoctane, 1,2-epithio-7-chloro-6-hydroxy-3,4-dithiaheptane, 1,2-epithio-8-chloro-7-hydroxy-4,5-dithiaoctane, 6-chloro-1-hexanol, Chloromercaptopropanol, epithiochlorohydrin, bis (1-chloro-2-hydroxypropane) disulfide, bis (1-chloro-2-hydroxypropane) sulfide, 2-bromoethanol, 2,3, -dibromo-1- Propanol, 1,2,3-tribromopropane, 1,7-dibromoheptane, 1,8-dibromooctane, 2, -Dibromotoluene, o-iodotoluene, o-diiodobenzene, p-iodophenol, diiodomethane, diiodoethane, trifluoroacetic acid, o-chlorofluorobenzene, ethyl p-fluorobenzoate, fluoroacetone, trifluoroacetic acid, trifluoro Ethanol, o- (trifluoromethyl) benzyl alcohol, m- (trifluoromethyl) benzyl alcohol, p- (trifluoromethyl) benzyl alcohol methylene chloride, chloroform, carbon tetrachloride, methylene bromide, bromoform, dichloroethane, dichloroethylene, Examples of the compound include trichloroethane, tetrachloroethane, dibromoethane, dibromoethylene, tribromoethane, and tetrabromoethane. That is, all compounds having a halogeno group are included in the compound, and are not limited to these exemplified compounds. Moreover, these compounds may contain 2 or more types individually.

  The polymerizable composition containing the episulfide compound in the present invention is obtained by combining the ratio of the compound having a halogeno group present in the polymerizable composition to the episulfide compound [(halogeno group in the compound having a halogeno group) / (in the episulfide compound It is important that the molar ratio of the functional group is 0.0009 or less. This [(halogeno group in a compound having a halogeno group) / (episulfide group in an episulfide compound)] (functional group) As a method for reducing the molar ratio) to 0.0009 or less, the following method may be mentioned.

  For example, when a polymerizable composition is taken out by reacting with a halogen-based solvent, the halogen-based solvent is sufficiently removed from the obtained polymerizable composition. Specifically, in a temperature range in which the polymerizable composition does not solidify or decompose, washing is performed with a method of treating under normal pressure or reduced pressure, or with a polar solvent or a nonpolar solvent composed of a compound having no halogeno group. Examples of the method include a method in which bubbling is performed with an inert gas with respect to the polymerizable composition, and a method in which each method is combined.

  If a halogen-based solvent is not used in the reaction and a compound having a halogeno group is not used in the raw material, reaction catalyst, reaction stabilizer, additive, etc. in the production of the episulfide compound, it exists in the polymerizable composition. Examples of the compound containing a halogeno group include a reaction intermediate and a halohydrin compound as a by-product compound.

  In this case, a method of reducing the halohydrin compound as the compound having a halogeno group in the step of synthesizing the episulfide compound can be mentioned. When an episulfide compound is synthesized after synthesizing an epoxy compound via a halohydrin compound, that is, a compound having a halogeno group and a hydroxyl group in the molecule, the reaction is carried out so that the halohydrin compound does not remain. Specifically, first, in consideration of the equivalent amount of a halohydrin group of a halohydrin compound, a method is used in which the equivalent amount of alkali used in the epoxidation reaction is limited and charged. In this case, depending on the structure and physical properties of the halohydrin compound used as a raw material compound, it is not possible to unconditionally limit it, but if alkali is used in an amount of 1.01 equivalent to 1.45 equivalent to the equivalent of the halohydrin group in the halohydrin compound, Ratio of compound having halogeno group present in polymerizable composition containing episulfide compound obtained through reaction to episulfide compound [(halogeno group in compound having halogeno group) / (episulfide group in episulfide compound) ] (Functional group molar ratio) is 0.0009 or less, and also improves the yield and hue of the resulting episulfide compound, and also the yield of the resin obtained by thermosetting the resulting polymerizable composition. Is possible. 1.05 to 1.39 equivalent is more preferable, and 1.08 to 1.34 equivalent is more preferable.

  Secondly, there is a method of limiting the reaction temperature when performing the epoxidation reaction. The reaction temperature varies depending on the structure, physical properties and stability of the halohydrin compound as a raw material compound, and also the stability of the resulting epoxy compound, and cannot be limited in general. However, when it is carried out at 10 to 40 ° C., it is obtained through a post reaction. Ratio of the compound having a halogeno group present in the polymerizable composition containing the obtained episulfide compound to the episulfide compound [(halogeno group in the compound having a halogeno group) / (episulfide group in the episulfide compound)] (functional group) (Molar ratio) becomes 0.0009 or less, and it is possible to improve the yield and hue of the resulting episulfide compound, and also the yield of the resin obtained by thermosetting the resulting polymerizable composition. . It is more preferable to carry out at 11 to 38 ° C., and a more preferable result can be derived from 12 to 35 ° C.

  Thirdly, there is a method of limiting the reaction time when performing the epoxidation reaction. The reaction time varies depending on the structure, physical properties and stability of the halohydrin compound used as the raw material compound, as well as the stability of the resulting epoxy compound, the type and amount of the solvent used, the cooling capacity for controlling the exothermic reaction, and the specifications of the reactor. Although it cannot be generally limited, halogeno groups present in the polymerizable composition containing the episulfide compound obtained through the post-reaction are a total of 4 to 10 hours of alkali charging time and aging time. The ratio of the compound to the episulfide compound [(halogeno group in the compound having a halogeno group) / (episulfide group in the episulfide compound)] (functional group molar ratio) is 0.0009 or less, and the yield of the obtained episulfide compound is It is possible to improve the rate, hue, and also the yield of the resin obtained by thermosetting the resulting polymerizable composition. That. It is more preferable if it is performed in 4.3 to 9.5 hours, and more preferable results can be obtained if it is performed in 4.5 to 9 hours.

  Here, specific examples of what can be used as an alkali used when synthesizing an epoxy compound as a reaction intermediate include ammonia, hydroxides of alkali metals and alkaline earth metals, alkali metals and alkaline earth metals Carbonates and ammonium salts and aqueous solutions of the compounds. Among them, specific examples of preferable ones include sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, and ammonium carbonate. Sodium hydroxide and potassium hydroxide are most preferable in view of reaction results, efficiency, and quality of the final product obtained.

  A method of distilling and purifying an epoxy compound as a reaction intermediate is also mentioned, but a rectifier for fractionating the compound having the halohydrin group is necessary, and a compound having a highly reactive halohydrin group is used. Heating may not be an industrially safe method. Although a method of distilling and purifying the synthesized episulfide compound is also conceivable, it may not be an industrially safe method by heating a compound having a highly reactive episulfide group.

  In addition, there is a method of adsorbing and removing a halohydrin compound by column chromatography of silica gel or activated carbon, but it may be difficult to remove a compound having a halogeno group industrially at low cost.

  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 episulfide compounds, epoxy compounds, thiol compounds, polyphenol compounds, iso (thio) cyanate compounds, mercapto organic acids, organic acids other than those included in the polymerizable composition according to the present invention. And olefins including anhydrides, amino acids and mercaptoamines, amines, (meth) acrylates and the like.

  Specific examples of preferred epoxy compounds as resin modifiers 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 compound obtained by condensation of polyvalent organic acid compound and epihalohydrin compound, amine epoxy obtained by condensation of primary and secondary diamine compounds and epihalohydrin compound Compounds, etc. and, there may be mentioned vinyl cyclohexene diepoxide and an aliphatic polyhydric epoxy compound such as, but not limited to only these exemplified compounds. These may be used alone or in combination of two or more.

  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 Aromatic thiols such as, but not limited to the exemplified compounds

  Specific examples of preferred polyphenols include those having one or more phenolic hydroxyl groups in the aromatic ring, and monophenols include phenol, o-cresol, m-cresol, p-cresol, 3-methoxyphenol, 4-ethoxyphenol, 4-n-propoxyphenol, 3-butoxyphenol, nonylphenol, 2-n-propylphenol, 3,5-xylenol, 2,4-dinitrophenol, 2-nitrophenol, 2-amino-4- Nitrophenol, thymol, carvacrol, α-naphthol, 2-aminophenol and the like are exemplified, and polyphenols include catechol, resorcin, hydroquinone, pyrogallol and the like, but are not limited to these exemplified compounds. . These polyphenol compounds may be used alone or in admixture of two or more.

  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'-tetramethylxyl 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 dii Cyanate, 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, these alkyl-substituted products, alkoxy-substituted products, nitro-substituted products, prepolymer-modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, burette-modified products, dimerization or trimerization reaction products are also used. it can.

  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, these alkyl-substituted products, alkoxy-substituted products, nitro-substituted products and prepolymer-modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, burette-modified products, dimerization or trimerization reaction products, etc. are also used. it can.

  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, these alkyl-substituted products, alkoxy-substituted products, nitro-substituted products and prepolymer-modified products with polyhydric alcohols, carbodiimide-modified products, urea-modified products, burette-modified products, dimerization or trimerization reaction products, etc. are also used. it can.

  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- 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, 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-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.

  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 Tertiary amines such as 4,0) -7-undecene, 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, tetra Quaternary phosphonium salts such as butylphosphonium chloride, tetrabutylphosphonium bromide, dimethyltin dichloride, dibutyltin dichloride, dibutyltin dilaurate, dibutyltin dichloride Lewis acids such as acetate, tetrachlorotin, dibutyltin oxide, diacetoxytetrabutyldistanoxane, zinc chloride, zinc acetylacetone, aluminum chloride, aluminum fluoride, triphenylaluminum, tetrachlorotitanium, calcium acetate, 2,2 ' -Azobis (2-cyclopropylpropionitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), t- Radical polymerization catalysts such as butyl peroxy-2-ethylhexanoate, n-butyl-4,4′-bis (t-butylperoxy) valerate, t-butylperoxybenzoate, diphenyliodonium hexafluorophosphate, diphenyliodonium Hexafluoroarsenic acid, diphenyliodonium Hexafluorobutene antimony, triphenylsulfonium 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 as the tertiary amine compounds are N, N-diisopropylethylamine, N-methyldicyclohexylmethylamine, N, N-dimethylcyclohexylamine, and N, N-diethylethanolamine. In some cases, good results may be obtained by using a mixture of two or more tertiary amines having different catalytic activities. Moreover, as a preferable example of the combination of tertiary amines having different catalytic activities, although it is not limited in general depending on the type of episulfide compound used or the type of resin modifier, N, N-dimethylcyclohexylamine and N- Examples thereof include combinations of methyldicyclohexylmethylamine, N, N-dimethylcyclohexylamine and N, N-diisopropylethylamine, N, N-diethylethanolamine and N-methyldicyclohexylmethylamine.

  Preferred as phosphine compounds are tri-n-butylphosphine and triphenylphosphine, and preferred as quaternary ammonium salts are preferred as tetramethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide and quaternary phosphonium salts. Those are tetramethylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide.

  These phosphine compounds, quaternary ammonium salts, and quaternary phosphonium salts may be preferably used in combination with tin-based catalysts having different catalytic activities. In this case, specific examples of preferred tin-based catalysts are dimethyltin dichloride, dibutyltin dichloride, dibutyltin dilaurate, dibutyltin diacetate, tetrachlorotin, dibutyltin oxide, and diacetoxytetrabutyldistanoxane.

  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 episulfide 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 an episulfide 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 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 episulfide 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 known molding methods, depending on the purpose. Various substances such as an external or internal mold release agent and an adhesion improver may be added.

  Further, the taken out 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 having excellent heat resistance and weather resistance, having no hue blur and excellent 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) that 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, the amount of the compound having a halogeno group in the polymerizable composition containing the episulfide compound, and the performance test of the obtained resin, the polymerizability, the resin hue, the heat resistance of the resin, and the optical strain are determined by the following test methods. evaluated.
Quantitative determination of compounds having a halogeno group in a polymerizable composition containing an episulfide compound (functional group molar ratio): A compound having a halogeno group by high-performance liquid chromatography or gas chromatography using a mass spectrometer as a detector The amount was quantified and the functional group molar ratio was calculated.
Polymerization: A thermocouple thermometer with a recorder was used to measure the resin temperature during the polymerization, and the time from the start of polymerization until the exothermic temperature reached the peak top was evaluated as the polymerization.
Resin hue: A resin flat plate having a thickness of 9 mm was prepared, and the yellowness (hereinafter referred to as YI) was measured with a color difference meter (manufactured by Minolta). In addition, YI in an Example table | surface represents the value of the resin hue after performing the heat processing for 3 hours at 120 degreeC.
Heat resistance: Tg temperature was measured by TMA penetration method (load 50 g, needle tip 0.5 mmφ, heating rate 10 ° C./min).
-Weather resistance test: After irradiating an accumulated illuminance of 450,000 lux using an artificial sunlamp, the hue is measured, and the color difference is calculated from the hue before and after irradiation in the following formula (1). A color difference value of less than 1.5 was judged as ◯, 1.5 or more and less than 3.0 as Δ, and 3 or more as x.

Optical distortion: observed visually under a high-pressure mercury lamp. A case where a large number of optical distortions were observed was rated as x, a number where some optical distortions were observed was marked as △, and a case where no optical distortion was observed was marked as ◯.

Reference example 1
As a polymerizable composition containing an episulfide compound, 100 g of bis (β-epithiopropyl) disulfide containing no halohydrin compound, 20 mg of N, N-dimethylcyclohexylamine and 100 mg of N-methyldicyclohexylamine as curing catalysts, Furthermore, 10 g of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane was added as a resin modifier and stirred, and degassed under reduced pressure for 0.5 hours. After filtration through a 3 μm Teflon (registered trademark) filter, the solution was injected into a molding mold composed of a glass mold and a gasket. The mold was allowed to stand at 30 ° C. for 10 hours and then gradually heated from 30 ° C. to 80 ° C., and polymerization was carried out in 21 hours. After completion of the polymerization, the mold was gradually cooled to room temperature, and the resin was removed from the mold. The obtained resin was annealed at 120 ° C. for 3 hours, and the physical properties were measured. Table 1 shows the polymerizability of the resin, the resin hue, and the heat resistance of the resin.

Example 2
The same operation as in Example 1 was carried out except that 100 g of bis (β-epithiopropyl) disulfide containing 200 ppm of chloromercaptopropanol, a polymerizable composition containing an episulfide compound, was used. Table 1 shows the polymerizability of the resin, the resin hue, and the heat resistance of the resin.

Example 3
Example 1 except that 100 g of bis (β-epithiopropyl) disulfide containing 500 ppm of 1,2-epithio-8-chloro-7-hydroxy-4,5-dithiaoctane is present as a polymerizable composition containing an episulfide compound The same operation as 1 was performed. Table 1 shows the polymerizability of the resin, the resin hue, and the heat resistance of the resin.

Example 4
Example 1 except that 100 g of bis (β-epithiopropyl) disulfide containing 750 ppm of 1,2-epithio-8-chloro-7-hydroxy-4,5-dithiaoctane is present as a polymerizable composition containing an episulfide compound The same operation as 1 was performed. Table 1 shows the polymerizability of the resin, the resin hue, and the heat resistance of the resin.

Example 5
The same operation as in Example 1 was carried out except that 100 g of a polymerizable composition containing an episulfide compound and 100 g of bis (β-epithiopropyl) disulfide containing 600 ppm of epichlorohydrin were used. Table 1 shows the polymerizability of the resin, the resin hue, and the heat resistance of the resin.

Example 6
The same operation as in Example 1 was carried out except that 100 g of a polymerizable composition containing an episulfide compound and 100 g of bis (β-epithiopropyl) disulfide containing 830 ppm of epithiochlorohydrin was used. Table 1 shows the polymerizability of the resin, the resin hue, and the heat resistance of the resin.

Example 7
The same operation as in Example 1 was carried out except that 100 g of bis (β-epithiopropyl) disulfide containing 720 ppm of bis (1-chloro-2-hydroxypropane) disulfide, a polymerizable composition containing an episulfide compound, was used. . Table 1 shows the polymerizability of the resin, the resin hue, and the heat resistance of the resin.

Example 8
The same operation as in Example 1 was performed except that 100 g of a polymerizable composition containing an episulfide compound and bis (β-epithiopropyl) disulfide containing 940 ppm of bis (1chloro-2-hydroxypropane) sulfide were used. Table 1 shows the polymerizability of the resin, the resin hue, and the heat resistance of the resin.

Comparative Example 1
The same operation as in Example 1 was carried out except that 100 g of bis (β-epithiopropyl) disulfide containing 1000 ppm of chloromercaptopropanol, a polymerizable composition containing an episulfide compound, was used. The polymerizability of the resin, the resin hue, and the heat resistance of the resin are shown in Table 1. However, the polymerization rate was slow, the resin hue was deteriorated, the heat resistance was lowered, and the weather resistance was further deteriorated. The optical distortion was x.

Comparative Example 2
A polymerizable composition containing an episulfide compound, except that 100 g of bis (β-epithiopropyl) disulfide containing 1500 ppm of 1,2-epithio-8-chloro-7-hydroxy-4,5-dithiaoctane was used. The same operation as 1 was performed. The polymerizability of the resin, the resin hue, and the heat resistance of the resin are shown in Table 1. However, the polymerization rate was slow, the resin hue was deteriorated, the heat resistance was lowered, and the weather resistance was further deteriorated. The optical distortion was Δ.

Comparative Example 3
A polymerizable composition containing an episulfide compound was carried out except that 100 g of bis (β-epithiopropyl) disulfide containing 2% of 1,2-epithio-8-chloro-7-hydroxy-4,5-dithiaoctane was used. Although the same operation as Example 1 was performed, it did not superpose | polymerize but resin was not able to be obtained. The results are shown in Table 1.

Comparative Example 4
The same operation as in Example 1 was carried out except that 100 g of bis (β-epithiopropyl) disulfide containing 1000 ppm of a polymerizable composition containing an episulfide compound and 3-chloro-1-propanol was used. The polymerizability of the resin, the resin hue, and the heat resistance of the resin are shown in Table 1. However, the polymerization rate was slow, the resin hue was deteriorated, the heat resistance was lowered, and the weather resistance was further deteriorated. The optical distortion was Δ.

Comparative Example 5
The same operation as in Example 1 was performed except that 100 g of bis (β-epithiopropyl) disulfide containing 1500 ppm of 1-chlorohexane, a polymerizable composition containing an episulfide compound, was used. The polymerizability of the resin, the resin hue, and the heat resistance of the resin are shown in Table 1. However, the polymerization rate was slow, the resin hue was deteriorated, the heat resistance was lowered, and the weather resistance was further deteriorated. The optical distortion was Δ.

Comparative Example 6
The same operation as in Example 1 was carried out except that 100 g of bis (β-epithiopropyl) disulfide containing 2000 ppm of 6-chloro-1-hexanol, a polymerizable composition containing an episulfide compound, was used. The polymerizability of the resin, the resin hue, and the heat resistance of the resin are shown in Table 1. However, the polymerization rate was slow, the resin hue was deteriorated, the heat resistance was lowered, and the weather resistance was further deteriorated. The optical distortion was Δ.

Comparative Example 7
The same operation as in Example 1 was carried out except that 100 g of a polymerizable composition containing an episulfide compound and bis (β-epithiopropyl) disulfide containing 2000 ppm of bis (1-chloro-2-hydroxypropane) disulfide was used. . The polymerizability of the resin, the resin hue, and the heat resistance of the resin are shown in Table 1. However, the polymerization rate was slow, the resin hue was deteriorated, the heat resistance was lowered, and the weather resistance was further deteriorated. The optical distortion was x.

Comparative Example 8
The same operation as in Example 1 was carried out except that 100 g of a polymerizable composition containing an episulfide compound and bis (β-epithiopropyl) disulfide containing 2000 ppm of bis (1-chloro-2-hydroxypropane) sulfide was used. However, it did not polymerize and the resin could not be obtained. The results are shown in Table 1.

Compound abbreviation A: Chloromercaptopropanol B: 1,2-epithio-8-chloro-7-hydroxy-4,5-dithiaoctane C: Epichlorohydrin D: Epithiochlorohydrin E: Bis (1-chloro-2-hydroxypropane) ) Disulfide F: Bis (1-chloro-2-hydroxypropane) sulfide G: 3-Chloro-1-propanol H: 1-Chlorohexane I: 6-Chloro-1-hexanol

Example 9
A reaction flask equipped with a stirrer and a thermometer was charged with 250 g of bis (1-chloro-2-hydroxypropane) disulfide, 200 g of water, 50 g of methanol, and 200 g of toluene as a halohydrin compound and stirred to make a slurry. Thereto was charged 416 g of 25% aqueous sodium hydroxide solution in 1 hour while maintaining the reaction temperature at 18 ° C. Subsequently, after aging at the same temperature for 4.0 hours, the reaction mass was allowed to stand and liquid separation, and the toluene layer obtained was washed with brine three times. Next, toluene was distilled off to obtain 160 g of bis (β-epoxypropyl) disulfide as a residue. The total amount of this epoxy compound was charged dropwise with 164 g of thiourea, 129 g of acetic acid and 300 g of water being added and stirred while maintaining the reaction temperature at 25 ° C. After aging, 400 g of toluene was charged, and then 122 g of 25% aqueous ammonia was added dropwise, followed by aging. After completion of aging, the toluene layer was taken out and washed 3 times with brine. After toluene was distilled off from the obtained toluene layer, 1400 g of cyclohexane was charged into the residue and extracted. Cyclohexane was distilled off from the obtained cyclohexane layer to obtain a residue. The obtained residue was filtered through a 3 μm Teflon (registered trademark) filter to obtain a polymerizable composition containing 130 g of bis (β-epithiopropyl) disulfide. As a result of analysis, the ratio of the compound having a halogeno group present in the resulting polymerizable composition to the episulfide compound [(halogeno group in the compound having a halogeno group) / (episulfide group in the episulfide compound)] (functional group) The molar ratio was 0.0004.

Example 10
The same operation as in Example 1 was performed using the polymerizable composition containing bis (β-epithiopropyl) disulfide obtained in Example 9 as the polymerizable composition containing an episulfide compound. Table 2 shows the polymerizability of the resin, the resin hue, and the heat resistance of the resin.

Comparative Example 9
A reaction flask equipped with a stirrer and a thermometer was charged with 250 g of bis (1-chloro-2-hydroxypropane) disulfide, 200 g of water, 50 g of methanol, and 200 g of toluene as a halohydrin compound and stirred to make a slurry. Thereto, 315 g of 25% aqueous sodium hydroxide solution was charged in 1 hour while maintaining the reaction temperature at 18 ° C. Subsequently, after aging at the same temperature for 8.0 hours, the toluene mass obtained after standing and separating the reaction mass was washed with brine three times. Subsequently, toluene was distilled off to obtain 140 g of bis (β-epoxypropyl) disulfide as a residue. Thereafter, a polymerizable composition containing 92 g of bis (β-epithiopropyl) disulfide was obtained in the same manner as in Example 9. As a result of analysis, the ratio of the compound having a halogeno group present in the resulting polymerizable composition to the episulfide compound [(halogeno group in the compound having a halogeno group) / (episulfide group in the episulfide compound)] (functional group) The molar ratio was 0.0054.

Comparative Example 10
The same operation as in Example 1 was performed using the polymerizable composition containing bis (β-epithiopropyl) disulfide obtained in Comparative Example 9 as the polymerizable composition containing the episulfide compound. The resin could not be obtained. The results are shown in Table 2.

Comparative Example 11
A reaction flask equipped with a stirrer and a thermometer was charged with 250 g of bis (1-chloro-2-hydroxypropane) disulfide, 200 g of water, 50 g of methanol, and 200 g of toluene as a halohydrin compound and stirred to make a slurry. Thereto, 416 g of 25% aqueous sodium hydroxide solution was charged in 1 hour while maintaining the reaction temperature at 5 ° C. Subsequently, after aging at the same temperature for 8.0 hours, the toluene mass obtained after standing and separating the reaction mass was washed with brine three times. Subsequently, toluene was distilled off to obtain 143 g of bis (β-epoxypropyl) disulfide as a residue. Thereafter, a polymerizable composition containing 113 g of bis (β-epithiopropyl) disulfide was obtained in the same manner as in Example 9. As a result of analysis, the ratio of the compound having a halogeno group present in the resulting polymerizable composition to the episulfide compound [(halogeno group in the compound having a halogeno group) / (episulfide group in the episulfide compound)] (functional group) The molar ratio was 0.0032.

Comparative Example 12
The same operation as in Example 1 was performed using the polymerizable composition containing bis (β-epithiopropyl) disulfide obtained in Comparative Example 11 as the polymerizable composition containing the episulfide compound. The resin could not be obtained. The results are shown in Table 2.

Comparative Example 13
A reaction flask equipped with a stirrer and a thermometer was charged with 250 g of bis (1-chloro-2-hydroxypropane) disulfide, 200 g of water, 50 g of methanol, and 200 g of toluene as a halohydrin compound and stirred to make a slurry. Thereto, 416 g of 25% aqueous sodium hydroxide solution was charged in 1 hour while maintaining the reaction temperature at 20 ° C. Subsequently, after aging at the same temperature for 2.0 hours, the toluene layer obtained after standing and separating the reaction mass was washed with brine three times. Next, toluene was distilled off to obtain 145 g of bis (β-epoxypropyl) disulfide as a residue. Thereafter, a polymerizable composition containing 125 g of bis (β-epithiopropyl) disulfide was obtained in the same manner as in Example 9. As a result of analysis, the ratio of the compound having a halogeno group present in the resulting polymerizable composition to the episulfide compound [(halogeno group in the compound having a halogeno group) / (episulfide group in the episulfide compound)] (functional group) The molar ratio was 0.0018.

Comparative Example 14
The same operation as in Example 1 was performed using the polymerizable composition containing bis (β-epithiopropyl) disulfide obtained in Comparative Example 11 as the polymerizable composition containing the episulfide compound. The polymerizability of the resin, the resin hue, and the heat resistance of the resin are shown in Table 2. However, the polymerization rate was slow, the resin hue was deteriorated, the heat resistance was lowered, and the weather resistance was further deteriorated. The optical distortion was x.

Claims (4)

The following formula (1) is formed in one molecule from the halohydrin compound via the epoxy compound.
(Wherein R1 is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R2, R3, and R4 are each a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom.) A step of producing a polymerizable composition containing an episulfide compound having the above,
A step of producing a lens by heat-curing the polymerizable composition,
In the step of producing the polymerizable composition, the ratio of the alkali used to the halohydrin compound (alkali / halohydrin group (molar ratio) in the halohydrin compound) is 1.01 to 1.45, and the reaction temperature is 10 ° C. The ratio of the compound having a halogeno group present in the polymerizable composition after the reaction to the episulfide compound is set to ˜40 ° C. and the total of the alkali charging time and the reaction aging time is 4 to 10 hours [( A method for producing a lens, comprising a step of reducing (halogeno group in compound having halogeno group) / (episulfide group in episulfide compound)] (functional group molar ratio) to 0.0009 or less. The method for producing a lens according to claim 1, wherein the episulfide compound is a compound represented by the following formula (2).
(In the formula, R5 to R10 each represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. Y represents a substituent or an unsubstituted linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms, (Represents a substituted or unsubstituted 1,4-dithiane group or arylene group, m represents an integer of 0 to 2, and n represents an integer of 0 to 4). The method for producing a lens according to claim 1, wherein the episulfide compound is a compound represented by the following formula (3).
(Wherein R11 to R16 each represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom.)   The method for producing a lens according to any one of claims 1 to 3, wherein the compound having a halogeno group present in the polymerizable composition is a halohydrin compound having a hydroxyl group at the same time.