Method for producing polymerizable composition, polymerizable composition, resin, molding, optical material, and lens

Abstract

To provide a method for producing a polymerizable composition which can produce a polymerizable composition that enables production of a resin excellent in heat resistance.SOLUTION: A method for producing a polymerizable composition includes the steps of: mixing episulphide, polythiol and amine to obtain a composition (A); mixing the composition (A) with an acidic compound to obtain a composition (B); and mixing the composition (B) with a polyiso(thio)cyanate compound to obtain a polymerizable composition.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a method for producing a polymerizable composition, a polymerizable composition, a resin, a molded article, an optical material, and a lens. [Background technology]

[0002] 2. Description of the Related Art Plastic lenses are lighter and less likely to break than inorganic lenses, and can be dyed, and therefore, in recent years, they have rapidly become popular for use as eyeglass lenses, camera lenses, and the like.

[0003] In recent years, various studies have been conducted on polymerizable compositions containing episulfide compounds as raw materials for producing resins for plastic lenses and the like. For example, Patent Document 1 discloses a polymerizable composition that contains a specific episulfide compound, a polyiso(thio)cyanate compound, a polythiol compound, and a specific epoxy compound, as a polymerizable composition that can produce a resin having a high refractive index and excellent strength. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2022 / 168892 Summary of the Invention [Problem to be solved by the invention]

[0005] However, for a polymerizable composition produced using at least an episulfide compound, a polyiso(thio)cyanate compound, and a polythiol compound, there are cases where it is required to improve the heat resistance of a resin produced using this polymerizable composition. An object of one aspect of the present disclosure is to provide a method for producing a polymerizable composition capable of producing a polymerizable composition capable of producing a resin having excellent heat resistance, a polymerizable composition capable of producing a resin having excellent heat resistance, and a resin, a molded body, an optical material, and a lens having excellent heat resistance. [Means for solving the problem]

[0006] Means for solving the above problems include the following aspects. <1> A step of obtaining a composition (A) by mixing an episulfide compound represented by the following formula (1), a polythiol compound, and an amine compound; A step of mixing the composition (A) with an acidic compound to obtain a composition (B); A step of mixing the composition (B) with a polyiso(thio)cyanate compound to obtain a polymerizable composition; A method for producing a polymerizable composition comprising the steps of:

[0007] [ka]

[0008] In formula (1), Y represents a substituted or unsubstituted linear alkylene group having 1 to 4 carbon atoms, a substituted or unsubstituted branched alkylene group having 2 to 4 carbon atoms, a substituted or unsubstituted cyclic cycloalkanediyl group having 3 to 6 carbon atoms, a substituted or unsubstituted alkylene group having 4 to 8 carbon atoms containing an alicyclic skeleton containing one or more sulfur atoms, a substituted or unsubstituted alkylenearylenealkylene group having 8 to 16 carbon atoms, a substituted or unsubstituted arylene group, or a substituted or unsubstituted aralkylene group, m represents an integer of 0 to 2, and n represents an integer of 0 to 3.

[0009] <2> The acidic compound includes at least one compound (b) selected from the group consisting of an acid (b1) having a pKa of less than 2.0 and an anhydride (b2) of an acid having a pKa of less than 2.0. <1> A method for producing the polymerizable composition according to claim 1. <3> The acid (b1) comprises a sulfonic acid having a pKa of less than 2.0, and the anhydride (b2) comprises an anhydride of a sulfonic acid having a pKa of less than 2.0; <2> A method for producing the polymerizable composition according to claim 1. <4> the acid (b1) comprises at least one selected from the group consisting of 10-camphorsulfonic acid, methanesulfonic acid, and p-toluenesulfonic acid; The anhydride (b2) includes at least one selected from the group consisting of 10-camphorsulfonic anhydride, methanesulfonic anhydride, and p-toluenesulfonic anhydride. <2> or <3> A method for producing the polymerizable composition according to claim 1. <5> further comprising mixing an epoxy compound. <1> ~ <4> 13. A method for producing the polymerizable composition according to claim 12. <6> The epoxy compound includes an epoxy compound (X) containing one or more epoxy groups in one molecule and not containing an episulfide group. <5> A method for producing the polymerizable composition according to claim 1. <7> The epoxy compound includes an epoxy compound (X1) containing two or more epoxy groups in one molecule. <5> or <6> A method for producing the polymerizable composition according to claim 1. <8> The total number of moles of mercapto groups contained in the total amount of the polythiol compound is M S year, The total number of moles of iso(thio)cyanate groups in the total amount of the polyiso(thio)cyanate compound is M N year, The total number of moles of episulfide groups contained in the total amount of the episulfide compound represented by the formula (1) is M E In this case, (M S -M N ) / M E The ratio is greater than 0 and less than or equal to 0.20. <1> ~ <7> 13. A method for producing the polymerizable composition according to claim 12. <9> The polythiol compound is 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,5-bis(mercaptomethyl)-1,4-dithiane, bis(mercaptomethyl)-1,4-dithiane, at least one selected from the group consisting of 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, and tris(mercaptomethylthio)methane; <1> ~ <8> 13. A method for producing the polymerizable composition according to claim 12. <10> The polyiso(thio)cyanate compound includes at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate. <1> ~ <9> 13. A method for producing the polymerizable composition according to claim 12.

[0010] <11> The amine compound includes at least one of a compound represented by the following formula (3) and a compound represented by the following formula (4): <1> ~ <10> 13. A method for producing the polymerizable composition according to claim 12.

[0011] [ka]

[0012] In formula (3), m R 1 each independently represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a halogen atom; Q represents a carbon atom, a nitrogen atom, or an oxygen atom; and m represents an integer of 0 to 5. In formula (4), R 2 , R 3 , and R 4 R each independently represents a linear alkyl group having 3 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an allyl group. 2 and R 3 may be bonded to each other to form a ring.

[0013] <12> the compound represented by formula (3) is at least one selected from the group consisting of 2-methylpyrazine, pyridine, α-picoline, β-picoline, γ-picoline, 2,6-lutidine, 3,5-lutidine, 2,4,6-trimethylpyridine, 3-chloropyridine, 2-ethylpyridine, and 3-ethylpyridine; The compound represented by the formula (4) is at least one selected from the group consisting of triallylamine and trioctylamine. <11> A method for producing the polymerizable composition according to claim 1. <13> The acidic compound includes a Lewis acid compound. <1> ~ <12> 13. A method for producing the polymerizable composition according to claim 12.

[0014] <14> 14. The method for producing a polymerizable composition according to claim 13, wherein the Lewis acid compound comprises a compound represented by the following formula (5):

[0015] [ka]

[0016] In formula (5), R 4 represents an alkyl group having 1 to 4 carbon atoms, and X represents a fluorine atom, a chlorine atom, a bromine atom, or -OC(=O)-R 5R 5 represents an alkyl group having 1 to 11 carbon atoms, and c represents an integer of 1 to 3.

[0017] <15> The compound represented by the formula (5) is at least one selected from the group consisting of dimethyltin dichloride, dibutyltin dichloride, and dibutyltin dilaurate. <14> A method for producing the polymerizable composition according to claim 1. <16> further comprising mixing a silicone compound. <1> ~ <15> 13. A method for producing the polymerizable composition according to claim 12. <17> <1> ~ <16> 1. A polymerizable composition obtained by the method for producing a polymerizable composition according to any one of the above items. <18> <17> A resin which is a cured product of the polymerizable composition described above. <19> <18> A molded article comprising the resin according to claim 1. <20> <18> An optical material comprising the resin according to claim 1. <21> <18> A lens comprising the resin described in claim 1. Effect of the Invention

[0018] According to one aspect of the present disclosure, there are provided a method for producing a polymerizable composition capable of producing a polymerizable composition capable of producing a resin having excellent heat resistance, the polymerizable composition capable of producing a resin having excellent heat resistance, and a resin, a molded body, an optical material, and a lens having excellent heat resistance. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] In the present disclosure, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In the present disclosure, the term "step" refers not only to an independent step, but also to a step that cannot be clearly distinguished from other steps, as long as the intended purpose of the step is achieved. In the present disclosure, when a plurality of substances corresponding to each component are present in the composition, the amount of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified. In the numerical ranges described in the present disclosure in stages, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. In addition, in the numerical ranges described in the present disclosure, the upper or lower limit value of the numerical range may be replaced with a value shown in the examples.

[0020] [Method for producing polymerizable composition] The method for producing the polymerizable composition of the present disclosure includes: A step of obtaining a composition (A) by mixing an episulfide compound represented by the formula (1) described below, a polythiol compound, and an amine compound; A step of mixing the composition (A) with an acidic compound to obtain a composition (B); A step of mixing the composition (B) with a polyiso(thio)cyanate compound to obtain a polymerizable composition; Includes.

[0021] The method for producing the polymerizable composition of the present disclosure may include other steps as necessary. In addition, in the step of obtaining the composition (A), other components may be further mixed in addition to the above-mentioned components (i.e., the episulfide compound represented by the formula (1) described below, the polythiol compound, and the amine compound). In the step of obtaining the composition (B), other raw materials may be further mixed in addition to the above-mentioned raw materials (that is, the composition (A) and the acidic compound). In the step of obtaining the polymerizable composition, other raw materials may be further mixed in addition to the raw materials described above (that is, the composition (B) and the polyiso(thio)cyanate compound).

[0022] According to the method for producing a polymerizable composition of the present disclosure, it is possible to produce a polymerizable composition that can be used to produce a resin having excellent heat resistance. In detail, according to the method for producing a polymerizable composition of the present disclosure, a polymerizable composition can be produced using at least an episulfide compound, a polyiso(thio)cyanate compound, and a polythiol compound, which is capable of producing a resin having excellent heat resistance. Although the details of why such an effect is achieved are not clear, it is speculated as follows. In the method for producing a polymerizable composition of the present disclosure, it is believed that in the step of obtaining composition (A), an amine compound functions as a catalyst, and a reaction between an episulfide compound represented by formula (1) described below and a polythiol compound proceeds. That is, it is believed that composition (A) contains a reaction product between an episulfide compound represented by formula (1) described below and a polythiol compound, and an amine compound. Next, in the step of mixing composition (A) with an acidic compound to obtain composition (B), it is considered that the catalytic action of the amine compound is inhibited by the acidic compound, and the reaction between the episulfide compound represented by formula (1) and the polythiol compound is suppressed. Next, the composition (B) and a polyiso(thio)cyanate compound are mixed to obtain a polymerizable composition. The polymerizable composition produced by the method for producing a polymerizable composition of the present disclosure is considered to have a different state of existence of each component (e.g., the composition of a reaction product by reaction of two or more components) compared with a polymerizable composition produced by a method other than the method for producing a polymerizable composition of the present disclosure using the same components (raw materials) (e.g., the polymerizable composition of Comparative Example 1 described below). It is believed that the method for producing a polymerizable composition according to the present disclosure can provide a polymerizable composition that can be used to produce a resin having excellent heat resistance.

[0023] Hereinafter, each step of the method for producing the polymerizable composition of the present disclosure will be described.

[0024] <Step of Obtaining Composition (A)> The method for producing a polymerizable composition of the present disclosure includes a step of mixing an episulfide compound represented by the following formula (1), a polythiol compound, and an amine compound to obtain composition (A). As described above, the composition (A) may contain the reaction product of the episulfide compound and the polythiol compound, and an amine compound. Furthermore, the composition (A) may or may not contain each of the episulfide compound and the polythiol compound.

[0025] In the step of obtaining composition (A), when the episulfide compound, the polythiol compound, and the amine compound are mixed in a container, the order in which the episulfide compound, the polythiol compound, and the amine compound are added to the container is not particularly limited. The mixing time is preferably 0.5 to 10 hours, more preferably 1 to 5 hours, and even more preferably 2 to 4 hours. The temperature of the mixture or composition (A) during mixing is preferably 10°C to 50°C, preferably 20°C to 40°C, and preferably 25°C to 35°C.

[0026] (Episulfide compound represented by formula (1)) In the step of obtaining the composition (A), an episulfide compound represented by the following formula (1) is used. The episulfide compound represented by formula (1) used in the step of obtaining composition (A) may be one type or two or more types.

[0027] [ka]

[0028] In formula (1), Y represents a substituted or unsubstituted linear alkylene group having 1 to 4 carbon atoms, a substituted or unsubstituted branched alkylene group having 2 to 4 carbon atoms, a substituted or unsubstituted cyclic cycloalkanediyl group having 3 to 6 carbon atoms, a substituted or unsubstituted alkylene group having 4 to 8 carbon atoms containing an alicyclic skeleton containing one or more sulfur atoms, a substituted or unsubstituted alkylenearylenealkylene group having 8 to 16 carbon atoms, a substituted or unsubstituted arylene group, or a substituted or unsubstituted aralkylene group, m represents an integer of 0 to 2, and n represents an integer of 0 to 3.

[0029] Examples of the substituted or unsubstituted linear alkylene group having 1 to 4 carbon atoms and the substituted or unsubstituted branched alkylene group having 2 to 4 carbon atoms represented by Y include unsubstituted alkylene groups such as a methylene group, an ethylene group, a 1,2-propylene group, a 1,3-propylene group, a 1,2-butylene group, a 1,3-butylene group, and a 1,4-butylene group, and groups in which the above-mentioned unsubstituted alkylene groups are substituted with a substituent such as an alkyl group, a hydroxyl group, a mercapto group, a carbonyl group, or a thiocarbonyl group. Examples of the substituted or unsubstituted cyclic cycloalkanediyl group having 3 to 6 carbon atoms represented by Y include unsubstituted cyclic alkylene groups such as a cyclopropylene group, a 1,2-cyclobutylene group, a 1,3-cyclobutylene group, a 1,2-cyclopentylene group, a 1,3-cyclopentylene group, a 1,2-cyclohexylene group, a 1,3-cyclohexylene group, and a 1,4-cyclohexylene group, and groups in which the unsubstituted cyclic alkylene groups are substituted with a substituent such as an alkyl group, a hydroxyl group, a mercapto group, a carbonyl group, or a thiocarbonyl group.

[0030] Examples of the substituted or unsubstituted alkylene group having 4 to 8 carbon atoms and containing an alicyclic skeleton containing one or more sulfur atoms, represented by Y, include divalent organic groups represented by the following formulas and groups in which the divalent organic groups are substituted with substituents such as alkyl groups and hydroxyl groups. In the following formula, * represents a bonding position, and x and y each independently represent an integer of 0 or 1.

[0031] [ka]

[0032] Examples of the substituted or unsubstituted alkylenearylenealkylene group having 8 to 16 carbon atoms represented by Y include a xylylene group and a group in which a xylylene group is substituted with a substituent such as an alkyl group, a hydroxyl group, a mercapto group, a carbonyl group or a thiocarbonyl group.

[0033] The substituted or unsubstituted arylene group represented by Y includes unsubstituted arylene groups such as a phenylene group and a naphthylene group, and groups in which the unsubstituted arylene groups are substituted with a substituent such as an alkyl group, a hydroxyl group, a mercapto group, a carbonyl group, a thiocarbonyl group, etc. Examples include:

[0034] Examples of the substituted or unsubstituted aralkylene group represented by Y include unsubstituted aralkylene groups such as a benzylene group, a phenethylene group, and a xylylene group, and groups in which the unsubstituted aralkylene groups are substituted with a substituent such as an alkyl group, a hydroxyl group, a mercapto group, a carbonyl group, or a thiocarbonyl group.

[0035] In the formula (1), m represents an integer of 0 to 2. m is preferably 0 or 1, and more preferably 0.

[0036] In the formula (1), n ​​represents an integer of 0 to 3. n is preferably 0, 1 or 3.

[0037] For the episulfide compound represented by formula (1), the description in paragraphs 0025 to 0038 of JP-A-2005-272778 can be appropriately referred to.

[0038] The episulfide compound represented by formula (1) is preferably Bis(2,3-epithiopropyl) sulfide, Bis(2,3-epithiopropylthio)methane, Bis(2,3-epithiopropylthio)ethane, 1,8-bis(2,3-epithiopropylthio)-3,6-dithiaoctane, and bis(2,3-epithiopropyl) disulfide (hereinafter also referred to as "episulfide compound (E1)"), More preferably, it contains at least one of bis(2,3-epithiopropyl)sulfide and bis(2,3-epithiopropyl)disulfide (hereinafter also referred to as "episulfide compound (E2)").

[0039] The proportion of the episulfide compound (E1) in the total amount of the episulfide compound represented by the formula (1) is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, and further preferably 80% by mass to 100% by mass. In the polymerizable composition, the preferred range of the proportion of the episulfide compound (E2) in the total amount of the episulfide compounds represented by the formula (1) is also similar to the preferred range of the proportion of the episulfide compound (E1) in the total amount of the episulfide compounds represented by the formula (1).

[0040] The proportion of the episulfide compound represented by Formula (1) in the total amount of raw materials used in the production method for the polymerizable composition of the present disclosure is preferably 30 mass% or more, and more preferably 40 mass% or more, from the viewpoint of obtaining a resin with a better refractive index. The proportion of the episulfide compound represented by Formula (1) in the total amount of raw materials used in the production method for a polymerizable composition of the present disclosure is, from the viewpoint of further improving the strength and hue of the obtained resin, preferably 85 mass% or less, more preferably 80 mass% or less, and even more preferably 70 mass% or less. A preferred range of the proportion of the episulfide compound represented by formula (1) in the total amount of raw materials used in the method for producing a polymerizable composition of the present disclosure is, for example, from 30% by mass to 85% by mass.

[0041] (Polythiol Compound) In the step of obtaining the composition (A), a polythiol compound is used. The polythiol compound used in the step of obtaining the composition (A) may be of one type or of two or more types.

[0042] In the present disclosure, a polythiol compound refers to a compound containing two or more mercapto groups (i.e., thiol groups) in one molecule.

[0043] For the polythiol compound, for example, the description in paragraphs 0039 to 0048 of JP-A-2005-272778 can be appropriately referred to.

[0044] The polythiol compounds are 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,5-bis(mercaptomethyl)-1,4-dithiane, bis(mercaptoethyl) sulfide, 1,1,3, It is preferable that the polythiol compound S1 contains at least one selected from the group consisting of 3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, and tris(mercaptomethylthio)methane (hereinafter also referred to as "polythiol compound S1").

[0045] The proportion of polythiol compound S1 in the total amount of polythiol compounds used (i.e., when polythiol compound S1 is composed of two or more compounds, the proportion of the total content of these two or more compounds) is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, and even more preferably 80% by mass to 100% by mass.

[0046] The proportion of the polythiol compound in the total amount of raw materials used in the method for producing a polymerizable composition of the present disclosure is preferably 5 mass% or more, more preferably 10 mass% or more, and even more preferably 15 mass% or more, from the viewpoint of further improving the hue and strength of the obtained resin. The proportion of the polythiol compound in the total amount of raw materials used in the method for producing a polymerizable composition of the present disclosure is preferably 60 mass% or less, more preferably 50 mass% or less, and even more preferably 40 mass% or less, from the viewpoint of obtaining a resin with a better refractive index and heat resistance. A preferred range for the proportion of the polythiol compound in the total amount of raw materials used in the method for producing a polymerizable composition of the present disclosure is, for example, from 5% by mass to 60% by mass.

[0047] (Amine compounds) In the step of obtaining the composition (A), an amine compound is used. As described above, the amine compound can function as a polymerization catalyst. The amine compound used in the step of obtaining the composition (A) may be one type or two or more types.

[0048] The amine compound preferably contains at least one of a compound represented by the following formula (3) and a compound represented by the following formula (4).

[0049] (Compound represented by formula (3))

[0050] [ka]

[0051] In formula (3), m R 1 each independently represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a halogen atom; Q represents a carbon atom, a nitrogen atom, or an oxygen atom; and m represents an integer of 0 to 5.

[0052] In the formula (3), m is preferably an integer of 0 to 3, and more preferably an integer of 1 to 3.

[0053] In formula (3), R 1Examples of the linear alkyl group having 1 to 20 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a pentyl group, a hexyl group, a heptyl group, an n-octyl group, a nonyl group, a decyl group, and a dodecyl group. In formula (3), R 1 Examples of the branched alkyl group having 3 to 20 carbon atoms represented by the formula (I) include an isopropyl group, an isobutyl group, a t-butyl group, an isopentyl group, an isooctyl group, a 2-ethylhexyl group, a 2-propylpentyl group, and an isodecyl group. In formula (3), R 1 Examples of the cycloalkyl group having 3 to 20 carbon atoms represented by the following formula include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

[0054] In formula (3), R 1 is preferably a linear alkyl group having 1 to 20 carbon atoms or a halogen atom, and more preferably a linear alkyl group having 1 to 3 carbon atoms or a chlorine atom.

[0055] The compound represented by formula (3) is preferably at least one selected from the group consisting of 2-methylpyrazine, pyridine, α-picoline, β-picoline, γ-picoline, 2,6-lutidine, 3,5-lutidine, 2,4,6-trimethylpyridine, 3-chloropyridine, 2-ethylpyridine, and 3-ethylpyridine.

[0056] (Compound represented by formula (4))

[0057] [ka]

[0058] In formula (4), R 2 , R 3 , and R 4 R each independently represents a linear alkyl group having 3 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an allyl group. 2 and R 3may be bonded to each other to form a ring.

[0059] In formula (4), R 2 , R 3 , and R 4 are each independently preferably a straight-chain alkyl group having 3 to 20 carbon atoms, more preferably a straight-chain alkyl group having 3 to 10 carbon atoms, and particularly preferably a straight-chain alkyl group having 5 to 10 carbon atoms.

[0060] R 2 , R 3 , or R 4 Examples of the linear alkyl group having 3 to 20 carbon atoms represented by the formula (I) include an n-propyl group, an n-butyl group, a pentyl group, a hexyl group, a heptyl group, an n-octyl group, a nonyl group, a decyl group, and a dodecyl group.

[0061] R 2 and R 3 may be bonded to each other to form a ring. That is, the compound represented by formula (4) is 2 and R 3 may be a cyclic amine compound having a structure in which the groups are bonded to each other to form a ring. Examples of the cyclic amine compound include 1-propylpiperidine, 1-butylpiperidine, 1-cyclohexylpiperidine, 1-butylpyrrolidine, and 1-cyclohexylpyrrolidine.

[0062] The compound represented by formula (4) is preferably at least one selected from the group consisting of triallylamine and trioctylamine.

[0063] The amount of the amine compound used (for example, the total amount of the compound represented by formula (3) and the compound represented by formula (4)) is preferably 0.01 to 1 mass%, more preferably 0.01 to 0.5 mass%, and even more preferably 0.01 to 0.5 mass%, based on the total amount of the episulfide compound represented by formula (1), the polyiso(thio)cyanate compound, and the polythiol compound used.

[0064] The total amount of the compound represented by formula (2) and the tertiary amine compound used in the polymerizable composition (for example, the total amount of the compounds represented by formulas (2) to (4) used) is preferably 0.01 to 1 mass%, more preferably 0.01 to 0.5 mass%, and even more preferably 0.01 to 0.5 mass%, based on the total amount of the episulfide compound represented by formula (1), the polyiso(thio)cyanate compound, and the polythiol compound used.

[0065] In the method for producing a polymerizable composition of the present disclosure, a compound other than the compounds represented by the above formulas (2) to (4) may be used as a polymerization catalyst. The polymerization catalyst can be selected from, for example, the polymerization catalysts described in paragraphs 0029 to 0033 of JP-A No. 2002-194083.

[0066] (Other ingredients) In the step of obtaining the composition (A), in addition to the above-mentioned raw materials (i.e., the episulfide compound represented by the formula (1) described later, the polythiol compound, and the amine compound), other raw materials may be further mixed.

[0067] <Step of Obtaining Composition (B)> The method for producing a polymerizable composition of the present disclosure includes a step of mixing the above-described composition (A) with an acidic compound to obtain composition (B). As described above, it is believed that in this step, the catalytic action of the amine compound in composition (A) is alleviated by the acidic compound, and the reaction between the episulfide compound represented by formula (1) and the polythiol compound is suppressed.

[0068] The time from the end of mixing to obtain composition (A) to the start of mixing the aforementioned composition (A) with an acidic compound to obtain composition (B) is preferably 3 hours or less, more preferably 2 hours or less, and even more preferably 1 hour or less. There is no particular restriction on the lower limit of this time, and the lower limit may be substantially 0 hours, or may exceed 0 hours.

[0069] In the step of obtaining composition (B), when composition (A) and an acidic compound are mixed in a container, the order in which composition (A) and the acidic compound are added to the container is not particularly limited. The mixing time is preferably 0.2 to 5 hours, more preferably 0.5 to 3 hours, and even more preferably 0.5 to 2 hours. The temperature of the mixture or composition (B) during mixing is preferably 10°C to 50°C, preferably 20°C to 40°C, and preferably 25°C to 35°C.

[0070] (acidic compound) In the step of obtaining the composition (B), an acidic compound is used. The acidic compound used in the step of obtaining the composition (B) may be one type or two or more types.

[0071] -Compound (b)- The acidic compound preferably contains at least one compound (b) selected from the group consisting of acids (b1) having a pKa of less than 2.0 and anhydrides (b2) of acids having a pKa of less than 2.0.

[0072] The acid (b1) is an acid having a pKa of less than 2.0. Examples of the acid (b1) include hydrochloric acid (pKa: -3.7), sulfuric acid (pKa: -3.0), nitric acid (pKa: -1.4), and sulfonic acids having a pKa of less than 2.0. Examples of sulfonic acids having a pKa of less than 2.0 include 10-camphorsulfonic acid (pKa: 1.2), methanesulfonic acid (pKa: -2.6), paratoluenesulfonic acid (pKa: -2.8), vinylsulfonic acid (pKa: -2.7), and benzenesulfonic acid (pKa: 0.7). The acid (b1) preferably comprises a sulfonic acid having a pKa of less than 2.0. The acid (b1) may form a hydrate.

[0073] The anhydride (b2) is an anhydride of an acid having a pKa of less than 2.0 (that is, an anhydride having a structure formed by dehydration condensation of an acid having a pKa of less than 2.0). Specific examples of the acid having a pKa of less than 2.0 for forming the anhydride (b2) are the same as the specific examples of the acid (b1) described above. The anhydride (b2) preferably comprises an anhydride of a sulfonic acid having a pKa of less than 2.0.

[0074] A preferred embodiment of compound (b) is one in which acid (b1) comprises a sulfonic acid having a pKa of less than 2.0, and anhydride (b2) comprises an anhydride of a sulfonic acid having a pKa of less than 2.0. In this embodiment, the proportion of the total amount of sulfonic acid having a pKa of less than 2.0 and sulfonic anhydride having a pKa of less than 2.0 in compound (b) is preferably 50% by mass to 100% by mass, more preferably 50% by mass to 80% by mass, and even more preferably 80% by mass to 100% by mass.

[0075] A more preferred embodiment of compound (b) is The acid (b1) comprises at least one selected from the group consisting of 10-camphorsulfonic acid, methanesulfonic acid, and paratoluenesulfonic acid; and The anhydride (b2) includes at least one selected from the group consisting of 10-camphorsulfonic anhydride, methanesulfonic anhydride, and paratoluenesulfonic anhydride. This is an embodiment. In this embodiment, the proportion of the total amount of 10-camphorsulfonic acid, methanesulfonic acid, paratoluenesulfonic acid, 10-camphorsulfonic anhydride, methanesulfonic anhydride, and paratoluenesulfonic anhydride in compound (b) is preferably 50% by mass to 100% by mass, more preferably 50% by mass to 80% by mass, and even more preferably 80% by mass to 100% by mass. Here, each of 10-camphorsulfonic acid and 10-camphorsulfonic anhydride may be a racemate or only one of the enantiomers.

[0076] A further preferred embodiment of the compound (b) is one in which the acid (b1) comprises 10-camphorsulfonic acid and the anhydride (b2) comprises 10-camphorsulfonic anhydride. In this embodiment, the total amount of 10-camphorsulfonic acid and 10-camphorsulfonic anhydride in compound (b) is preferably 50% by mass to 100% by mass, more preferably 50% by mass to 80% by mass, and even more preferably 80% by mass to 100% by mass.

[0077] The amount of compound (b) used is preferably 0.0001 mass% to 1.000 mass%, more preferably 0.0005 mass% to 0.100 mass%, and even more preferably 0.001 mass% to 0.050 mass%, based on the total amount of the episulfide compound represented by formula (1), the polyiso(thio)cyanate compound, and the polythiol compound used.

[0078] -Lewis acid compounds- The acidic compound also preferably includes a Lewis acid compound. The step of obtaining the composition (B) is preferably a step of mixing the above-mentioned composition (A), the compound (b) as an acidic compound, and a Lewis acid compound as an acidic compound.

[0079] When the acidic compound contains a Lewis acid compound, the Lewis acid compound contained may be of only one type, or of two or more types.

[0080] The Lewis acid compound is not particularly limited, but examples thereof include organotin compounds, zinc chloride, zinc acetylacetonate, aluminum chloride, aluminum fluoride, triphenylaluminum, titanium tetrachloride, calcium acetate, and the like. For the Lewis acid compound, the descriptions in known documents such as JP-A-2000-256435 (particularly, paragraphs 0059 to 0060), JP-A-2005-272778 (particularly, paragraph 0058), and JP-A-2001-131257 (particularly, paragraph 0027) may be referred to as appropriate.

[0081] The organotin compound is not particularly limited, but examples thereof include: Dialkyltin halides such as dibutyltin dichloride and dimethyltin dichloride; dialkyltin dicarboxylates such as dimethyltin diacetate, dibutyltin dioctanoate and dibutyltin dilaurate; Tin tetrachloride; Dibutyltin oxide; etc.

[0082] The dialkyltin halides may include monoalkyltin halides and trialkyltin halides. The dialkyltin dicarboxylates may include monoalkyltin tricarboxylates and trialkyltin carboxylates.

[0083] The Lewis acid compound preferably contains a compound represented by the following formula (5), which is a specific organotin compound.

[0084] [ka]

[0085] In formula (5), R 4 represents an alkyl group having 1 to 4 carbon atoms, and X represents a fluorine atom, a chlorine atom, a bromine atom, or -OC(=O)-R 5 R 5 represents an alkyl group having 1 to 11 carbon atoms, and c represents an integer of 1 to 3.

[0086] The compound represented by formula (5) is preferably at least one selected from the group consisting of dimethyltin dichloride, dibutyltin dichloride, and dibutyltin dilaurate.

[0087] The amount of the Lewis acid compound (for example, an organotin compound such as a compound represented by formula (5)) used is preferably 100 ppm by mass to 500 ppm by mass, and more preferably 200 ppm by mass to 400 ppm by mass, based on the total amount of raw materials used in the method for producing the polymerizable composition.

[0088] (Other ingredients) In the step of obtaining the composition (B), other raw materials may be further mixed in addition to the above-mentioned raw materials (that is, the composition (A) and the acidic compound).

[0089] <Step of Obtaining Polymerizable Composition> The method for producing a polymerizable composition of the present disclosure includes a step of mixing the above-mentioned composition (B) with a polyiso(thio)cyanate compound to obtain a polymerizable composition.

[0090] The time from the end of mixing to obtain composition (B) to the start of mixing composition (B) with a polyiso(thio)cyanate compound to obtain a polymerizable composition is preferably 20 hours or less, more preferably 15 hours or less, and even more preferably 10 hours or less. There is no particular restriction on the lower limit of this time, and the lower limit may be substantially 0 hours, or may exceed 0 hours.

[0091] In the step of obtaining a polymerizable composition, when the composition (B) and the polyiso(thio)cyanate compound are mixed in a container, the order in which the composition (B) and the polyiso(thio)cyanate compound are added to the container is not particularly limited. The mixing time is preferably 0.01 to 6 hours, more preferably 0.01 to 4 hours, and even more preferably 0.01 to 2 hours. The temperature of the mixture or composition (B) during mixing is preferably 10°C to 50°C, preferably 20°C to 40°C, and preferably 25°C to 35°C.

[0092] (Polyiso(thio)cyanate compounds) In the step of obtaining the polymerizable composition, a polyiso(thio)cyanate compound is used. The polyiso(thio)cyanate compound used in the step of obtaining the polymerizable composition may be one type or two or more types.

[0093] In the present disclosure, a polyiso(thio)cyanate compound means a compound containing two or more iso(thio)cyanate groups in one molecule. In this disclosure, an "iso(thio)cyanate group" means an isocyanate group or an isothiocyanate group.

[0094] For the polyiso(thio)cyanate compound, for example, the description in paragraphs 0049 to 0051 of JP-A-2005-272778 can be appropriately referred to.

[0095] It is particularly preferable that the polyiso(thio)cyanate compound contains at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate (hereinafter, "polyisocyanate compound N1").

[0096] The proportion of the polyisocyanate compound N1 in the total amount of the polyiso(thio)cyanate compounds is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, and even more preferably 80% by mass to 100% by mass.

[0097] The amount of the polyiso(thio)cyanate compound used in the total amount of raw materials used in the production method for the polymerizable composition of the present disclosure is preferably 2 mass% or more, more preferably 5 mass% or more, and even more preferably 10 mass% or more. The amount of the polyiso(thio)cyanate compound used in the total amount of raw materials used in the production method of the polymerizable composition of the present disclosure is preferably 50 mass% or less, more preferably 40 mass% or less, and even more preferably 30 mass% or less. A preferred range of the amount of the polyiso(thio)cyanate compound used in the total amount of raw materials used in the method for producing a polymerizable composition of the present disclosure is, for example, from 2% by mass to 50% by mass.

[0098] ((M S -M N ) / M E ratio) In the method for producing a polymerizable composition according to the present disclosure, The total number of moles of mercapto groups contained in the entire amount of polythiol compound is M S year, The total number of moles of iso(thio)cyanate groups in the total amount of polyiso(thio)cyanate compounds is M N year, The total number of moles of episulfide groups contained in the total amount of the episulfide compound represented by formula (1) is M E In this case, (M S -M N ) / M E The ratio is preferably greater than 0 and less than or equal to 0.20, and more preferably greater than 0 and less than or equal to 0.15.

[0099] (M S -M N ) / M E When the ratio exceeds 0, the strength of the resulting resin is further improved. (M S -M N ) / M E When the ratio is 0.20 or less, the heat resistance of the resulting resin is further improved.

[0100] (Other ingredients) In the step of obtaining the polymerizable composition, other raw materials may be further mixed in addition to the raw materials described above (that is, the composition (B) and the polyiso(thio)cyanate compound). Other raw materials that can be used in the step of obtaining the polymerizable composition include, for example, epoxy compounds, silicone compounds, ultraviolet absorbers, and the like.

[0101] <Epoxy compounds> A method for making a polymerizable composition of the present disclosure may include mixing an epoxy compound. There is no particular limitation on the timing of mixing the epoxy compounds, and for example, it may be during or between each of the above-mentioned steps. The epoxy compounds may be used alone or in combination of two or more.

[0102] In the present disclosure, an epoxy compound means a compound containing one or more epoxy groups in one molecule.

[0103] The epoxy compound in the present disclosure preferably contains the following epoxy compound (X). Here, the epoxy compound (X) is an epoxy compound that contains one or more epoxy groups in one molecule and does not contain an episulfide group. The proportion of the epoxy compound (X) in the total amount of epoxy compounds in the present disclosure is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, and even more preferably 80% by mass to 100% by mass.

[0104] The epoxy compound in the present disclosure also preferably includes the following epoxy compound (X1). Here, the epoxy compound (X1) is a compound containing two or more epoxy groups (preferably 2 to 4, more preferably 2 or 3, and even more preferably 2) in one molecule. In the present disclosure, the proportion of the epoxy compound (X1) in the total amount of epoxy compounds is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, and even more preferably 80% by mass to 100% by mass.

[0105] The epoxy compound (X1) may correspond to the epoxy compound (X). In this case, the epoxy compound (X1) is an epoxy compound containing two or more epoxy groups in one molecule and containing no episulfide group.

[0106] Specific examples of the epoxy compound (e.g., epoxy compound (X) and / or epoxy compound (X1); the same applies below) in the present disclosure include: Phenolic epoxy compounds produced by reacting aromatic hydroxy compounds such as phenol, cresol, xylenol, naphthol, hydroquinone, catechol, resorcin, bisphenol A, bisphenol F, bis(hydroxyphenyl)sulfone, bis(hydroxyphenyl)ether, bis(hydroxyphenyl)sulfide, and halogenated bisphenol A novolac resins with epihalohydrin; Alcohol-based epoxy compounds produced by reacting an alcohol compound such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, isopropanol, isobutanol, tert-butanol, neopentyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, bisphenol A·ethylene oxide adduct, or bisphenol A·propylene oxide adduct with epihalohydrin;

[0107] glycidyl ester-based epoxy compounds produced by reacting a carboxylic acid compound such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, isobutyric acid, isovaleric acid, benzoic acid, benzoylacetic acid, naphthalene carboxylic acid, adipic acid, sebacic acid, dodecane dicarboxylic acid, dimer acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, HET acid, nadic acid, maleic acid, succinic acid, fumaric acid, trimellitic acid, benzenetetracarboxylic acid, benzophenonetetracarboxylic acid, naphthalene dicarboxylic acid, or diphenyl dicarboxylic acid with epihalohydrin;

[0108] Methylamine, ethylamine, propylamine, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, bis-(3-aminopropyl)ether, 1,2-bis-(3-aminopropoxy)ethane, 1,3-bis-(3-aminopropoxy)-2,2'-dimethylpropane, 1,2-, 1,3- or 1,4-bisaminocyclohexane, 1,3- or 1,4- Primary amines such as bisaminomethylcyclohexane, 1,3- or 1,4-bisaminoethylcyclohexane, 1,3- or 1,4-bisaminopropylcyclohexane, hydrogenated 4,4'-diaminodiphenylmethane, isophoronediamine, 1,4-bisaminopropylpiperazine, m- or p-phenylenediamine, 2,4- or 2,6-tolylenediamine, m- or p-xylylenediamine, 1,5- or 2,6-naphthalenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, and 2,2-bis(4,4'-diaminodiphenyl)propane;

[0109] Dimethylamine, diethylamine, dibutylamine, N-ethylmethylamine, N-methylpropylamine, N-methylbutylamine, N-methylpentylamine, N-methylhexylamine, N-ethylpropylamine, N-ethyl-n-butylamine, N-ethylpentylamine, N-ethylhexylamine, 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 amine-based epoxy compounds produced by reacting secondary amines such as 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-1,6-diaminohexane, piperazine, 2-methylpiperazine, 2,5- or 2,6-dimethylpiperazine, homopiperazine, di-(4-piperidyl)-methane, 1,2-di-(4-piperidyl)-ethane, 1,3-di-(4-piperidyl)-propane, and 1,4-di-(4-piperidyl)-butane with epihalohydrin;

[0110] Alicyclic epoxy compounds such as cyclohexene oxide, 3,4-epoxycyclohexyl-3,4-epoxycyclohexane carboxylate, vinylcyclohexene dioxide, 1,2:8,9-diepoxylimonene, 2-(3,4-epoxycyclohexyl)-5,5-spiro-3,4-epoxycyclohexane-meta-dioxane, and bis(3,4-epoxycyclohexyl)adipate; Epoxy compounds produced by epoxidation of unsaturated compounds such as styrene oxide, dicyclopentadiene diepoxide, epoxidized soybean oil, epoxidized polybutadiene, vinylcyclohexene epoxide, etc.; urethane-based epoxy compounds produced from polyhydric alcohols or phenolic compounds, diisocyanates and glycidol; etc.

[0111] From the viewpoint of further improving the heat resistance of the obtained resin, the epoxy compound in the present disclosure preferably contains an aromatic ring, more preferably contains an aromatic ring and a glycidyloxy group, and even more preferably contains an aromatic ring and two or more (preferably 2 to 4, more preferably 2 or 3, and even more preferably 2) glycidyloxy groups. From the viewpoint of further improving the heat resistance of the obtained resin, the molecular weight of the epoxy compound in the present disclosure is preferably 1,000 or less, more preferably 500 or less, and even more preferably 400 or less. The lower limit of the molecular weight of the epoxy compound in the present disclosure is preferably 100, and more preferably 200.

[0112] The epoxy compound in the present disclosure preferably contains at least one selected from the group consisting of bisphenol A diglycidyl ether (hereinafter also referred to as "BGPP") (molecular weight 340) and resorcinol diglycidyl ether (molecular weight 222). In this case, the total proportion of bisphenol A diglycidyl ether and resorcinol diglycidyl ether in the total amount of the epoxy compounds in the present disclosure is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, and even more preferably 80% by mass to 100% by mass.

[0113] When an epoxy compound is used, the content of the epoxy compound in the total amount of raw materials used in the production method of the polymerizable composition of the present disclosure is preferably 0.05 mass% or more, more preferably 0.10 mass% or more, and even more preferably 0.20 mass% or more. When an epoxy compound is used, the content of the epoxy compound in the total amount of raw materials used in the production method of the polymerizable composition of the present disclosure is preferably 20 mass% or less, more preferably 10 mass% or less, and even more preferably 3 mass% or less. When an epoxy compound is used, the content of the epoxy compound in the total amount of raw materials used in the production method of the polymerizable composition of the present disclosure is preferably in the range of, for example, 0.05% by mass to 20% by mass.

[0114] <Silicone compounds> A method of making a polymerizable composition of the present disclosure may include mixing a silicone compound. There is no particular limitation on the timing of mixing the silicone compounds, and for example, it may be during or between each of the above-mentioned steps. The silicone compound may be used alone or in combination of two or more kinds.

[0115] There is no particular limitation on the weight average molecular weight of the silicone compound. The weight average molecular weight of the silicone compound is preferably 200 to 100,000, and more preferably 1,000 to 80,000.

[0116] When a silicone compound is used, the content of the silicone compound in the total amount of raw materials used in the production method of the polymerizable composition is preferably 0.0001 mass% to 1 mass%, more preferably 0.0005 mass% to 0.100 mass%, and even more preferably 0.001 mass% to 0.020 mass%, relative to the total amount of the episulfide compound represented by Formula (1), the polyiso(thio)cyanate compound, and the polythiol compound.

[0117] The silicone compound preferably contains at least one of dimethylpolysiloxane and a polyether-modified silicone compound. From the viewpoint of further improving the releasability of the resulting resin, the silicone compound more preferably contains a polyether-modified silicone compound.

[0118] When the silicone compound contains a polyether-modified silicone compound, the proportion of the polyether-modified silicone compound in the total amount of the silicone compounds is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, and even more preferably 80% by mass to 100% by mass.

[0119] The silicone compound that can be used for producing the polymerizable composition of the present disclosure preferably contains at least one selected from the group consisting of a polyether-modified silicone compound represented by the following formula (S1) (hereinafter also referred to as compound (S1)) and a polyether-modified silicone compound represented by the following formula (S2) (hereinafter also referred to as compound (S2)), and more preferably contains compound (S1) (i.e., contains compound (S1), or contains compound (S1) and compound (S2)).

[0120] When the silicone compound contains at least one of the compound (S1) and the compound (S2), the total proportion of the compound (S1) and the compound (S2) in the total amount of the silicone compound is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, and even more preferably 80% by mass to 100% by mass. When the silicone compound contains the compound (S1), or contains the compound (S1) and the compound (S2), the proportion of the compound (S1) in the total amount of the silicone compound is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, and even more preferably 80% by mass to 100% by mass.

[0121] [ka]

[0122] In formula (S1), m and n each independently represent an integer of 1 or more. a and b each independently represent an integer of 0 or more (except when both a and b are 0). R 1represents a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkenyl group having 2 to 10 carbon atoms, an acryloyl group, a methacryloyl group, or a hydrogen atom. In formula (S2), p represents an integer of 1 or more, and c, d, e, and f each independently represent an integer of 0 or more (except when c, d, e, and f are all 0). 2 and R 3 each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkenyl group having 2 to 10 carbon atoms, an acryloyl group, a methacryloyl group, or a hydrogen atom.

[0123] In formula (S1) and formula (S2), (OC 3 H 6 The unit represented by is an oxypropylene unit (i.e., O-CH(CH 3 )-CH 2 (unit) and Si-C 3 H 6 -(OC 2 H 4 ) at the site represented by C 3 H 6 is a trimethylene group (also known as the 1,3-propanediyl group; i.e., -CH 2 CH 2 CH 2 -).

[0124] In formula (S1), m is preferably an integer of 1 to 500, more preferably an integer of 10 to 300. n is preferably an integer of 1 to 100, more preferably an integer of 1 to 50. a is preferably an integer of 0 to 1000, more preferably an integer of 1 to 500. b is preferably an integer of 0 to 1000, more preferably an integer of 0 to 500.

[0125] The weight average molecular weight of the polyether-modified silicone compound represented by formula (S1) is preferably 200 to 100,000, and more preferably 1,000 to 80,000.

[0126] In the formula (S2), p is preferably an integer of 1-500, and more preferably an integer of 10-300. Each of c and f is preferably an integer of 0 to 1000, more preferably an integer of 1 to 500. Each of d and e is preferably an integer of 0 to 1000, more preferably an integer of 0 to 500.

[0127] The weight average molecular weight of the polyether-modified silicone compound represented by formula (S2) is preferably 200 to 100,000, and more preferably 1,000 to 80,000.

[0128] In formula (S1), the molar fraction of the silicone unit [that is, (m+n) / (m+n+a+b)] is preferably 0.08 to 0.60. When the molar fraction of the silicone unit is 0.08 or more, releasability can be sufficiently maintained. When the molar fraction of the silicone unit is 0.60 or less, cloudiness, opacity, and the like in the cured product can be suppressed, and transparency can be maintained. From the same viewpoint as above, in formula (S1), the molar fraction of the silicone unit is more preferably 0.10 to 0.50. In the formula (S1), the molar fraction of the polyether unit [that is, (a+b) / (a+b+m+n)] is preferably 0.40 to 0.92. When the molar fraction of the polyether unit is 0.40 or more, cloudiness, opacity, and the like in the cured product can be suppressed, and transparency can be maintained. When the molar fraction of the polyether unit is 0.92 or less, releasability can be sufficiently maintained. From the same viewpoint as above, in the formula (S1), the molar fraction of the polyether unit is more preferably 0.50 to 0.90.

[0129] In formula (S2), the molar fraction of the silicone unit [that is, p / (p+c+d+e+f)] is preferably 0.08 to 0.60. In the formula (S2), when the molar fraction of the silicone unit is 0.08 or more, releasability can be sufficiently maintained. In formula (S2), when the molar fraction of the silicone unit is 0.60 or less, cloudiness, opacity, and the like in the cured product can be suppressed, and transparency can be maintained. From the same viewpoint as above, in formula (S2), the molar fraction of the silicone unit is more preferably 0.10 to 0.50. In the formula (S2), the molar fraction of the polyether unit [that is, (c+d+e+f) / (c+d+e+f+p)] is preferably 0.40 to 0.92. In formula (S2), when the molar fraction of the polyether unit is 0.40 or more, cloudiness, opacity, and the like in the cured product can be suppressed, and transparency can be maintained. In the formula (S2), when the molar fraction of the polyether unit is 0.92 or less, releasability can be sufficiently maintained. From the same viewpoint as above, in the formula (S2), the molar fraction of the polyether unit is more preferably 0.50 to 0.90.

[0130] The method for measuring the molar fractions of the silicone unit and the polyether unit is the same as that described above.

[0131] In formula (S1) and formula (S2), the molar fraction of the total silicone units [that is, (m+n+p) / (m+n+p+a+b+c+d+e+f)] is preferably 0.08 to 0.60. In formula (S1) and formula (S2), when the total molar fraction of silicone units is 0.08 or more, releasability can be sufficiently maintained. In formula (S1) and formula (S2), when the total molar fraction of silicone units is 0.60 or less, cloudiness, opacity, etc. in the cured product can be suppressed and transparency can be maintained. From the same viewpoint as above, in formula (S1) and formula (S2), the total molar fraction of silicone units is more preferably 0.10 to 0.50. In the formulas (S1) and (S2), the molar fraction of the total polyether units [that is, (a+b+c+d+e+f) / (a+b+c+d+e+f+m+n+p)] is preferably 0.40 to 0.92. In formula (S1) and formula (S2), when the molar fraction of the total polyether units is 0.40 or more, cloudiness, opacity, and the like in the cured product can be suppressed, and transparency can be maintained. In the formula (S1) and the formula (S2), when the molar fraction of the total polyether units is 0.92 or less, releasability can be sufficiently maintained. From the same viewpoint as above, in the formulae (S1) and (S2), the molar fraction of the total polyether units is more preferably 0.50 to 0.90.

[0132] When the polyether-modified silicone compound contains both the compound (S1) and the compound (S2), From the viewpoint of the effects of the present disclosure, the ratio of compound (S1) to compound (S2) (S1:S2) may be 5:95 to 95:5, preferably 10:90 to 90:10, and more preferably 20:80 to 80:20. The polyether-modified silicone compound may contain at least one type each of the compound (S1) and the compound (S2), or may contain two or more types.

[0133] In addition, a, b, c, d, e, f, m, n, and p, as well as the molar fraction of the silicone unit and the molar fraction of the polyether unit, are 1 This value is determined by the integral value of the signal in H-NMR.

[0134] <Compound represented by formula (2)> The method for producing the polymerizable composition of the present disclosure may include mixing a compound represented by the following formula (2): There is no particular limitation on the timing of mixing the compound represented by the following formula (2), and it may be during or between each of the above-mentioned steps. The compound represented by the following formula (2) may be used alone or in combination of two or more kinds.

[0135] (R 1 ) 4 Y + X - …(2)

[0136] In formula (2), the four R 1 each independently represents a linear hydrocarbon group having 1 to 10 carbon atoms or a branched hydrocarbon group having 3 to 10 carbon atoms, X represents a halogen atom, and Y represents a nitrogen atom or a phosphorus atom.

[0137] In formula (2), R 1 The "straight-chain hydrocarbon group having 1 to 10 carbon atoms or branched hydrocarbon group having 3 to 10 carbon atoms" represented by the above formula is preferably a straight-chain alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms. In order to improve the appearance of the resulting resin, R 1 The "straight-chain hydrocarbon group having 1 to 10 carbon atoms or branched hydrocarbon group having 3 to 10 carbon atoms" represented by the above formula is more preferably a straight-chain alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms, and even more preferably a straight-chain alkyl group having 1 to 6 carbon atoms.

[0138] In formula (2), the halogen atom represented by X is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom, a chlorine atom, or a bromine atom, and even more preferably a chlorine atom or a bromine atom. From the viewpoint of improving the appearance of the resulting resin, the halogen atom represented by X is particularly preferably a bromine atom.

[0139] In formula (2), Y may be a nitrogen atom or a phosphorus atom, but is preferably a nitrogen atom.

[0140] The compound represented by formula (2) is preferably tetra-n-butylammonium bromide (TBAB) or tri-n-octylmethylammonium chloride (TOMAC). Tetra-n-butylammonium bromide (TBAB) is a compound represented by the formula (2) 1 is a n-butyl group, Y is a nitrogen atom, and X is a bromine atom.

[0141] When the compound represented by formula (2) is used, the content of the compound represented by formula (2) in the total amount of raw materials used in the production method of the polymerizable composition is preferably 0.01 to 1 mass%, more preferably 0.01 to 0.5 mass%, and still more preferably 0.01 to 0.3 mass%, relative to the total amount of the episulfide compound represented by formula (1), the polyiso(thio)cyanate compound, and the polythiol compound.

[0142] <Other ingredients> The method for producing the polymerizable composition of the present disclosure may include mixing other components in addition to the components described above. There is no particular limitation on the timing of mixing the other components, and for example, they may be mixed during or between each of the above-mentioned steps. Other components include bluing agents, resins (for example, acrylic resins, olefin resins, etc.), crosslinking agents, light stabilizers, ultraviolet absorbers, antioxidants, coloring inhibitors, dyes, fillers, internal mold release agents, and the like. As the other components, known components can be used. For other components, reference may be made, for example, to JP-A-2002-194083.

[0143] [Polymerizable composition] The polymerizable composition of the present disclosure is a polymerizable composition produced by the above-mentioned method for producing a polymerizable composition of the present disclosure. For this reason, a resin produced from the polymerizable composition of the present disclosure has excellent heat resistance.

[0144] As described above, the polymerizable composition of the present disclosure is considered to have a different state of existence of each component (e.g., the composition of a reaction product resulting from the reaction of two or more components) compared with a polymerizable composition produced by a method other than the production method of the polymerizable composition of the present disclosure using the same components (raw materials) (e.g., the polymerizable composition of Comparative Example 1 described later). The reason is that the heat resistance of the resins produced from these two polymerizable compositions is different.

[0145] [Resin, Molded Body] The resin of the present disclosure is a cured product of the polymerizable composition of the present disclosure described above. The molded article of the present disclosure contains the resin of the present disclosure.

[0146] That is, the resin of the present disclosure can be produced by curing the above-described polymerizable composition of the present disclosure, specifically, by polymerizing and curing the monomers in the polymerizable composition of the present disclosure.

[0147] Examples of methods for polymerizing the monomer in the polymerizable composition of the present disclosure include cast polymerization. Cast polymerization can provide a molded article of the present disclosure that includes the resin of the present disclosure (i.e., the cured product of the polymerizable composition of the present disclosure).

[0148] In the cast polymerization, first, the polymerizable composition according to one example of the present disclosure is injected between a pair of molds held by a gasket, a tape, etc. At this time, degassing treatment, filtration treatment, etc. may be performed as necessary. Next, the monomer in the composition injected between the molds is polymerized to cure the composition between the molds, and the cured product is then removed from the molds to obtain the cured product. Polymerization of the monomer may be carried out by heating the polymerizable composition of the present disclosure, for example, using a heating device equipped with a mechanism for heating an object to be heated in an oven, water, etc.

[0149] The polymerization conditions (e.g., polymerization temperature, polymerization time, etc.) for polymerizing the monomers in the polymerizable composition of the present disclosure are appropriately set in consideration of the composition of the composition, the type and amount of the monomers used in the composition, the type and amount of the polymerization catalyst used in the composition, the shape of the mold, etc. The polymerization temperature may be, for example, from -50°C to 150°C, or from 10°C to 150°C. The polymerization time may be, for example, 1 hour to 200 hours, or 1 hour to 80 hours.

[0150] The resin or resin-containing molded article of the present disclosure may be obtained by subjecting the monomer to polymerization and then to a treatment such as annealing. The annealing temperature may be 50°C to 150°C, 90°C to 140°C, 100°C to 130°C, or the like.

[0151] [Optical materials] The optical material of the present disclosure contains the resin of the present disclosure described above. The optical material of the present disclosure can be produced, for example, by the cast polymerization described above. The optical material of the present disclosure has a refractive index (n e The refractive index (n e ) can be determined, for example, by using a Pulfrich refractometer KPR-30 manufactured by Shimadzu Corporation to measure the refractive index at wavelengths of 546.1 nm (mercury e-line), 480.0 nm (Cd F'-line), and 643.9 nm (Cd C'-line), and based on the measurement results.

[0152] The optical material of the present disclosure may be made of the resin of the present disclosure, or may contain the resin of the present disclosure and other elements. The other elements include other members, a coating layer provided on the resin of the present disclosure, and the like.

[0153] Optical materials of the present disclosure include lenses (e.g., eyeglass lenses, camera lenses, polarized lenses, etc.), light-emitting diodes (LEDs), and the like.

[0154] 〔lens〕 The lens of the present disclosure is an example of the optical material of the present disclosure, and contains the resin of the present disclosure described above. Lenses of the present disclosure may be manufactured, for example, by cast polymerization as described above.

[0155] The lens of the present disclosure may be made of the resin of the present disclosure, or may contain the resin of the present disclosure and other elements. The other elements include other members, a coating layer provided on the resin of the present disclosure, and the like.

[0156] Lenses of the present disclosure include eyeglass lenses, camera lenses, polarized lenses, and the like. Below, a spectacle lens will be described as an example of the lens of the present disclosure. The eyeglass lenses include a resin of the present disclosure molded into a desired lens shape. The eyeglass lens preferably further comprises a coating layer provided on one or both sides of the resin.

[0157] Specific examples of the coating layer include a primer layer, a hard coat layer, an anti-reflection layer, an anti-fogging coating layer, an anti-fouling layer, a water-repellent layer, etc. Each of these coating layers can be used alone or in combination of a plurality of coating layers. When coating layers are applied to both sides of the cured product, the same coating layer may be applied to each side, or different coating layers may be applied to each side.

[0158] The components of the coating layer can be appropriately selected depending on the purpose. Examples of components of the coating layer include resins (e.g., urethane resins, epoxy resins, polyester resins, melamine resins, polyvinyl acetal resins, etc.), infrared absorbers, light stabilizers, antioxidants, photochromic compounds, dyes, pigments, and antistatic agents.

[0159] For details about eyeglass lenses and coating layers, the descriptions in publicly known documents such as JP 2002-194083 A and WO 2017 / 047745 can be referenced as appropriate. EXAMPLES

[0160] Examples of the present disclosure will be described below, but the present disclosure is not limited to the following examples. In addition, unless otherwise specified, "parts" are based on mass.

[0161] Example 1 <Production of polymerizable composition> (Step of Obtaining Composition (A)) 42.6 parts by mass of bis(2,3-epithiopropyl)disulfide (hereinafter also referred to as "EPS-1") as an episulfide compound represented by formula (1); 32.0 parts by mass of a polythiol compound (hereinafter also referred to as "PT-1") mainly composed of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane; 0.0224 parts by mass of 3,5-lutidine as a polymerization catalyst, which is a compound represented by formula (3); The mixture was mixed at 30° C. for 3 hours to obtain composition (A). It was confirmed by liquid chromatography that PT-1 had disappeared from composition (A) due to the reaction between PT-1 and EPS-1.

[0162] (Step of Obtaining Composition (B)) Within 1 hour after obtaining the composition (A) as described above, The composition (A) obtained above, 0.72 parts by mass of xylylene diisocyanate (hereinafter also referred to as "PI-2") as a polyiso(thio)cyanate compound in which 0.0298 parts by mass of (±)-10-camphorsulfonic acid (hereinafter also referred to as "CSA") as compound (b) and 0.0187 parts by mass of di-n-butyltin dichloride (hereinafter also referred to as "DBC") as a Lewis acid compound (specifically, a compound represented by formula (5)) are dissolved; The mixture was mixed at 30° C. for 3 hours to obtain composition (B).

[0163] (Step of Obtaining Polymerizable Composition) Within 10 hours after obtaining the composition (B) as described above, The composition (B) obtained above, 24.68 parts by mass of xylylene diisocyanate (PI-2) as a polyiso(thio)cyanate compound; 1.5 parts by mass of bisphenol A diglycidyl ether (hereinafter also referred to as "BGPP") as an epoxy compound (X); 0.005 parts by mass of "KF-615A" (product name; KF-615A by Shin-Etsu Silicone Co., Ltd.) as a silicone compound, 1,000 parts by mass of "TinuvinPS" (manufactured by BASF Japan) as an ultraviolet absorber, The mixture was mixed at 30° C. for 0.1 hour to obtain a polymerizable composition. Here, "KF-615A" corresponds to compound (S1), and is a compound having a molar fraction of silicone units [i.e., (m+n) / (m+n+a+b)] of 0.16 and a molar fraction of polyether units [i.e., (a+b) / (a+b+m+n)] of 0.84.

[0164] The types and amounts of each of the above components are summarized in Table 1. In Table 1, the episulfide compound, the polythiol compound, the amine compound, the Lewis acid compound, the epoxy compound, the polyiso(thio)cyanate compound, and the silicone compound are abbreviated as episulfide, polythiol, amine, Lewis acid, epoxy, polyiso(thio)cyanate, and silicone, respectively.

[0165] Table 1 also shows the (M S -M N ) / M E The ratio is also shown. Here, (M S -M N ) / M E The ratio is the total mole number of mercapto groups contained in the total amount of polythiol compound, M S The total number of moles of iso(thio)cyanate groups in the total amount of polyiso(thio)cyanate compounds is M N The total number of moles of episulfide groups contained in the total amount of the episulfide compound represented by formula (1) is M E In this case, (M S -M N ) / M E Ratio (simply put, excess thiol groups (M S -M N ) to the episulfide group (M E ) is the ratio of

[0166] <Preparation of resin molded body> The polymerizable composition obtained above was thoroughly degassed under reduced pressure of 600 Pa until no foaming was observed. The degassed polymerizable composition was filtered through a 1 μm PTFE (polytetrafluoroethylene) filter, and then injected between a pair of glass molds fixed with tape. Next, the pair of glass molds into which the polymerizable composition was injected were placed in an oven, and the temperature inside the oven was gradually increased from 20° C. to 120° C. over 23 hours. Through the above process, the monomers (i.e., the episulfide compound represented by formula (1), the polyiso(thio)cyanate compound, the polythiol compound, etc.) in the degassed polymerizable composition were polymerized, and a resin molded body (i.e., a resin molded body that is a cured product of the polymerizable composition) was formed between the pair of glass molds. The oven was then cooled, and the pair of glass molds were then removed from the oven, and the resin molded body was then removed from the pair of glass molds to obtain a resin molded body. The resin molded body was then annealed at 120° C. for 1 hour to obtain a lens containing the resin.

[0167] <Evaluation> The above polymerizable compositions and resin molded articles were evaluated as follows. The results are shown in Table 1.

[0168] Optical properties (refractive index (n e ) and Abbe number (ν e )) A test piece having a length of 10 mm, a width of 10 mm and a thickness of 2.5 mm was obtained by the same procedure as in the above <Preparation of resin molded body>, except that the shape and size of the pair of glass molds were appropriately selected. The refractive index of the obtained test piece was measured at wavelengths of 546.1 nm (mercury e-line), 480.0 nm (Cd F'-line), and 643.9 nm (Cd C'-line) using a Pulfrich refractometer KPR-3000 manufactured by Shimadzu Corporation, and the refractive index (n e ) and Abbe number (ν e ) were calculated respectively.

[0169] ·Heat resistance A test piece having a length of 10 mm, a width of 10 mm and a thickness of 2.5 mm was obtained by the same procedure as in the above <Preparation of resin molded body>, except that the shape and size of the pair of glass molds were appropriately selected. The glass transition temperature Tg of the above test piece was measured by the TMA penetration method (load of 50 g, pin tip of 0.5 mmφ, heating rate of 10° C. / min) using a thermomechanical analyzer TMA-60 manufactured by Shimadzu Corporation, and was used as an index of heat resistance. The higher the glass transition temperature Tg, the better the heat resistance.

[0170] Example 2 The same procedure as in Example 1 was carried out except that the type and amount of the Lewis acid compound were changed as shown in Table 1. In Table 1, DMC means di-n-methyltin dichloride. The results are shown in Table 1.

[0171] Example 3 The same procedure as in Example 1 was carried out, except that no Lewis acid compound was used. The results are shown in Table 1. In Table 1, "-" means that the corresponding component was not used.

[0172] Comparative Example 1 The polymerizable composition was produced in the same manner as in Example 1, except that the order of adding the components was changed. The results are shown in Table 1.

[0173] In the production of the polymerizable composition of Comparative Example 1, the step of obtaining composition (A) and the step of obtaining composition (B) were not included, and instead, polyiso(thio)cyanate and an acidic compound were mixed, and then episulfide, polythiol, and amine were added thereto to produce the polymerizable composition. Details are given below.

[0174] 25.4 parts by mass of xylylene diisocyanate ("PI-2") as a polyiso(thio)cyanate compound; 0.010 parts by weight of (±)-10-camphorsulfonic acid ("CSA") as compound (b); 1.5 parts by weight of bisphenol A diglycidyl ether ("BGPP") as an epoxy compound (X); 0.02 parts by mass of di-n-butyltin dichloride ("DBC") as a Lewis acid compound (specifically, a compound represented by formula (5)); 0.005 parts by mass of "KF-615A" (product name; KF-615A by Shin-Etsu Silicone Co., Ltd.) as a silicone compound, 1,000 parts by mass of "TinuvinPS" (manufactured by BASF Japan) as an ultraviolet absorber, The mixture was mixed and dissolved at 20°C. The resulting solution was After charging 42.6 parts by mass of bis(2,3-epithiopropyl)disulfide ("EPS-1") as the episulfide compound represented by formula (1), A mixture of 32.0 parts by mass of a polythiol compound ("PT-1") mainly composed of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 0.024 parts by mass of 3,5-lutidine as a polymerization catalyst, which is a compound represented by formula (3), was charged and mixed at 5 to 10°C to obtain a polymerizable composition.

[0175] Comparative Example 2 The same procedure as in Comparative Example 1 was carried out, except that the mass ratios of CSA, DBC, and 3,5-lutidine were kept the same, but the amounts of each were changed to 1.25 times.

[0176] Comparative Example 3 The same procedure as in Comparative Example 2 was carried out except that the type and amount of the Lewis acid compound was changed to DMC (di-n-methyltin dichloride) as shown in Table 1. The results are shown in Table 1.

[0177] Comparative Example 4 The same procedure as in Comparative Example 2 was carried out, except that no Lewis acid compound was used. The results are shown in Table 1.

[0178] [Table 1]

[0179] As shown in Table 1, in Examples 1 to 3, the polymerizable compositions were produced by a method for producing a polymerizable composition including a step of mixing an episulfide, a polythiol, and an amine to obtain a composition (A), a step of mixing the composition (A) with an acidic compound to obtain a composition (B), and a step of mixing the composition (B) with a polyiso(thio)cyanate compound to obtain a polymerizable composition. On the other hand, in Comparative Examples 1 to 4, the step of obtaining composition (A) and the step of obtaining composition (B) were not included, and a polymerizable composition was produced by mixing a polyiso(thio)cyanate and an acidic compound, and then mixing the mixture with an episulfide, a polythiol, and an amine. The resins produced using the polymerizable compositions obtained in Examples 1 to 3 were superior in heat resistance to the resins produced using the polymerizable compositions obtained in Comparative Examples 1 to 4. The resins produced using the polymerizable compositions obtained in Examples 1 to 3 maintained the same level of optical properties as the resins produced using the polymerizable compositions obtained in Comparative Examples 1 to 4.

Claims

1. A step of mixing an episulfide compound represented by the following formula (1), a polythiol compound, and an amine compound to obtain a composition (A); A step of mixing the composition (A) with an acidic compound to obtain a composition (B); A step of mixing the composition (B) with a polyiso(thio)cyanate compound to obtain a polymerizable composition; A method for producing a polymerizable composition comprising the steps of: 【Chemistry 1】 [In formula (1), Y represents a substituted or unsubstituted linear alkylene group having 1 to 4 carbon atoms, a substituted or unsubstituted branched alkylene group having 2 to 4 carbon atoms, a substituted or unsubstituted cyclic cycloalkanediyl group having 3 to 6 carbon atoms, a substituted or unsubstituted alkylene group having 4 to 8 carbon atoms containing an alicyclic skeleton containing one or more sulfur atoms, a substituted or unsubstituted alkylenearylenealkylene group having 8 to 16 carbon atoms, a substituted or unsubstituted arylene group, or a substituted or unsubstituted aralkylene group, m represents an integer of 0 to 2, and n represents an integer of 0 to 3.]

2. 2. The method for producing a polymerizable composition according to claim 1, wherein the acidic compound comprises at least one compound (b) selected from the group consisting of an acid (b1) having a pKa of less than 2.0 and an anhydride (b2) of an acid having a pKa of less than 2.

0.

3. 3. The method for producing a polymerizable composition according to claim 2, wherein the acid (b1) comprises a sulfonic acid having a pKa of less than 2.0, and the anhydride (b2) comprises an anhydride of a sulfonic acid having a pKa of less than 2.

0.

4. the acid (b1) comprises at least one selected from the group consisting of 10-camphorsulfonic acid, methanesulfonic acid, and p-toluenesulfonic acid; The method for producing a polymerizable composition according to claim 2, wherein the anhydride (b2) includes at least one selected from the group consisting of 10-camphorsulfonic anhydride, methanesulfonic anhydride, and p-toluenesulfonic anhydride.

5. The method for producing the polymerizable composition according to claim 1 , further comprising mixing an epoxy compound.

6. The method for producing a polymerizable composition according to claim 5 , wherein the epoxy compound comprises an epoxy compound (X) which contains one or more epoxy groups in one molecule and does not contain an episulfide group.

7. The method for producing a polymerizable composition according to claim 5 , wherein the epoxy compound comprises an epoxy compound (X1) containing two or more epoxy groups in one molecule.

8. The total number of moles of mercapto groups contained in the entire amount of the polythiol compound is M Ｓ year, The total number of moles of iso(thio)cyanate groups in the total amount of the polyiso(thio)cyanate compound is M Ｎ year, The total number of moles of episulfide groups contained in the total amount of the episulfide compound represented by the formula (1) is M Ｅ In this case, (M Ｓ -M Ｎ ) / M Ｅ The method for producing a polymerizable composition according to claim 1 , wherein the ratio is greater than 0 and not greater than 0.

20.

9. The polythiol compound is 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,5-bis(mercaptomethyl)-1,4-dithiane, bis(mercaptoethyl)sulfide, 1 2,3-Dithiane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithietane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, and tris(mercaptomethylthio)methane.

10. The method for producing a polymerizable composition according to claim 1, wherein the polyiso(thio)cyanate compound comprises at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate.

11. The method for producing a polymerizable composition according to claim 1 , wherein the amine compound includes at least one of a compound represented by the following formula (3) and a compound represented by the following formula (4): 【Chemistry 2】 [In formula (3), m R １ each independently represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a halogen atom; Q represents a carbon atom, a nitrogen atom, or an oxygen atom; and m represents an integer of 0 to 5. In formula (4), R ２ , R ３ , and R ４ R each independently represents a linear alkyl group having 3 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an allyl group. ２ and R ３ may be bonded to each other to form a ring.

12. the compound represented by formula (3) is at least one selected from the group consisting of 2-methylpyrazine, pyridine, α-picoline, β-picoline, γ-picoline, 2,6-lutidine, 3,5-lutidine, 2,4,6-trimethylpyridine, 3-chloropyridine, 2-ethylpyridine, and 3-ethylpyridine; The compound represented by formula (4) is at least one selected from the group consisting of triallylamine and trioctylamine. A method for producing the polymerizable composition according to claim 11.

13. The method for producing a polymerizable composition according to claim 1 , wherein the acidic compound comprises a Lewis acid compound.

14. The method for producing a polymerizable composition according to claim 13 , wherein the Lewis acid compound includes a compound represented by the following formula (5): 【Chemistry 3】 [In formula (5), R ４ represents an alkyl group having 1 to 4 carbon atoms, and X represents a fluorine atom, a chlorine atom, a bromine atom, or -O-C(=O)-R ５ represents R ５ represents an alkyl group having 1 to 11 carbon atoms, and c represents an integer of 1 to 3.

15. The method for producing a polymerizable composition according to claim 14, wherein the compound represented by formula (5) is at least one selected from the group consisting of dimethyltin dichloride, dibutyltin dichloride, and dibutyltin dilaurate.

16. The method for producing the polymerizable composition according to claim 1 , further comprising mixing a silicone compound.

17. A polymerizable composition obtained by the method for producing a polymerizable composition according to any one of claims 1 to 16.

18. A resin which is a cured product of the polymerizable composition according to claim 17.

19. A molded article comprising the resin according to claim 18.

20. An optical material comprising the resin according to claim 18.

21. A lens comprising the resin of claim 18.

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