Polymerizable composition, resin, molded article, optical material, and lens

Abstract

Provided is a polymerizable composition containing an episulfide compound represented by formula (1), a polyiso(thio)cyanate compound, a polythiol compound, an epoxy compound, and a salt of a compound having an amidine skeleton. In formula (1), Y represents an alkylene group, a cycloalkanediyl group, an alkylene group having an alicyclic skeleton including one or more sulfur atoms, an alkylene-arylene-alkylene group, an arylene group, or an aralkylene group, m represents an integer of 0-2, and n represents an integer of 0-3.

Description

Polymerizable composition, resin, molded article, optical material, and lens

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

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

[0003] In recent years, various studies have been conducted on resin compositions containing episulfide compounds as raw materials for plastic lenses. For example, Patent Document 1 aims to develop a method for adjusting the polymerization rate and improving the heat resistance of resin optical materials having a sufficiently high refractive index and a good Abbe number, and discloses a resin composition comprising a compound having a specific thiirane ring (i.e., a specific episulfide compound), a compound having one or more epoxy groups per molecule, and a polymerization catalyst. Furthermore, Patent Document 2 discloses a polymerizable composition capable of producing a resin having a high refractive index and excellent strength, the polymerizable composition containing a specific episulfide compound, a polyiso(thio)cyanate compound, a polythiol compound, and a specific epoxy compound.

[0004] Patent Document 1: JP 2005-298742 A Patent Document 2: WO 2022 / 168892

[0005] Paragraphs 0085 to 0093 of Patent Document 2 disclose that the pot life of a polymerizable composition can be improved by adding a Lewis acid compound such as an organotin compound to the polymerizable composition. However, there are cases where it is desired to further improve the pot life of a polymerizable composition containing an episulfide compound, a polyiso(thio)cyanate compound, a polythiol compound, and an epoxy compound. An object of one aspect of the present disclosure is to provide a polymerizable composition containing an episulfide compound, a polyiso(thio)cyanate compound, a polythiol compound, and an epoxy compound, which has an excellent pot life, as well as a resin, a molded article, an optical material, and a lens that can be produced using this polymerizable composition.

[0006] Means for solving the above problems include the following aspects: <1> A polymerizable composition containing: an episulfide compound represented by the following formula (1), a polyiso(thio)cyanate compound, a polythiol compound, an epoxy compound, and a salt of a compound having an amidine skeleton:

[0007]

[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 and 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 polymerizable composition according to <1>, wherein the salt is a carboxylic acid salt or a phenol compound salt. <3> The polymerizable composition according to <1> or <2>, wherein the compound having an amidine skeleton is at least one selected from the group consisting of 1,8-diazabicyclo[5.4.0]-7-undecene and 1,5-diazabicyclo[4.3.0]-5-nonene. <4> The polymerizable composition according to any one of <1> to <3>, wherein the salt of the compound having an amidine skeleton is at least one selected from the group consisting of a phenol salt of 1,8-diazabicyclo[5.4.0]-7-undecene, 2-ethylhexanoate of 1,8-diazabicyclo[5.4.0]-7-undecene, and 2-ethylhexanoate of 1,5-diazabicyclo[4.3.0]-5-nonene. <5> The polymerizable composition according to any one of <1> to <3>, wherein the epoxy compound includes an epoxy compound (X) containing one or more epoxy groups in one molecule and not containing an episulfide group. <6> The polymerizable composition according to any one of <1> to <5>, wherein the epoxy compound includes an epoxy compound (X1) containing two or more epoxy groups in one molecule. <7> The polymerizable composition according to any one of <1> to <5>, wherein the total number of moles of mercapto groups contained in the total amount of the polythiol compound is M Ｓ The total number of moles of iso(thio)cyanate groups in the total amount of the polyiso(thio)cyanate compound is M Ｎ 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<8> The polymerizable composition according to any one of <1> to <6>, wherein the ratio is greater than 0 and not greater than 0.20. <8> The polythiol compound is selected from the group consisting of 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, The polymerizable composition according to any one of <1> to <7>, which contains at least one selected from the group consisting of 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. <9> The polymerizable composition according to any one of <1> to <7>, wherein 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. <10> A resin that is a cured product of the polymerizable composition according to any one of <1> to <9>. <11> A molded product comprising the resin according to <10>. <12> An optical material comprising the resin according to <10>. <13> A lens containing the resin according to <10>.

[0010] According to one aspect of the present disclosure, there are provided a polymerizable composition containing an episulfide compound, a polyiso(thio)cyanate compound, a polythiol compound, and an epoxy compound, the polymerizable composition having an excellent pot life, as well as a resin, a molded article, an optical material, and a lens that can be produced using the polymerizable composition.

[0011] In the present disclosure, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. In the present disclosure, when a composition contains multiple substances corresponding to each component, the amount of each component refers to the total amount of the multiple substances present in the composition, unless otherwise specified. In the numerical ranges described in stages in the present disclosure, the upper or lower limit described in one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in the numerical ranges described in the present disclosure, the upper or lower limit of that numerical range may be replaced with a value shown in the examples.

[0012] [Polymerizable Composition] The polymerizable composition of the present disclosure contains an episulfide compound represented by the below-described formula (1), a polyiso(thio)cyanate compound, a polythiol compound, an epoxy compound, and a salt of a compound having an amidine skeleton.

[0013] The polymerizable composition of the present disclosure is a polymerizable composition containing an episulfide compound, a polyiso(thio)cyanate compound, a polythiol compound, and an epoxy compound, and has the effect of being excellent in pot life (i.e., long pot life). The reason for this effect is thought to be that the activity of the polymerization catalyst (specifically, a salt of a compound having an amidine skeleton) is suppressed in an unheated state during storage of the polymerizable composition, thereby suppressing an increase in viscosity of the polymerizable composition during storage.

[0014] Specifically, the salt of the compound having an amidine skeleton as a polymerization catalyst is thought to function as a thermal base generator. When the polymerizable composition of the present disclosure is cured by polymerizing the monomers (i.e., episulfide compounds, polyiso(thio)cyanate compounds, polythiol compounds, and epoxy compounds) in the polymerizable composition to obtain a resin, the salt of the compound having an amidine skeleton is thought to dissociate into a cation (base) derived from the compound having an amidine skeleton and a counter anion upon heating (e.g., heating at 70°C or higher). The cation (base) derived from the compound having an amidine skeleton, generated by the dissociation, is thought to have activity as a polymerization catalyst.

[0015] Furthermore, a resin obtained from the polymerizable composition of the present disclosure has a high refractive index and excellent strength. In the polymerizable composition of the present disclosure, the episulfide compound represented by formula (1) is a component that contributes to increasing the refractive index of the resin, and the polyiso(thio)cyanate compound, polythiol compound, and epoxy compound (X) are components that ensure the strength of the resin (see Patent Document 2 mentioned above).

[0016] Hereinafter, each component that can be contained in the polymerizable composition of the present disclosure will be described.

[0017] <Episulfide Compound Represented by Formula (1)> The polymerizable composition of the present disclosure contains at least one episulfide compound represented by the following formula (1):

[0018]

[0019] 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 and 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.

[0020] 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 above-mentioned 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.

[0021] 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 this divalent organic group is substituted with a substituent such as an alkyl group or a hydroxyl group. In the following formulas, * indicates a bonding position. x and y each independently represent an integer of 0 or 1.

[0022]

[0023] 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.

[0024] Examples of the substituted or unsubstituted arylene group represented by Y include 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, or a thiocarbonyl group.

[0025] 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.

[0026] In formula (1), m represents an integer of 0 to 2. m is preferably 0 or 1, and more preferably 0.

[0027] In formula (1), n ​​represents an integer of 0 to 3. n is preferably 0, 1 or 3.

[0028] For the episulfide compound represented by formula (1), reference can be made, for example, to the description in paragraphs 0025 to 0038 of JP-A No. 2005-272778, as appropriate.

[0029] The episulfide compound represented by formula (1) preferably contains at least one selected from the group consisting of 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)"), and more preferably contains at least one of bis(2,3-epithiopropyl)sulfide and bis(2,3-epithiopropyl)disulfide (hereinafter also referred to as "episulfide compound (E2)").

[0030] In the polymerizable composition, the proportion of the episulfide compound (E1) in the total amount of the episulfide compounds represented by formula (1) 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. 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 formula (1) is also the same as the preferred range of the proportion of the episulfide compound (E1) in the total amount of the episulfide compounds represented by formula (1).

[0031] The content of the episulfide compound represented by formula (1) relative to the total amount of the polymerizable composition of the present disclosure is preferably 30% by mass or more, and more preferably 40% by mass or more, from the viewpoint of obtaining a resin with a better refractive index. The content of the episulfide compound represented by formula (1) relative to the total amount of the polymerizable composition of the present disclosure is preferably 85% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less, from the viewpoint of obtaining a resin with a better strength and hue. A preferred range for the content of the episulfide compound represented by formula (1) relative to the total amount of the polymerizable composition of the present disclosure is, for example, 30% by mass to 85% by mass.

[0032] <Polyiso(thio)cyanate Compound> The polymerizable composition of the present disclosure contains at least one polyiso(thio)cyanate compound. In the present disclosure, a polyiso(thio)cyanate compound refers to a compound containing two or more iso(thio)cyanate groups in one molecule. In the present disclosure, an "iso(thio)cyanate group" refers to an isocyanate group or an isothiocyanate group.

[0033] For the polyiso(thio)cyanate compound, the description in paragraphs 0049 to 0051 of JP-A-2005-272778 can be appropriately referred to.

[0034] It is particularly preferable that the polyiso(thio)cyanate compound in the polymerizable composition of the present disclosure 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 also referred to as “polyisocyanate compound N1”).

[0035] In the polymerizable composition, the proportion of the polyisocyanate compound N1 in the total amount of 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.

[0036] The content of the polyiso(thio)cyanate compound relative to the total amount of the polymerizable composition of the present disclosure is preferably 2% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, from the viewpoint of further improving the Abbe number, hue, and strength of the resulting resin. The content of the polyiso(thio)cyanate compound relative to the total amount of the polymerizable composition of the present disclosure is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, from the viewpoint of achieving a superior refractive index of the resulting resin. A preferred range for the content of the polyiso(thio)cyanate compound relative to the total amount of the polymerizable composition of the present disclosure is, for example, 2% by mass to 50% by mass.

[0037] <Polythiol Compound> The polymerizable composition of the present disclosure contains at least one polythiol compound. In the present disclosure, a polythiol compound refers to a compound containing two or more mercapto groups (i.e., thiol groups) in one molecule. In the present disclosure, two or more polythiol compounds may be referred to as a "polythiol composition."

[0038] For the polythiol compound, reference can be made, for example, to the description in paragraphs 0039 to 0048 of JP-A No. 2005-272778.

[0039] The polythiol compound in the polymerizable composition of the present disclosure 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. , 1,1,3,3-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 (hereinafter also referred to as "polythiol compound S1").

[0040] In the polymerizable composition, the proportion of polythiol compound S1 in the total amount of polythiol compounds (i.e., when polythiol compound S1 consists 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.

[0041] The content of the polythiol compound relative to the total amount of the polymerizable composition of the present disclosure is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, from the viewpoint of further improving the hue and strength of the resulting resin. The content of the polythiol compound relative to the total amount of the polymerizable composition of the present disclosure is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less, from the viewpoint of achieving better refractive index and heat resistance of the resulting resin. A preferred range of the content of the polythiol compound relative to the total amount of the polymerizable composition of the present disclosure is, for example, a range of 5% by mass to 60% by mass.

[0042] The total content of the episulfide compound represented by Formula (1), the polyiso(thio)cyanate compound, and the polythiol compound relative to the total amount of the polymerizable composition of the present disclosure is preferably 80% by mass or more, and more preferably 90% by mass or more.

[0043] The polymerizable composition of the present disclosure contains at least one epoxy compound. The epoxy compound contained in the polymerizable composition of the present disclosure (hereinafter also referred to as the “epoxy compound in the present disclosure”) is not particularly limited as long as it is a compound containing one or more epoxy groups in one molecule.

[0044] 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 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.

[0045] The epoxy compound in the present disclosure also preferably contains 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. The proportion of the epoxy compound (X1) 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.

[0046] The epoxy compound (X1) may be one corresponding 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 not containing an episulfide group.

[0047] Specific examples of the epoxy compound (e.g., epoxy compound (X) and / or epoxy compound (X1); the same applies hereinafter) in the present disclosure include: phenolic epoxy compounds produced by reacting an aromatic hydroxy compound such as phenol, cresol, xylenol, naphthol, hydroquinone, catechol, resorcinol, bisphenol A, bisphenol F, bis(hydroxyphenyl)sulfone, bis(hydroxyphenyl)ether, bis(hydroxyphenyl)sulfide, or halogenated bisphenol A novolac resin with an 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;

[0048] Glycidyl ester 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, naphthalenecarboxylic acid, adipic acid, sebacic acid, dodecanedicarboxylic 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, naphthalenedicarboxylic acid, or diphenyldicarboxylic acid with an epihalohydrin;

[0049] 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;

[0050] 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 a secondary amine such as 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-1,6-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, or 1,4-di-(4-piperidyl)-butane with an epihalohydrin;

[0051] Alicyclic epoxy compounds such as cyclohexene oxide, 3,4-epoxycyclohexyl-3,4-epoxycyclohexanecarboxylate, 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, and vinylcyclohexene epoxide; urethane-based epoxy compounds produced from polyhydric alcohols or phenolic compounds, diisocyanates, and glycidol; and the like.

[0052] From the viewpoint of further improving the heat resistance of the resulting 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 resulting 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, more preferably 200.

[0053] 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 compound 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.

[0054] The content of the epoxy compound in the present disclosure relative to the total amount of the polymerizable composition of the present disclosure is preferably 0.05% by mass or more, more preferably 0.10% by mass or more, and even more preferably 0.20% by mass or more, from the viewpoint of further improving the hue of the resulting resin. The content of the epoxy compound in the present disclosure relative to the total amount of the polymerizable composition of the present disclosure is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 3% by mass or less, from the viewpoint of achieving superior strength of the resulting resin. A preferred range of the content of the epoxy compound in the present disclosure relative to the total amount of the polymerizable composition of the present disclosure is, for example, a range of 0.05% by mass to 20% by mass.

[0055] <(M Ｓ -M Ｎ ) / M Ｅ In the polymerizable composition of the present disclosure, the total number of moles of mercapto groups contained in the total amount of polythiol compounds is 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 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.

[0056] (M Ｓ -M Ｎ ) / M Ｅ When the ratio is greater than 0, the strength of the resulting resin is further improved. Ｓ -M Ｎ ) / M Ｅ When the ratio is 0.20 or less, the heat resistance of the resulting resin is further improved.

[0057] <Salt of Compound Having Amidine Skeleton> The polymerizable composition of the present disclosure contains at least one salt of a compound having an amidine skeleton. As described above, the salt of a compound having an amidine skeleton functions as a polymerization catalyst.

[0058] Examples of the salts (i.e., salts of compounds having an amidine skeleton) include carboxylates, phenolic compound salts, and sulfonic acid salts. Examples of the carboxylates include formates, acetates, propionates, butyrates, hexanoates (e.g., 2-ethylhexanoate), heptanoates, octanoates, lactates, malates, citrates, benzoates, phthalates, isophthalates, terephthalates, salicylates, gallates, mellitates, cinnamates, oxalates, malonates, succinates, glutarates, adipates, fumarates, and maleates. Examples of the carboxylates include 2-ethylhexanoates, formates, and o-phthalates, and more preferably 2-ethylhexanoates. Examples of the phenolic compound salts include phenol salts, cresol salts, picrates, naphthol salts, catechol salts, resorcinol salts, and hydroquinone salts. Sulfonates include, for example, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and camphorsulfonic acid.

[0059] The above salt (i.e., the salt of the compound having an amidine skeleton) is preferably a carboxylate or a phenol salt.

[0060] The compound having an amidine skeleton that forms the salt of the compound having an amidine skeleton may be one kind or two or more kinds. Examples of the compound having an amidine skeleton include 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene, and the like.

[0061] The compound having an amidine skeleton that forms a salt of the compound having an amidine skeleton is preferably at least one selected from the group consisting of 1,8-diazabicyclo[5.4.0]-7-undecene and 1,5-diazabicyclo[4.3.0]-5-nonene.

[0062] The salt of the compound having an amidine skeleton is preferably at least one selected from the group consisting of a phenol salt of 1,8-diazabicyclo[5.4.0]-7-undecene, a 2-ethylhexanoate of 1,8-diazabicyclo[5.4.0]-7-undecene, and a 2-ethylhexanoate of 1,5-diazabicyclo[4.3.0]-5-nonene. Specific examples of these salts include commercially available products. Examples of commercially available products include products manufactured by San-Apro Co., Ltd. 1,8-diazabicyclo[5.4.0]-7-undecene is also known as DBU (registered trademark), and 1,5-diazabicyclo[4.3.0]-5-nonene is also known as DBN. The structures of the above specific examples are as follows:

[0063]

[0064] In the polymerizable composition of the present disclosure, the content of the salt of the compound having an amidine skeleton is preferably 0.0100% by mass to 1.0000% by mass, more preferably 0.0100 to 0.5000% by mass, even more preferably 0.0100 to 0.3000% by mass, and still more preferably 0.0200 to 0.1000% by mass, relative to the total amount of the episulfide compound represented by Formula (1), the polyiso(thio)cyanate compound, and the polythiol compound.

[0065] <Ultraviolet Absorber> The polymerizable composition of the present disclosure preferably contains at least one ultraviolet absorber.

[0066] Examples of the ultraviolet absorber include benzophenone-based ultraviolet absorbers such as 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-acryloyloxybenzophenone, 2-hydroxy-4-acryloyloxy-5-tert-butylbenzophenone, and 2-hydroxy-4-acryloyloxy-2',4'-dichlorobenzophenone; 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4dimethylphenyl)-1,3,5-triazine, and 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]- triazine-based ultraviolet absorbers such as 2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, and 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine; Benzotriazole-based ultraviolet absorbers such as 2-(2H-benzotriazol-2-yl)-4-methylphenol, 2-(2H-benzotriazol-2-yl)-4-tert-octylphenol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol, 2-(5-chloro-2H-benzotriazol-2-yl)-4-methyl-6-tert-butylphenol, 2-(5-chloro-2H-benzotriazol-2-yl)-2,4-tert-butylphenol, and 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol]; and the like.The ultraviolet absorber is preferably 2-(2H-benzotriazol-2-yl)-4-tert-octylphenol or 2-(5-chloro-2H-benzotriazol-2-yl)-4-methyl-6-tert-butylphenol.

[0067] The content of the ultraviolet absorber in the polymerizable composition is preferably 0.100% by mass to 5.000% by mass, and more preferably 0.200% by mass to 3.000% by mass, based on the total amount of the episulfide compound represented by Formula (1), the polyiso(thio)cyanate compound, and the polythiol compound.

[0068] <Silicone Compound> The polymerizable composition of the present disclosure preferably contains at least one silicone compound from the viewpoint of further improving the appearance and releasability of the resin.

[0069] There are no particular restrictions on the weight-average molecular weight of the silicone compound, but the weight-average molecular weight of the silicone compound is preferably 200 to 100,000, and more preferably 1,000 to 80,000.

[0070] The content of the silicone compound in the polymerizable composition is preferably 0.0001% by mass to 1% by mass, more preferably 0.0005% by mass to 0.100% by mass, and even more preferably 0.001% by mass to 0.020% by mass, relative to the total amount of the episulfide compound represented by Formula (1), the polyiso(thio)cyanate compound, and the polythiol compound.

[0071] The silicone compound preferably contains at least one of dimethylpolysiloxane and a polyether-modified silicone compound from the viewpoint of further improving the appearance of the resin, and more preferably contains a polyether-modified silicone compound from the viewpoint of further improving the releasability of the resulting resin.

[0072] 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.

[0073] From the viewpoint of further improving the demolding releasability of the resulting resin, the silicone compound contained in 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)).

[0074] When the silicone compound contains at least one of compound (S1) and compound (S2), the total proportion of compound (S1) and 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 compound (S1) or compound (S1) and compound (S2), the total proportion of compound (S1) in 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.

[0075]

[0076] In formula (S1), m and n each independently represent an integer of 1 or greater, a and b each independently represent an integer of 0 or greater (excluding the case where both a and b are 0). 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 (excluding the case where c, d, e, and f are all 0). R 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.

[0077] In formula (S1) and formula (S2), (OC ３ H ６ ) is an oxypropylene unit (i.e., O—CH(CH ３ )-CH ２ unit), and Si—C ３ H ６ - (OC ２ H ４ ) C at the site represented by ３ H ６ is a trimethylene group (also known as a 1,3-propanediyl group; i.e., -CH ２ CH ２ CH ２ -).

[0078] 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.

[0079] 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.

[0080] In formula (S2), p is preferably an integer of 1 to 500, more preferably an integer of 10 to 300. c and f are preferably integers of 0 to 1000, more preferably an integer of 1 to 500. d and e are preferably integers of 0 to 1000, more preferably an integer of 0 to 500.

[0081] 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.

[0082] In formula (S1), the molar fraction of the silicone unit [i.e., (m + n) / (m + n + a + b)] is preferably 0.08 to 0.60. A molar fraction of the silicone unit of 0.08 or more can adequately maintain releasability. A molar fraction of the silicone unit of 0.60 or less can suppress cloudiness, opacity, etc. in the cured product, thereby maintaining transparency. From the same viewpoint as above, the molar fraction of the silicone unit in formula (S1) is more preferably 0.10 to 0.50. In formula (S1), the molar fraction of the polyether unit [i.e., (a + b) / (a + b + m + n)] is preferably 0.40 to 0.92. A molar fraction of the polyether unit of 0.40 or more can suppress cloudiness, opacity, etc. in the cured product, thereby maintaining transparency. A molar fraction of the polyether unit of 0.92 or less can adequately maintain releasability. From the same viewpoint as above, the molar fraction of the polyether unit in formula (S1) is more preferably 0.50 to 0.90.

[0083] In formula (S2), the molar fraction of the silicone unit [i.e., p / (p+c+d+e+f)] is preferably 0.08 to 0.60. When the molar fraction of the silicone unit in formula (S2) is 0.08 or more, releasability can be sufficiently maintained. When the molar fraction of the silicone unit in formula (S2) 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, the molar fraction of the silicone unit in formula (S2) is more preferably 0.10 to 0.50. In formula (S2), the molar fraction of the polyether unit [i.e., (c+d+e+f) / (c+d+e+f+p)] is preferably 0.40 to 0.92. When the molar fraction of the polyether unit in formula (S2) is 0.40 or more, cloudiness, opacity, etc. in the cured product can be suppressed, and transparency can be maintained. In 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, the molar fraction of the polyether unit in formula (S2) is more preferably 0.50 to 0.90.

[0084] The method for measuring the molar fractions of silicone units and polyether units is the same as the method described above.

[0085] In formulas (S1) and (S2), the molar fraction of the total silicone units [i.e., (m+n+p) / (m+n+p+a+b+c+d+e+f)] is preferably 0.08 to 0.60. When the molar fraction of the total silicone units in formulas (S1) and (S2) is 0.08 or more, releasability can be sufficiently maintained. When the molar fraction of the total silicone units in formulas (S1) and (S2) 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, the molar fraction of the total silicone units in formulas (S1) and (S2) is more preferably 0.10 to 0.50. In formulas (S1) and (S2), the molar fraction of the total polyether units [i.e., (a+b+c+d+e+f) / (a+b+c+d+e+f+m+n+p)] is preferably 0.40 to 0.92. When the molar fraction of the total polyether units in formulas (S1) and (S2) is 0.40 or more, cloudiness, opacity, etc. in the cured product can be suppressed, and transparency can be maintained. When the molar fraction of the total polyether units in formulas (S1) and (S2) is 0.92 or less, mold releasability can be sufficiently maintained. From the same viewpoint as above, the molar fraction of the total polyether units in formulas (S1) and (S2) is more preferably 0.50 to 0.90.

[0086] When the polyether-modified silicone compound contains both compound (S1) and compound (S2), 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, from the viewpoint of the effects of the present disclosure. The polyether-modified silicone compound may contain at least one type of compound (S1) and at least one type of compound (S2), or may contain two or more types.

[0087] The molar fractions of a, b, c, d, e, f, m, n, and p, as well as the molar fractions of the silicone unit and polyether unit, are as follows: １ It is a value determined by the integral value of the signal in H-NMR.

[0088] <Other Polymerization Catalysts> The polymerizable composition of the present disclosure may contain at least one other polymerization catalyst other than the above-mentioned "salt of a compound having an amidine skeleton."

[0089] (Compound Represented by Formula (2)) Other polymerization catalysts include compounds represented by the following formula (2).

[0090] (R １ ) ４ Y ＋ X － …(2)

[0091] In formula (2), 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.

[0092] 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 formula (I) is preferably a straight-chain alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms. From the viewpoint of improving 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 formula (I) 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.

[0093] 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.

[0094] In formula (2), Y may be a nitrogen atom or a phosphorus atom, but is preferably a nitrogen atom.

[0095] 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 formula (2) in which four R １ is an n-butyl group, Y is a nitrogen atom, and X is a bromine atom.

[0096] The content of the compound represented by formula (2) in the polymerizable composition of the present disclosure is preferably 0.01% by mass to 1% by mass, more preferably 0.01% by mass to 0.5% by mass, and still more preferably 0.01% by mass to 0.3% by mass, relative to the total amount of the episulfide compound represented by formula (1), the polyiso(thio)cyanate compound, and the polythiol compound.

[0097] <Nitrogen-Containing Compound (C)> Other examples of the polymerization catalyst include the nitrogen-containing compound (C), which is at least one of a nitrogen-containing aromatic heterocyclic compound and a tertiary amine compound.

[0098] The nitrogen-containing compound (C) may contain at least one of a compound represented by the following formula (3) and a compound represented by the following formula (4).

[0099] (Compound represented by formula (3))

[0100]

[0101] 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.

[0102] In formula (3), m is preferably an integer of 0 to 3, and more preferably an integer of 1 to 3.

[0103] In formula (3), R １Examples of the linear alkyl group having 1 to 20 carbon atoms represented by the formula (3) 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. １ Examples of the branched alkyl group having 3 to 20 carbon atoms represented by the formula (3) 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. １ Examples of the cycloalkyl group having 3 to 20 carbon atoms represented by the formula (I) include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

[0104] 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.

[0105] 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.

[0106] (Compound represented by formula (4))

[0107]

[0108] 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.

[0109] In formula (4), R ２ , R ３ , and R ４are each independently preferably a linear alkyl group having 3 to 20 carbon atoms, more preferably a linear alkyl group having 3 to 10 carbon atoms, and particularly preferably a linear alkyl group having 5 to 10 carbon atoms.

[0110] 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.

[0111] R ２ and R ３ may be bonded to each other to form a ring. That is, the compound represented by formula (4) ２ and R ３ may be a cyclic amine compound having a structure in which the groups bond 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.

[0112] The compound represented by formula (4) is preferably at least one selected from the group consisting of triallylamine and trioctylamine.

[0113] The content of the nitrogen-containing compound (C) in the polymerizable composition (for example, the total content 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.

[0114] The total content of the compound represented by formula (2) and the nitrogen-containing compound (C) in the polymerizable composition (for example, the total content of the compounds represented by formulas (2) to (4)) is preferably 0.01 to 1 mass%, more preferably 0.01 to 0.5 mass%, and still 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.

[0115] Other examples of the polymerization catalyst include those described in paragraphs 0029 to 0033 of JP-A No. 2002-194083.

[0116] <Lewis Acid Compound> The polymerizable composition of the present disclosure may contain a Lewis acid compound. This can further improve the pot life of the polymerizable composition. When the polymerizable composition of the present disclosure contains a Lewis acid compound, the Lewis acid compound contained may be only one type, or two or more types.

[0117] The Lewis acid compound is not particularly limited, and examples thereof include organotin compounds, zinc chloride, zinc acetylacetonate, aluminum chloride, aluminum fluoride, triphenylaluminum, titanium tetrachloride, calcium acetate, etc. For Lewis acid compounds, reference may be made as appropriate to 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).

[0118] The organic tin compound is not particularly limited, and 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; and the like.

[0119] The dialkyltin halides may include monoalkyltin halides and trialkyltin halides. The dialkyltin dicarboxylates may include monoalkyltin tricarboxylates and trialkyltin carboxylates.

[0120] From the viewpoint of further improving the pot life of the polymerizable composition, the Lewis acid compound preferably contains a compound represented by the following formula (5), which is a specific organotin compound.

[0121]

[0122] 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.

[0123] The compound represented by formula (5) is preferably at least one selected from the group consisting of dimethyltin dichloride, dibutyltin dichloride, and dibutyltin dilaurate.

[0124] The content of the Lewis acid compound (for example, an organotin compound such as a compound represented by formula (5)) is preferably 100 ppm by mass to 500 ppm by mass, and more preferably 200 ppm by mass to 400 ppm by mass, relative to the total amount of the polymerizable composition.

[0125] <Compound (b)> The polymerizable composition of the present disclosure may contain the following compound (b). The compound (b) is at least one 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. The compound (b) can contribute to suppressing striae in the resulting resin. The pKa of each of the acid and the anhydride in the compound (b) being less than 2.0 can contribute to reducing the viscosity of the polymerizable composition.

[0126] 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 includes a sulfonic acid having a pKa of less than 2.0. The acid (b1) may form a hydrate.

[0127] The anhydride (b2) is an anhydride of an acid having a pKa of less than 2.0 (i.e., an anhydride having a structure formed by dehydration condensation of an acid having a pKa of less than 2.0). Specific examples of acids 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 includes an anhydride of a sulfonic acid having a pKa of less than 2.0.

[0128] A preferred embodiment of compound (b) is one in which acid (b1) contains a sulfonic acid having a pKa of less than 2.0, and anhydride (b2) contains a sulfonic acid anhydride having a pKa of less than 2.0. In this embodiment, the total amount of sulfonic acid having a pKa of less than 2.0 and sulfonic acid 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.

[0129] A more preferred embodiment of compound (b) is one in which 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) comprises at least one selected from the group consisting of 10-camphorsulfonic anhydride, methanesulfonic anhydride, and paratoluenesulfonic anhydride. In this embodiment, 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 racemic or optically active form.

[0130] A further preferred embodiment of compound (b) is one in which acid (b1) comprises 10-camphorsulfonic acid and 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.

[0131] From the viewpoint of the striae-inhibiting effect, the content of the compound (b) in the polymerizable composition is preferably 0.0001% by mass to 1.000% by mass, more preferably 0.0005% by mass to 0.100% by mass, and even more preferably 0.001% by mass to 0.050% by mass, relative to the total amount of the episulfide compound represented by Formula (1), the polyiso(thio)cyanate compound, and the polythiol compound.

[0132] <Other Components> The polymerizable composition of the present disclosure may contain other components in addition to the components described above. Examples of the other components include bluing agents, resins (e.g., acrylic resins, olefin resins, etc.), crosslinking agents, light stabilizers, antioxidants, coloring inhibitors, dyes, fillers, and internal mold release agents. Known components can be used as the other components. For details of the other components, see, for example, JP 2002-194083 A.

[0133] The polymerizable composition of the present disclosure is obtained by mixing the above-described components (raw materials). The order of mixing the components (raw materials) is not particularly limited; all of the raw materials may be added to a container at once and mixed, or the raw materials may be added to a container in multiple batches and mixed. Furthermore, during the mixing process, some of the monomers in the polymerizable composition of the present disclosure may polymerize to form a prepolymer. The monomers in the polymerizable composition of the present disclosure refer to at least the episulfide compound represented by formula (1), the polyiso(thio)cyanate compound, and the polythiol compound. In addition to these compounds, the epoxy compound (X) may also function as a monomer.

[0134] [Resin, Molded Article] The resin of the present disclosure is a cured product of the polymerizable composition of the present disclosure. The molded article of the present disclosure contains the resin of the present disclosure.

[0135] 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.

[0136] Examples of methods for polymerizing the monomers in the polymerizable composition of the present disclosure include cast polymerization, which can produce a molded article of the present disclosure containing the resin of the present disclosure (i.e., a cured product of the polymerizable composition of the present disclosure).

[0137] In cast polymerization, first, a polymerizable composition according to one example of the present disclosure is injected between a pair of molds held together by a gasket, tape, or the like. At this time, degassing, filtration, or the like may be performed as necessary. Next, the monomer in the composition injected between the molds is polymerized to harden the composition between the molds and obtain a cured product. The cured product is then removed from the molds to obtain a cured product. Polymerization of the monomer may be performed by heating the polymerizable composition according to the present disclosure. This heating can be performed, for example, using a heating device equipped with a mechanism for heating an object to be heated in an oven, water, or the like.

[0138] 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, the type and amount of monomers used in the composition, the type and amount of polymerization catalyst used in the composition, the shape of the mold, etc. Examples of the polymerization temperature include −50° C. to 150° C., 10° C. to 150° C., etc. Examples of the polymerization time include 1 hour to 200 hours, 1 hour to 80 hours, etc.

[0139] The resin or resin-containing molded article of the present disclosure may be obtained by subjecting the monomer to polymerization followed by treatment such as annealing, etc. Annealing temperatures include 50°C to 150°C, 90°C to 140°C, and 100°C to 130°C.

[0140] [Optical Material] The optical material of the present disclosure includes the resin of the present disclosure described above. The optical material of the present disclosure can be produced, for example, by the above-mentioned cast polymerization. The optical material of the present disclosure has a refractive index (n ｅ The refractive index (n ｅ ) can be determined, for example, by measuring 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) using a Pulfrich refractometer KPR-30 manufactured by Shimadzu Corporation, and based on the measurement results.

[0141] 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, such as other members and a coating layer provided on the resin of the present disclosure.

[0142] Optical materials of the present disclosure include lenses (e.g., eyeglass lenses, camera lenses, polarized lenses, etc.), light-emitting diodes (LEDs), and the like.

[0143] [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. The lens of the present disclosure can be manufactured, for example, by the cast polymerization described above.

[0144] The lens of the present disclosure may be made of the resin of the present disclosure, or may include the resin of the present disclosure and other elements, such as other members and a coating layer provided on the resin of the present disclosure.

[0145] Lenses according to the present disclosure include eyeglass lenses, camera lenses, polarized lenses, etc. Hereinafter, eyeglass lenses will be described as an example of lenses according to the present disclosure. The eyeglass lenses contain the resin according to the present disclosure molded into a desired lens shape. The eyeglass lenses preferably further contain a coating layer provided on one or both sides of the resin.

[0146] Specific examples of the coating layer include a primer layer, a hard coat layer, an antireflection layer, an antifogging coat layer, an antifouling layer, and a water-repellent layer. Each of these coating layers can be used alone, or multiple coating layers can be used in combination. When coating layers are applied to both sides of the cured product, the same coating layer or different coating layers can be applied to each side.

[0147] The components of the coating layer can be appropriately selected depending on the purpose, and examples of the 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.

[0148] For details about eyeglass lenses and coating layers, reference can be made to the descriptions in publicly known documents such as JP 2002-194083 A and WO 2017 / 047745 A, as appropriate.

[0149] Examples of the present disclosure will be shown below, but the present disclosure is not limited to the following examples. Unless otherwise specified, "parts" are based on mass.

[0150] Example 1 Preparation of Polymerizable Composition 25.4 parts by mass of xylylene diisocyanate (hereinafter also referred to as "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" (trade name: KF-615A manufactured by Shin-Etsu Silicones Co., Ltd.) as a silicone compound, and 1.000 parts by mass of "Tinuvin PS" (manufactured by BASF Japan Ltd.) as an ultraviolet absorber were mixed and dissolved at 20°C. To the resulting solution, 42.6 parts by mass of bis(2,3-epithiopropyl)disulfide (hereinafter also referred to as "EPS-1") as the episulfide compound represented by formula (1) was added, followed by 32.0 parts by mass of a polythiol composition (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, and a phenol salt of 1,8-diazabicyclo[5.4.0]undecene-7 (DBU (registered trademark)) ("U-CAT" manufactured by San-Apro Co., Ltd.) as a polymerization catalyst. 0.0689 parts by mass of "DBU PhOH salt" (hereinafter also referred to as "DBU PhOH salt") was added to the flask and mixed at 5 to 10° C. for 5 minutes to obtain a polymerizable composition.

[0151] In this Example 1 (M Ｓ -M Ｎ ) / M ＥThe ratios are as shown in Table 1. "KF-615A" corresponds to compound (S1), and is a compound in which the molar fraction of silicone units [i.e., (m+n) / (m+n+a+b)] is 0.16 and the molar fraction of polyether units [i.e., (a+b) / (a+b+m+n)] is 0.84.

[0152] <Evaluation> The polymerizable compositions obtained above were evaluated as follows.

[0153] (Slope of Viscosity Increase Rate) 80 g of the polymerizable composition was placed in a 100 mL container and stored at 10° C. under a nitrogen atmosphere, and the viscosity of the polymerizable composition during storage was measured. The viscosity of the polymerizable composition was measured using a Brookfield B-type viscometer (spindle No. 62) while stirring the polymerizable composition at 10° C.

[0154] Based on the viscosity measurement results during storage, the change in viscosity over time was plotted with the horizontal axis (X) representing time (h) and the vertical axis (Y) representing the viscosity of the polymerizable composition (mPa·s). The obtained change in viscosity over time was approximated by the following formula, and the value "b" in the formula was taken as the viscosity increase rate slope: Y=a*exp(b*X)

[0155] The values ​​of "a" and "b" are shown in Table 1. The smaller the value of "b" (i.e., the slope of the viscosity increase rate), the better the pot life (i.e., the longer the pot life).

[0156] Example 2 The same operation as in Example 1 was carried out, except that the polymerization catalyst was changed to 0.0830 parts by mass of 2-ethylhexanoate of 1,8-diazabicyclo[5.4.0]undecene-7-ene (DBU (registered trademark)) (U-CAT SA102, a product of San-Apro Co., Ltd.; hereinafter, also referred to as "2EH salt of DBU"). The values ​​of "a" and "b" are shown in Table 1.

[0157] Example 3 The same operation as in Example 1 was carried out, except that the polymerization catalyst was changed to 0.0751 parts by mass of 2-ethylhexanoate of 1,5-diazabicyclo[4.3.0]nonene-5-(DBN) (trade name: U-CAT 1102, manufactured by San-Apro Co., Ltd.). The values ​​of "a" and "b" are shown in Table 1.

[0158] Comparative Example 1 The same procedure as in Example 1 was carried out except that the polymerization catalyst was changed to 0.0300 parts by mass of 3,5-lutidine. The values ​​of "a" and "b" are shown in Table 1.

[0159] Comparative Example 2 The same procedure as in Example 1 was carried out except that the polymerization catalyst was changed to 0.0425 parts by mass of dibutyltin dichloride (DBC). The values ​​of "a" and "b" are shown in Table 1.

[0160]

[0161] It was confirmed that the polymerizable compositions of Examples 1 to 3, which contained the episulfide compound represented by Formula (1), a polyiso(thio)cyanate compound, a polythiol compound, an epoxy compound, and a salt of a compound having an amidine skeleton, had a smaller value of "b," i.e., a smaller slope of the viscosity increase rate, and were excellent in pot life, compared to the polymerizable composition of Comparative Example 1, which did not contain a salt of a compound having an amidine skeleton.

[0162] The disclosure of Japanese Patent Application No. 2023-142443, filed on September 1, 2023, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A polymerizable composition comprising: an episulfide compound represented by the following formula (1); a polyiso(thio)cyanate compound; a polythiol compound; an epoxy compound; and a salt of a compound having an amidine skeleton. [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. The polymerizable composition according to claim 1, wherein the salt is a carboxylate or a phenolic compound salt.

3. The polymerizable composition according to claim 1, wherein the compound having an amidine skeleton is at least one selected from the group consisting of 1,8-diazabicyclo[5.4.0]-7-undecene and 1,5-diazabicyclo[4.3.0]-5-nonene.

4. The polymerizable composition according to claim 1, wherein the salt of the compound having an amidine skeleton is at least one selected from the group consisting of a phenol salt of 1,8-diazabicyclo[5.4.0]-7-undecene, a 2-ethylhexanoate salt of 1,8-diazabicyclo[5.4.0]-7-undecene, and a 2-ethylhexanoate salt of 1,5-diazabicyclo[4.3.0]-5-nonene.

5. The polymerizable composition according to claim 1, 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.

6. The polymerizable composition according to claim 1, wherein the epoxy compound comprises an epoxy compound (X1) containing two or more epoxy groups in one molecule.

7. The total number of moles of mercapto groups contained in the total amount of the polythiol compound is M Ｓ The total number of moles of iso(thio)cyanate groups in the total amount of the polyiso(thio)cyanate compound is M Ｎ 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 2. The polymerizable composition of claim 1, wherein the ratio is greater than 0 and less than or equal to 0.

20.

8. 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.

2. The polymerizable composition according to claim 1, comprising at least one member 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.

9. The 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.

10. A resin which is a cured product of the polymerizable composition according to any one of claims 1 to 9.

11. A molded article comprising the resin according to claim 10.

12. An optical material comprising the resin according to claim 10.

13. A lens comprising the resin of claim 10.

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