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

Abstract

A polymerizable composition containing: an episulfide compound represented by formula (1); a polyiso (thio) cyanate compound; a polythiol compound; an epoxy compound (X) that contains one or more epoxy groups in each molecule and does not contain an epithio group; and at least one compound (b) selected from the group consisting of an acid (b1) having a pKa of less than 2.0 and an acid anhydride (b2) of an acid having a pKa of less than 2.0. In formula (1), Y represents an alkylene group, a cycloalkanediyl group, an alkylene group containing an alicyclic skeleton containing 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. # imgabs0 #

Description

Technical Field

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

[0002] Plastic lenses are lighter and less prone to breakage than inorganic lenses, and can be dyed. Therefore, in recent years, plastic lenses have rapidly become popular for applications such as eyeglass lenses and camera lenses.

[0003] In recent years, various studies have been conducted on resin compositions containing episulfide compounds as raw materials for plastic lenses.

[0004] For example, Patent Document 1 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 in one molecule, and a polymerization catalyst, with the aim of developing a method for adjusting the polymerization rate and improving the heat resistance of a resin optical material having a sufficiently high refractive index and a good Abbe number.

[0005] Patent Document 1: Japanese Patent Application Publication No. 2005-298742 Summary of the invention

[0006] Problems to be solved by the invention

[0007] However, there is a need to suppress striae in a resin obtained from a resin composition containing an episulfide compound (hereinafter also referred to as a "polymerizable composition").

[0008] An object of one embodiment of the present disclosure is to provide a polymerizable composition capable of producing a resin in which striae are suppressed, and a resin, a molded product, an optical material, and a lens in which striae are suppressed.

[0009] Means for solving problems

[0010] Means for solving the above-mentioned problems include the following aspects.

[0011] <1> A polymerizable composition comprising:

[0012] An episulfide compound represented by the following formula (1);

[0013] Polyiso(thio)cyanate compounds;

[0014] Polythiol compounds;

[0015] Epoxides; and

[0016] The compound (b) is at least one compound selected from the group consisting of an acid (b1) having a pKa of less than 2.0 and an acid anhydride (b2) having a pKa of less than 2.0.

[0017] [Chemical formula 1]

[0018]

[0019] In formula (1), Y represents a substituted or unsubstituted straight-chain 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 alkylene arylene alkylene 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] <2> like <1> In the polymerizable composition, the acid (b1) comprises a sulfonic acid having a pKa of less than 2.0, and the acid anhydride (b2) comprises an anhydride of a sulfonic acid having a pKa of less than 2.0.

[0021] <3> like <1> The polymerizable composition, wherein the acid (b1) comprises at least one selected from the group consisting of 10-camphorsulfonic acid, methanesulfonic acid, and p-toluenesulfonic acid,

[0022] The acid anhydride (b2) includes at least one selected from the group consisting of 10-camphorsulfonic anhydride, methanesulfonic anhydride, and p-toluenesulfonic anhydride.

[0023] <4> like <1> ~ <3> The polymerizable composition according to any one of the preceding claims, wherein the epoxy compound comprises an epoxy compound (X) having one or more epoxy groups and no episulfide group in one molecule.

[0024] <5> like <1> ~ <4> The polymerizable composition according to any one of the preceding claims, wherein the epoxy compound contains an epoxy compound (X1) having two or more epoxy groups in one molecule.

[0025] <6> like <1> ~ <5> The polymerizable composition according to any one of the preceding claims, wherein the total number of moles of mercapto groups contained in the total amount of the polythiol compounds is defined as M S ,

[0026] The total number of moles of iso(thio)cyanate groups in the total amount of the polyiso(thio)cyanate compounds is defined as M. N ,

[0027] The total number of moles of episulfide groups contained in the total amount of episulfide compounds represented by the above formula (1) is defined as M E In the case of

[0028] (M S -MN ) / M E The ratio is greater than 0 and less than 0.20.

[0029] <7> like <1> ~ <6> The polymerizable composition according to any one of the preceding claims, wherein the polythiol compound comprises a compound 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 , at least one of the group consisting of 4-dithiocyclohexane, bis(mercaptoethyl) sulfide, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiocyclohexane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiocyclohexane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, and tris(mercaptomethylthio)methane.

[0030] <8> like <1> ~ <7> The polymerizable composition according to any one of the preceding claims, 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(isocyanate methyl)cyclohexane, bis(isocyanate cyclohexyl)methane, 2,5-bis(isocyanate methyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanate methyl)bicyclo-[2.2.1]-heptane, toluene diisocyanate, 4,4′-diphenylmethane diisocyanate, and phenylene diisocyanate.

[0031] <9> like <1> ~ <8> The polymerizable composition described above further contains a tertiary amine compound.

[0032] <10> like <9> The polymerizable composition described above, wherein the tertiary amine compound includes at least one of a compound represented by the following formula (3) and a compound represented by the following formula (4).

[0033] [Chemical formula 2]

[0034]

[0035] In formula (3), m R1s each independently represent a straight-chain 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.

[0036] In formula (4), R2, R3, and R4 each independently represent 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. R2 and R3 may be bonded to each other to form a ring.

[0037] <11> like <10> The polymerizable composition, wherein the compound represented by the formula (3) is at least one selected from the group consisting of 2-methylpyrazine, pyridine, α-methylpyridine, β-methylpyridine, γ-methylpyridine, 2,6-lutidine, 3,5-lutidine, 2,4,6-trimethylpyridine, 3-chloropyridine, 2-ethylpyridine, and 3-ethylpyridine,

[0038] The compound represented by the formula (4) is at least one selected from the group consisting of triallylamine and trioctylamine.

[0039] <12> like <1> ~ <11> The polymerizable composition according to any one of the above aspects further comprises a Lewis acid compound.

[0040] <13> like <12> The polymerizable composition described above, wherein the Lewis acid compound includes a compound represented by the following formula (5).

[0041] [Chemical formula 3]

[0042] (R4) c -Sn-X 4-c (5)

[0043] In formula (5), R4 represents an alkyl group having 1 to 4 carbon atoms, X represents a fluorine atom, a chlorine atom, a bromine atom, or -OC(=O)-R5, R5 represents an alkyl group having 1 to 11 carbon atoms, and c represents an integer of 1 to 3.

[0044] <14> like <13> The polymerizable composition is characterized in that the compound represented by the formula (5) is at least one selected from the group consisting of dimethyltin dichloride, dibutyltin dichloride, and dibutyltin dilaurate.

[0045] <15> like <1> ~ <13> The polymerizable composition described above further contains an organic silicon compound.

[0046] <16> Resin, which is <1> ~ <15> A cured product of any one of the polymerizable compositions.

[0047] <17> A molded body comprising <16> The resin.

[0048] <18> Optical material comprising <16> The resin.

[0049] <19> The lens comprises <16> The resin.

[0050] Effects of the Invention

[0051] According to one embodiment of the present disclosure, a polymerizable composition capable of producing a resin in which striae are suppressed, and a resin, a molded product, an optical material, and a lens in which striae are suppressed are provided. DETAILED DESCRIPTION

[0052] In the present disclosure, a numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0053] In the present disclosure, when there are plural kinds of substances belonging to each component in the composition, the amount of each component in the composition refers to the total amount of the plural kinds of substances present in the composition unless otherwise specified.

[0054] In the numerical range recorded in stages in this disclosure, the upper limit or lower limit recorded in one numerical range can be replaced by the upper limit or lower limit of the numerical range recorded in other stages. In addition, in the numerical range recorded in this disclosure, the upper limit or lower limit of the numerical range can be replaced by the value shown in the embodiment.

[0055] [Polymerizable composition]

[0056] The polymerizable composition of the present disclosure contains:

[0057] an episulfide compound represented by the formula (1) described later;

[0058] Polyiso(thio)cyanate compounds;

[0059] Polythiol compounds;

[0060] Epoxides; and

[0061] The compound (b) is at least one compound selected from the group consisting of an acid (b1) having a pKa of less than 2.0 and an acid anhydride (b2) having a pKa of less than 2.0.

[0062] According to the polymerizable composition of the present disclosure, a resin with suppressed striae can be produced.

[0063] Specifically, since the polymerizable composition containing the episulfide compound represented by the formula (1) described later, the polyiso(thio)cyanate compound, the polythiol compound, and the epoxy compound (X) further contains the compound (b), striae in the obtained resin can be suppressed.

[0064] Furthermore, the obtained resin is excellent in heat resistance and has reduced haze.

[0065] The polymerizable compositions of the present disclosure have reduced viscosity.

[0066] The episulfide compound represented by the formula (1) is a component that is a prerequisite for obtaining a resin having a high refractive index.

[0067] The polyiso(thio)cyanate compound, the polythiol compound, and the epoxy compound (X) are components for ensuring the strength of the above-mentioned high refractive index resin.

[0068] Hereinafter, each component that may be contained in the polymerizable composition of the present disclosure will be described.

[0069] <Episulfide compound represented by formula (1)>

[0070] The polymerizable composition of the present disclosure contains at least one episulfide compound represented by the following formula (1).

[0071] [Chemical formula 4]

[0072]

[0073] In formula (1), Y represents a substituted or unsubstituted straight-chain 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 alkylene arylene alkylene 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.

[0074] Examples of the substituted or unsubstituted straight-chain 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 methylene, ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene and 1,4-butylene, and groups in which the unsubstituted alkylene groups are substituted with substituents such as alkyl, hydroxyl, mercapto, carbonyl and thiocarbonyl.

[0075] 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 cyclopropylene, 1,2-cyclobutylene, 1,3-cyclobutylene, 1,2-cyclopentylene, 1,3-cyclopentylene, 1,2-cyclohexylene, 1,3-cyclohexylene, and 1,4-cyclohexylene, and groups in which the unsubstituted cyclic alkylene groups are substituted with substituents such as alkyl, hydroxyl, mercapto, carbonyl, and thiocarbonyl.

[0076] 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.

[0077] In the following formula, * represents a bonding position. x and y are each independently an integer of 0 or 1.

[0078] [Chemical formula 5]

[0079]

[0080] Examples of the substituted or unsubstituted alkylene arylene alkylene group having 8 to 16 carbon atoms represented by Y include xylylene groups and groups in which xylylene groups are substituted with substituents such as alkyl groups, hydroxyl groups, mercapto groups, carbonyl groups, and thiocarbonyl groups.

[0081] Examples of the substituted or unsubstituted arylene group represented by Y include unsubstituted arylene groups such as phenylene and naphthylene, and groups in which the unsubstituted arylene groups are substituted with substituents such as alkyl, hydroxyl, mercapto, carbonyl, and thiocarbonyl groups.

[0082] Examples of the substituted or unsubstituted aralkylene group represented by Y include unsubstituted aralkylene groups such as benzylene, styreneethyl and xylylene, and groups in which the unsubstituted aralkylene groups are substituted with substituents such as alkyl, hydroxyl, mercapto, carbonyl and thiocarbonyl.

[0083] In the formula (1), m represents an integer of 0 to 2.

[0084] m is preferably 0 or 1, more preferably 0.

[0085] In the formula (1), n ​​represents an integer of 0 to 3.

[0086] n is preferably 0, 1 or 3.

[0087] Regarding the episulfide compound represented by the formula (1), for example, the description in paragraphs 0025 to 0038 of JP-A-2005-272778 can be appropriately referred to.

[0088] The episulfide compound represented by formula (1) preferably includes a compound selected from the group consisting of

[0089] Bis(2,3-epithiopropyl)sulfide,

[0090] Bis(2,3-epithiopropylthio)methane,

[0091] Bis(2,3-epithiopropylthio)ethane,

[0092] 1,8-bis(2,3-epithiopropylthio)-3,6-dithiaoctane, and

[0093] At least one selected from the group consisting of bis(2,3-epithiopropyl)disulfide (hereinafter also referred to as "episulfide compound (E1)"),

[0094] More preferably, at least one of bis(2,3-epithiopropyl)sulfide and bis(2,3-epithiopropyl)disulfide (hereinafter also referred to as “episulfide compound (E2)”) is contained.

[0095] In the polymerizable composition, the ratio of the episulfide compound (E1) to the total amount of the episulfide compounds represented by the formula (1) is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and even more preferably 80 to 100% by mass.

[0096] In the polymerizable composition, the preferred range of the ratio of the episulfide compound (E2) to the total amount of the episulfide compounds represented by the formula (1) is also the same as the preferred range of the ratio of the episulfide compound (E1) to the total amount of the episulfide compounds represented by the formula (1).

[0097] From the viewpoint of obtaining a resin with a more excellent refractive index, the content of the episulfide compound represented by formula (1) based on 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.

[0098] From the viewpoint of further improving the strength and hue of the obtained resin, the content of the episulfide compound represented by formula (1) is preferably 85% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less, based on the total amount of the polymerizable composition of the present disclosure.

[0099] As a preferred range of the content of the episulfide compound represented by formula (1) based on the total amount of the polymerizable composition of the present disclosure, for example, there is mentioned a range of 30% by mass to 85% by mass.

[0100] <Polyiso(thio)cyanate compounds>

[0101] The polymerizable composition of the present disclosure contains at least one polyiso(thio)cyanate compound.

[0102] In the present disclosure, the polyiso(thio)cyanate compound refers to a compound containing two or more iso(thio)cyanate groups in one molecule.

[0103] In the present disclosure, the so-called "iso(thio)cyanate group" refers to an isocyanate group or an isothiocyanate group.

[0104] Regarding the polyiso(thio)cyanate compound, for example, the description in paragraphs 0049 to 0051 of JP-A-2005-272778 can be appropriately referred to.

[0105] The polyiso(thio)cyanate compound in the polymerizable composition of the present disclosure particularly preferably contains at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatemethyl)cyclohexane, bis(isocyanatecyclohexyl)methane, 2,5-bis(isocyanatemethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatemethyl)bicyclo-[2.2.1]-heptane, toluene diisocyanate, 4,4′-diphenylmethane diisocyanate, and phenylene diisocyanate (hereinafter referred to as “polyisocyanate compound N1”).

[0106] In the polymerizable composition, the ratio of the polyisocyanate compound N1 to the total amount of the polyiso(thio)cyanate compounds is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and further preferably 80 to 100% by mass.

[0107] From the viewpoint of further improving the Abbe number, hue, and strength of the obtained resin, 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.

[0108] From the viewpoint of obtaining a more excellent refractive index of the obtained resin, the content of the polyiso(thio)cyanate compound based on 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.

[0109] As a preferred range of the content of the polyiso(thio)cyanate compound based on the total amount of the polymerizable composition of the present disclosure, for example, there is mentioned a range of 2% by mass to 50% by mass.

[0110] <Polythiol Compound>

[0111] The polymerizable composition of the present disclosure contains at least one polythiol compound.

[0112] In the present disclosure, the polythiol compound refers to a compound containing two or more mercapto groups (ie, thiol groups) in one molecule.

[0113] In the present disclosure, two or more polythiol compounds may be referred to as a "polythiol composition".

[0114] Regarding the polythiol compound, for example, the description in paragraphs 0039 to 0048 of JP-A-2005-272778 can be appropriately referred to.

[0115] The polythiol compound in the polymerizable composition of the present disclosure preferably comprises a compound 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-dithiacyclohexane, At least one of the group consisting of 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-dithiane, 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").

[0116] In the polymerizable composition, the proportion of the polythiol compound S1 in the total amount of the polythiol compounds (i.e., when the 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 further preferably 80% by mass to 100% by mass.

[0117] From the viewpoint of further improving the hue and strength of the obtained resin, 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.

[0118] From the viewpoint of obtaining a resin with better refractive index and heat resistance, 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.

[0119] As a preferred range of the content of the polythiol compound based on the total amount of the polymerizable composition of the present disclosure, for example, there is mentioned a range of 5% by mass to 60% by mass.

[0120] <Epoxy Compounds>

[0121] The polymerizable composition of the present disclosure contains at least one epoxy compound.

[0122] The epoxy compound contained in the polymerizable composition of the present disclosure (hereinafter also referred to as “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.

[0123] The epoxy compound in the present disclosure preferably includes the epoxy compound (X) described below.

[0124] Here, the epoxy compound (X) is an epoxy compound containing one or more epoxy groups in one molecule and containing no episulfide group.

[0125] The proportion of the epoxy compound (X) in the total amount of the epoxy compounds in the present disclosure is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and even more preferably 80 to 100% by mass.

[0126] The epoxy compound in the present disclosure also preferably includes the epoxy compound (X1) described below.

[0127] Here, the epoxy compound (X1) is a compound containing two or more (preferably 2 to 4, more preferably 2 or 3, and even more preferably 2) epoxy groups in one molecule.

[0128] The proportion of the epoxy compound (X1) in the total amount of the epoxy compounds in the present disclosure is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and further preferably 80 to 100% by mass.

[0129] The epoxy compound (X1) may be a compound belonging to the epoxy compound (X).

[0130] The epoxy compound (X1) in this case is an epoxy compound containing two or more epoxy groups in one molecule and containing no episulfide group.

[0131] Specific examples of the epoxy compound (for example, epoxy compound (X) and / or epoxy compound (X1). The same applies hereinafter) in the present disclosure include:

[0132] Phenolic epoxy compounds produced by the reaction of aromatic hydroxy compounds such as phenol, cresol, xylenol, naphthol, hydroquinone, catechol, resorcinol, bisphenol A, bisphenol F, bis(hydroxyphenyl) sulfone, bis(hydroxyphenyl) ether, bis(hydroxyphenyl) sulfide, halogenated bisphenol A Novolac resin, and epihalohydrin;

[0133] Alcohol epoxy compounds produced by the reaction of 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, glycerol, trimethylolpropane, pentaerythritol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, bisphenol A·ethylene oxide adduct, bisphenol A·propylene oxide adduct, and an epihalohydrin;

[0134] Glycidyl ester epoxy compounds produced by the reaction of carboxylic acid compounds such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, isobutyric acid, isovaleric acid, benzoic acid, benzoylacetic acid, naphthoic 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, chlorobridged acid, nadic acid, maleic acid, succinic acid, fumaric acid, trimellitic acid, benzenetetracarboxylic acid, benzophenonetetracarboxylic acid, naphthalene dicarboxylic acid, and diphenyl dicarboxylic acid with epihalohydrins;

[0135] By 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-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-diaminotoluene, m- or p-phenylenediamine, 1,5- or 2,6-naphthalenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 2,2-bis(4,4'-diaminodiphenyl)propane and other primary amines,

[0136] 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-1,7- Amine epoxy compounds produced by the reaction of secondary amines such as 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-piperidinyl)-methane, 1,2-di-(4-piperidinyl)-ethane, 1,3-di-(4-piperidinyl)-propane, and 1,4-di-(4-piperidinyl)-butane with epihalohydrins;

[0137] Alicyclic epoxy compounds such as epoxycyclohexane, 3,4-epoxycyclohexyl 3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide, 1,2:8,9-diepoxylimonene, 2-(3,4-epoxycyclohexyl)-5,5-spiro-3,4-epoxycyclohexane-dioxane, and bis(3,4-epoxycyclohexyl) adipate;

[0138] Epoxides made by epoxidation of unsaturated compounds such as styrene oxide, dicyclopentadiene diepoxide, epoxidized soybean oil, epoxidized polybutadiene, vinylcyclohexene epoxide;

[0139] Urethane epoxy compounds made from polyols or phenolic compounds, diisocyanates and glycidol;

[0140] etc.

[0141] 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 further preferably contains an aromatic ring and two or more (preferably 2 to 4, more preferably 2 or 3, and further preferably 2) glycidyloxy groups.

[0142] 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.

[0143] The lower limit of the molecular weight of the epoxy compound in the present disclosure is preferably 100, more preferably 200.

[0144] The epoxy compound in the present disclosure preferably includes 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).

[0145] 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 further preferably 80% by mass to 100% by mass.

[0146] From the viewpoint of further improving the hue of the obtained resin, the content of the epoxy compound in 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 relative to the total amount of the polymerizable composition of the present disclosure.

[0147] From the viewpoint of obtaining a resin with better strength, 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.

[0148] As 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, for example, there is mentioned a range of 0.05 mass % to 20 mass %.

[0149] <(M S -M N ) / M E >

[0150] In the polymerizable composition of the present disclosure,

[0151] The total number of moles of mercapto groups contained in the total amount of the polythiol compound is defined as M. S ,

[0152] The total number of moles of iso(thio)cyanate groups in the total amount of polyiso(thio)cyanate compounds is defined as M. N ,

[0153] The total number of moles of episulfide groups contained in the total amount of episulfide compounds represented by formula (1) is defined as M E In the case of

[0154] (M S -M N ) / M E The ratio is preferably greater than 0 and not more than 0.20, more preferably greater than 0 and not more than 0.15.

[0155] (M S -M N ) / M E When the ratio is larger than 0, the strength of the obtained resin is further improved.

[0156] (M S -M N ) / M E When the ratio is 0.20 or less, the heat resistance of the obtained resin is further improved.

[0157] <Compound (b)>

[0158] The polymerizable composition of the present disclosure contains a compound (b).

[0159] The compound (b) in the present disclosure is at least one selected from the group consisting of an acid (b1) having a pKa of less than 2.0 and an acid anhydride (b2) having a pKa of less than 2.0.

[0160] As described above, the compound (b) contributes to suppressing striae in the resulting resin.

[0161] The fact that the pKa of each of the acid and the acid anhydride in the compound (b) is less than 2.0 contributes to the reduction in the viscosity of the polymerizable composition.

[0162] The acid (b1) is an acid having a pKa of less than 2.0.

[0163] Examples of the acid (b1) include hydrochloric acid (pKa: -3.7), sulfuric acid (pKa: -3.0), nitric acid (pKa: -1.4), and sulfonic acid having a pKa of less than 2.0.

[0164] Examples of sulfonic acids having a pKa of less than 2.0 include 10-camphorsulfonic acid (pKa: 1.2), methanesulfonic acid (pKa: -2.6), p-toluenesulfonic acid (pKa: -2.8), vinylsulfonic acid (pKa: -2.7), and benzenesulfonic acid (pKa: 0.7).

[0165] From the viewpoint of the striae suppressing effect, the acid (b1) preferably contains a sulfonic acid having a pKa of less than 2.0.

[0166] The acid (b1) may also form a hydrate.

[0167] The acid anhydride (b2) is an acid anhydride of an acid having a pKa of less than 2.0 (that is, an acid anhydride having a structure in which an acid having a pKa of less than 2.0 is subjected to dehydration condensation).

[0168] Specific examples of the acid having a pKa of less than 2.0 for forming the acid anhydride (b2) are the same as the specific examples of the acid (b1) described above.

[0169] From the viewpoint of the striae suppressing effect, the acid anhydride (b2) preferably comprises an anhydride of a sulfonic acid having a pKa of less than 2.0.

[0170] From the viewpoint of the striae suppressing effect, a preferred embodiment of the compound (b) is an embodiment in which the acid (b1) comprises a sulfonic acid having a pKa of less than 2.0, and the acid anhydride (b2) comprises an anhydride of a sulfonic acid having a pKa of less than 2.0.

[0171] In this embodiment, the total amount of the sulfonic acid having a pKa of less than 2.0 and the anhydride of the sulfonic acid having a pKa of less than 2.0 in compound (b) is preferably 50 to 100% by mass, more preferably 50 to 80% by mass, and even more preferably 80 to 100% by mass.

[0172] From the viewpoint of the striae suppression effect, a more preferred embodiment of the compound (b) is the following embodiment:

[0173] The acid (b1) comprises at least one selected from the group consisting of 10-camphorsulfonic acid, methanesulfonic acid, and p-toluenesulfonic acid, and

[0174] The acid anhydride (b2) contains at least one selected from the group consisting of 10-camphorsulfonic anhydride, methanesulfonic anhydride, and p-toluenesulfonic anhydride.

[0175] In this embodiment, the total amount of 10-camphorsulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, 10-camphorsulfonic anhydride, methanesulfonic anhydride, and p-toluenesulfonic 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.

[0176] Here, 10-camphorsulfonic acid and 10-camphorsulfonic anhydride may each be a racemate or may be only one of the enantiomers.

[0177] From the viewpoint of the striae suppressing effect, a further preferred embodiment of the compound (b) is an embodiment in which the acid (b1) contains 10-camphorsulfonic acid and the acid anhydride (b2) contains 10-camphorsulfonic anhydride.

[0178] In this embodiment, the total amount of 10-camphorsulfonic acid and 10-camphorsulfonic anhydride in compound (b) is preferably 50 to 100% by mass, more preferably 50 to 80% by mass, and even more preferably 80 to 100% by mass.

[0179] From the viewpoint of the striae suppressing 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, the polyiso(thio)cyanate compound, and the polythiol compound represented by formula (1).

[0180] <Compound represented by formula (2)>

[0181] The polymerizable composition of the present disclosure preferably contains a compound represented by the following formula (2).

[0182] The compound represented by the following formula (2) can function as a curing catalyst.

[0183] When the polymerizable composition of the present disclosure contains a compound represented by the following formula (2), the strength of the obtained resin can be further improved.

[0184] When the polymerizable composition of the present disclosure contains a compound represented by the following formula (2), the compound represented by the formula (2) contained may be only one kind or two or more kinds.

[0185] (R 1 )4Y + X - …(2)

[0186] 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.

[0187] In formula (2), as R 1 The "linear hydrocarbon group having 1 to 10 carbon atoms or a branched hydrocarbon group having 3 to 10 carbon atoms" represented by alkyl is preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms.

[0188] From the viewpoint of improving the appearance of the obtained resin, R 1 The "linear hydrocarbon group having 1 to 10 carbon atoms or a branched hydrocarbon group having 3 to 10 carbon atoms" represented by alkyl is more preferably a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms, and further preferably a linear alkyl group having 1 to 6 carbon atoms.

[0189] 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 still more preferably a chlorine atom or a bromine atom.

[0190] From the viewpoint of improving the appearance of the obtained resin, the halogen atom represented by X is particularly preferably a bromine atom.

[0191] In formula (2), Y may be a nitrogen atom or a phosphorus atom, but is preferably a nitrogen atom.

[0192] The compound represented by formula (2) is preferably tetra-n-butylammonium bromide (TBAB) or tri-n-octylmethylammonium chloride (TOMAC).

[0193] Tetrabutylammonium bromide (TBAB) is the four R 1 A compound wherein each is an n-butyl group, Y is a nitrogen atom, and X is a bromine atom.

[0194] The content of the compound represented by formula (2) in the polymerizable composition is preferably 0.01% by mass to 1% by mass, more preferably 0.01 to 0.5% by mass, and even more preferably 0.01 to 0.3% by mass, relative to the total amount of the episulfide compound, the polyiso(thio)cyanate compound, and the polythiol compound represented by formula (1).

[0195] <Tertiary amine compound>

[0196] The polymerizable composition of the present disclosure preferably contains a tertiary amine compound.

[0197] The tertiary amine compound can function as a curing catalyst.

[0198] When the polymerizable composition of the present disclosure contains a tertiary amine compound, the appearance of the obtained resin can be improved.

[0199] When the polymerizable composition of the present disclosure contains a tertiary amine compound, the tertiary amine compound contained may be only one kind or two or more kinds.

[0200] The polymerizable composition of the present disclosure may contain both a compound represented by formula (2) and a tertiary amine compound (for example, at least one of a compound represented by formula (3) and a compound represented by formula (4)).

[0201] The tertiary 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).

[0202] (Compound represented by formula (3))

[0203] When the polymerizable composition of the present disclosure contains a compound represented by the following formula (3), the compound represented by the formula (3) contained may be only one kind or two or more kinds.

[0204] [Chemical formula 6]

[0205]

[0206] In formula (3), m R1s each independently represent a straight-chain 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.

[0207] In the formula (3), m is preferably an integer of 0 to 3, and more preferably an integer of 1 to 3.

[0208] In the formula (3), examples of the linear alkyl group having 1 to 20 carbon atoms represented by R1 include methyl, ethyl, n-propyl, n-butyl, pentyl, hexyl, heptyl, n-octyl, nonyl, decyl, and dodecyl.

[0209] In the formula (3), examples of the branched alkyl group having 3 to 20 carbon atoms represented by R1 include isopropyl, isobutyl, tert-butyl, isopentyl, isooctyl, 2-ethylhexyl, 2-propylpentyl, and isodecyl.

[0210] In the formula (3), examples of the cycloalkyl group having 3 to 20 carbon atoms represented by R1 include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

[0211] In the formula (3), R1 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.

[0212] The compound represented by formula (3) is preferably at least one selected from the group consisting of 2-methylpyrazine, pyridine, α-methylpyridine, β-methylpyridine, γ-methylpyridine, 2,6-lutidine, 3,5-lutidine, 2,4,6-trimethylpyridine, 3-chloropyridine, 2-ethylpyridine, and 3-ethylpyridine.

[0213] (Compound represented by formula (4))

[0214] When the polymerizable composition of the present disclosure contains a compound represented by the following formula (4), the compound represented by the formula (4) contained may be only one kind or two or more kinds.

[0215] [Chemical formula 7]

[0216]

[0217] In formula (4), R2, R3, and R4 each independently represent 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. R2 and R3 may be bonded to each other to form a ring.

[0218] In formula (4), R2, R3, and R4 are 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.

[0219] Examples of the linear alkyl group having 3 to 20 carbon atoms represented by R2, R3 or R4 include n-propyl, n-butyl, pentyl, hexyl, heptyl, n-octyl, nonyl, decyl and dodecyl.

[0220] R2 and R3 may be bonded to each other to form a ring.

[0221] That is, the compound represented by formula (4) may be a cyclic amine compound having a structure in which R2 and R3 are bonded to each other to form a ring.

[0222] Examples of the cyclic amine compound include 1-propylpiperidine, 1-butylpiperidine, 1-cyclohexylpiperidine, 1-butylpyrrolidine, and 1-cyclohexylpyrrolidine.

[0223] The compound represented by formula (4) is preferably at least one selected from the group consisting of triallylamine and trioctylamine.

[0224] The content of the tertiary amine compound 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% by mass to 1% by mass, more preferably 0.01% by mass to 0.5% by mass, and even more preferably 0.01% by mass to 0.5% by mass, relative to the total amount of the episulfide compound represented by formula (1), the polyiso(thio)cyanate compound, and the polythiol compound.

[0225] The total content of the compound represented by formula (2) and the tertiary amine compound in the polymerizable composition (for example, the total content of the compounds represented by formula (2) to formula (4)) is preferably 0.01% by mass to 1% by mass, more preferably 0.01% by mass to 0.5% by mass, and even more preferably 0.01% by mass to 0.5% by mass, relative to the total amount of the episulfide compound, polyiso(thio)cyanate compound, and polythiol compound represented by formula (1).

[0226] The polymerizable composition of the present disclosure may contain other compounds other than the compounds represented by the above-mentioned formulae (2) to (4) as a curing catalyst.

[0227] The curing catalyst can be selected from the curing catalysts described in, for example, paragraphs 0029 to 0033 of JP-A-2002-194083.

[0228] <Lewis acid compound>

[0229] The polymerizable composition of the present disclosure preferably contains a Lewis acid compound.

[0230] Thereby, the pot life of the polymerizable composition can be further improved.

[0231] When the polymerizable composition of the present disclosure contains a Lewis acid compound, the Lewis acid compound contained may be only one kind or two or more kinds.

[0232] The Lewis acid compound is not particularly limited, and examples thereof include organic tin compounds, zinc chloride, zinc acetylacetonate, aluminum chloride, aluminum fluoride, triphenylaluminum, tetrachlorotitanium, and calcium acetate.

[0233] Regarding the Lewis acid compound, for example, the descriptions in known documents such as JP-A-2000-256435 (especially paragraphs 0059 to 0060), JP-A-2005-272778 (especially paragraph 0058), and JP-A-2001-131257 (especially paragraph 0027) can be appropriately referred to.

[0234] The organotin compound is not particularly limited, and examples thereof include:

[0235] Dialkyltin halides such as dibutyltin dichloride and dimethyltin dichloride; dialkyltin dicarboxylates such as dimethyltin diacetate, dibutyltin dioctoate and dibutyltin dilaurate;

[0236] Tin tetrachloride;

[0237] Dibutyltin oxide;

[0238] etc.

[0239] The dialkyltin halides may include monoalkyltin halides and trialkyltin halides.

[0240] The dialkyltin dicarboxylates may include monoalkyltin tricarboxylates and trialkyltin carboxylates.

[0241] 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) as a specific organic tin compound.

[0242] [Chemical formula 8]

[0243] (R4) c-Sn-X 4-c (5)

[0244] In formula (5), R4 represents an alkyl group having 1 to 4 carbon atoms, X represents a fluorine atom, a chlorine atom, a bromine atom, or -OC(=O)-R5, R5 represents an alkyl group having 1 to 11 carbon atoms, and c represents an integer of 1 to 3.

[0245] The compound represented by formula (5) is preferably at least one selected from the group consisting of dimethyltin dichloride, dibutyltin dichloride, and dibutyltin dilaurate.

[0246] The content of the Lewis acid compound (for example, an organic tin compound such as the compound represented by formula (5)) is preferably 100 to 500 ppm by mass, and more preferably 200 to 400 ppm by mass, based on the total amount of the polymerizable composition.

[0247] <Organic silicon compounds>

[0248] From the viewpoint of further improving the appearance and releasability of the resin, the polymerizable composition of the present disclosure preferably contains at least one organosilicon compound.

[0249] The weight average molecular weight of the organosilicon compound is not particularly limited.

[0250] The weight average molecular weight of the organic silicon compound is preferably 200 to 100,000, more preferably 1,000 to 80,000.

[0251] The content of the organosilicon 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, the polyiso(thio)cyanate compound, and the polythiol compound represented by formula (1).

[0252] From the viewpoint of further improving the appearance of the resin, the organosilicon compound preferably contains at least one of dimethyl polysiloxane and a polyether-modified organosilicon compound.

[0253] From the viewpoint of further improving the releasability of the obtained resin, the organosilicon compound more preferably contains a polyether-modified organosilicon compound.

[0254] When the organosilicon compound includes a polyether-modified organosilicon compound, the proportion of the polyether-modified organosilicon compound in the total amount of the organosilicon compound is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and even more preferably 80 to 100% by mass.

[0255] From the viewpoint of further improving the releasability of the obtained resin, the organosilicon compound contained in the polymerizable composition of the present disclosure preferably includes at least one selected from the group consisting of a polyether-modified organosilicon compound represented by the following formula (S1) (hereinafter also referred to as compound (S1)) and a polyether-modified organosilicon compound represented by the following formula (S2) (hereinafter also referred to as compound (S2)), and more preferably includes compound (S1) (i.e., includes compound (S1), or includes compound (S1) and compound (S2)).

[0256] When the organosilicon 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 organosilicon compound 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.

[0257] When the organosilicon compound includes compound (S1) or includes compound (S1) and compound (S2), the proportion of compound (S1) in the total amount of the organosilicon compound 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.

[0258] [Chemical formula 9]

[0259]

[0260] In formula (S1), m and n each independently represent an integer greater than 1. a and b each independently represent an integer greater than 0 (excluding the case where both a and b are 0). R1 ​​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.

[0261] In formula (S2), p represents an integer greater than 1, and c, d, e, and f each independently represent an integer greater than 0 (excluding the case where c, d, e, and f are all 0). R2 and R3 each independently represent 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.

[0262] In formula (S1) and formula (S2), the unit represented by (OC3H6) represents an oxypropylene unit (i.e., O-CH(CH3)-CH2 unit), and C3H6 in the portion represented by Si-C3H6-(OC2H4) represents a trimethylene group (also known as 1,3-propanediyl; i.e., -CH2CH2CH2-).

[0263] In formula (S1), m is preferably an integer of 1 to 500, and more preferably an integer of 10 to 300. n is preferably an integer of 1 to 100, and more preferably an integer of 1 to 50.

[0264] a is preferably an integer of 0 to 1000, and more preferably an integer of 1 to 500. b is preferably an integer of 0 to 1000, and more preferably an integer of 0 to 500.

[0265] The weight average molecular weight of the polyether-modified silicone compound represented by the formula (S1) is preferably 200 to 100,000, more preferably 1,000 to 80,000.

[0266] In formula (S2), p is preferably an integer of 1-500, more preferably an integer of 10-300.

[0267] c and f are preferably integers of 0 to 1000, and more preferably integers of 1 to 500. d and e are preferably integers of 0 to 1000, and more preferably integers of 0 to 500.

[0268] The weight average molecular weight of the polyether-modified silicone compound represented by the formula (S2) is preferably 200 to 100,000, more preferably 1,000 to 80,000.

[0269] In formula (S1), the molar fraction of the silicone unit [ie, (m+n) / (m+n+a+b)] is preferably 0.08 to 0.60.

[0270] By setting the molar fraction of the silicone unit to 0.08 or more, the mold releasability can be sufficiently maintained.

[0271] By setting the molar fraction of the silicone unit to 0.60 or less, fogging, opacity, and the like in the cured product can be suppressed, and transparency can be maintained.

[0272] From the same viewpoint as above, in formula (S1), the molar fraction of the silicone unit is more preferably 0.10 to 0.50.

[0273] In formula (S1), the molar fraction of the polyether unit [ie, (a+b) / (a+b+m+n)] is preferably 0.40 to 0.92.

[0274] By setting the molar fraction of the polyether unit to be 0.40 or more, fogging, opacity, and the like in the cured product can be suppressed, and transparency can be maintained.

[0275] By setting the molar fraction of the polyether unit to be 0.92 or less, the mold releasability can be sufficiently maintained.

[0276] From the same viewpoint as above, in formula (S1), the molar fraction of the polyether unit is more preferably 0.50 to 0.90.

[0277] In formula (S2), the molar fraction of the silicone unit [ie, p / (p+c+d+e+f)] is preferably 0.08 to 0.60.

[0278] By setting the molar fraction of the silicone unit in the formula (S2) to 0.08 or more, the mold releasability can be sufficiently maintained.

[0279] By setting the molar fraction of the silicone unit in the formula (S2) to 0.60 or less, fogging, opacity, etc. in the cured product can be suppressed, and transparency can be maintained.

[0280] From the same viewpoint as above, in formula (S2), the molar fraction of the silicone unit is more preferably 0.10 to 0.50.

[0281] In 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.

[0282] By setting the molar fraction of the polyether unit in the formula (S2) to 0.40 or more, fogging, opacity, etc. in the cured product can be suppressed, and transparency can be maintained.

[0283] By setting the molar fraction of the polyether unit in the formula (S2) to 0.92 or less, the mold releasability can be sufficiently maintained.

[0284] From the same viewpoint as above, in formula (S2), the molar fraction of the polyether unit is more preferably 0.50 to 0.90.

[0285] The method for measuring the molar fractions of the silicone unit and the polyether unit is the same as the above-mentioned method.

[0286] In formula (S1) and formula (S2), the total molar fraction of the silicone unit [that is, (m+n+p) / (m+n+p+a+b+c+d+e+f)] is preferably 0.08 to 0.60.

[0287] By setting the molar fraction of the total silicone unit in the formula (S1) and the formula (S2) to be 0.08 or more, the mold releasability can be sufficiently maintained.

[0288] By setting the molar fraction of the total silicone unit in the formula (S1) and the formula (S2) to 0.60 or less, fogging, opacity, etc. in the cured product can be suppressed, and transparency can be maintained.

[0289] From the same viewpoint as above, in Formula (S1) and Formula (S2), the total molar fraction of the silicone unit is more preferably 0.10 to 0.50.

[0290] In formula (S1) and formula (S2), the total molar fraction of the 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.

[0291] By setting the molar fraction of the total polyether unit in the formula (S1) and the formula (S2) to 0.40 or more, fogging, opacity, etc. in the cured product can be suppressed, and transparency can be maintained.

[0292] By setting the molar fraction of the total polyether unit in the formula (S1) and the formula (S2) to 0.92 or less, the mold releasability can be sufficiently maintained.

[0293] From the same viewpoint as above, in Formula (S1) and Formula (S2), the total molar fraction of the polyether units is more preferably 0.50 to 0.90.

[0294] When the polyether-modified silicone compound contains both the compound (S1) and the compound (S2),

[0295] 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.

[0296] The polyether-modified silicone compound may contain at least one kind of the compound (S1) and the compound (S2), or may contain two or more kinds of the compound (S1) and the compound (S2).

[0297] It should be noted that the molar fractions of a, b, c, d, e, f, m, n and p, as well as the molar fractions of the aforementioned silicone units and polyether units are given by 1 The value obtained by integrating the signal in H-NMR.

[0298] <Other ingredients>

[0299] The polymerizable composition of the present disclosure may contain other components in addition to the above-mentioned components.

[0300] Examples of other components include bluing agents, resins (eg, acrylic resins, olefin resins, etc.), crosslinking agents, light stabilizers, ultraviolet absorbers, antioxidants, anti-coloring agents, dyes, fillers, and internal mold release agents.

[0301] As other components, known components can be used.

[0302] Regarding other components, for example, Japanese Patent Application Laid-Open No. 2002-194083 can be appropriately referred to.

[0303] The polymerizable composition of the present disclosure can be obtained by mixing the above-mentioned respective components (raw materials).

[0304] The order of mixing the components (raw materials) is not particularly limited, and all the raw materials may be put into a container at once and mixed, or the raw materials may be put into a container in multiple portions and mixed.

[0305] In addition, a part of the monomers in the polymerizable composition of the present disclosure may be polymerized during the mixing to form a prepolymer.

[0306] The monomers in the polymerizable composition of the present disclosure are at least the episulfide compound, the polyiso(thio)cyanate compound, and the polythiol compound represented by formula (1). In addition to these compounds, the epoxy compound (X) may also function as a monomer.

[0307] 〔Resin, molded article〕

[0308] The resin of the present disclosure is a cured product of the above-mentioned polymerizable composition of the present disclosure.

[0309] The molded article of the present disclosure contains the resin of the present disclosure.

[0310] That is, the resin of the present disclosure can be produced by curing the above-mentioned polymerizable composition of the present disclosure, specifically, by polymerizing and curing the monomers in the polymerizable composition of the present disclosure.

[0311] As a method for polymerizing the monomers in the polymerizable composition of the present disclosure, for example, cast polymerization can be mentioned. By cast polymerization, a molded article of the present disclosure containing the resin of the present disclosure (that is, a cured product of the polymerizable composition of the present disclosure) can be obtained.

[0312] In 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 or tape, etc. At this time, a degassing treatment, a filtration treatment, etc. may be performed as necessary.

[0313] Next, the monomers in the composition injected into the mold are polymerized, thereby curing the composition in the mold to obtain a cured product. Next, the cured product is removed from the mold to obtain a cured product.

[0314] The polymerization of the above-mentioned monomers can be carried out by heating the polymerizable composition of the present disclosure. The heating can be carried out, for example, using a heating device having a mechanism for heating a heating object in an oven, water, or the like.

[0315] The polymerization conditions (e.g., polymerization temperature, polymerization time, etc.) for polymerizing the monomers in the polymerizable composition of the present disclosure can be appropriately set in consideration of the composition of the composition, the type and amount of the monomers in the composition, the type and amount of the polymerization catalyst in the composition, the shape of the mold, etc.

[0316] Examples of the polymerization temperature include -50°C to 150°C and 10°C to 150°C.

[0317] Examples of the polymerization time include 1 hour to 200 hours and 1 hour to 80 hours.

[0318] The resin or the molded article containing the resin of the present disclosure may be obtained by subjecting the monomers to polymerization and then subjecting them to treatment such as annealing.

[0319] Examples of the annealing temperature include 50°C to 150°C, 90°C to 140°C, and 100°C to 130°C.

[0320] 〔Optical Materials〕

[0321] The optical material of the present disclosure includes the above-mentioned resin of the present disclosure.

[0322] The optical material of the present disclosure can be produced, for example, by the aforementioned casting polymerization.

[0323] The refractive index (n e ) is preferably 1.67 to 1.74, more preferably 1.69 to 1.73. e ) For example, the refractive index at each wavelength of 546.1 nm (mercury e-line), 480.0 nm (Cd F' line), and 643.9 nm (Cd C' line) can be measured using a Pulfrich refractometer KPR-30 manufactured by Shimadzu Corporation, and the refractive index can be calculated based on these measurement results.

[0324] The optical material of the present disclosure may be formed of the resin of the present disclosure, or may include the resin of the present disclosure and other elements.

[0325] As other elements, other members, coatings provided on the resin of the present disclosure, and the like can be cited.

[0326] Examples of the optical material of the present disclosure include lenses (for example, eyeglass lenses, camera lenses, polarizing lenses, etc.), light emitting diodes (LEDs), and the like.

[0327] 〔lens〕

[0328] The lens of the present disclosure is an example of the optical material of the present disclosure, and includes the above-mentioned resin of the present disclosure.

[0329] The lens of the present disclosure can be manufactured, for example, by the aforementioned cast polymerization.

[0330] The lens of the present disclosure may be formed of the resin of the present disclosure, or may include the resin of the present disclosure and other elements.

[0331] As other elements, other members, coatings provided on the resin of the present disclosure, and the like can be cited.

[0332] Examples of the lens of the present disclosure include eyeglass lenses, camera lenses, polarizing lenses, and the like.

[0333] Hereinafter, a spectacle lens will be described as an example of the lens of the present disclosure.

[0334] The eyeglass lens includes the resin of the present disclosure molded into a desired lens shape.

[0335] The eyeglass lens preferably further includes a coating layer provided on one or both surfaces of the resin.

[0336] Specific examples of the coating layer include a primer layer, a hard coating layer, an antireflection layer, an antifogging layer, an antifouling layer, a water-repellent layer, etc. These coating layers may be used alone or in a plurality of layers.

[0337] When coating is applied to both surfaces of the cured product, the same coating may be applied to each surface, or different coatings may be applied to each surface.

[0338] The components of the coating layer can be appropriately selected according to the purpose.

[0339] Examples of the coating component 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, antistatic agents, and the like.

[0340] Regarding the eyeglass lenses and coatings, for example, the descriptions of known documents such as Japanese Patent Application Publication No. 2002-194083 and International Publication No. 2017 / 047745 can be appropriately referred to.

[0341] 〔Reference method〕

[0342] Next, reference embodiments of each of the polymerizable composition of the present disclosure, the resin of the present disclosure, the molded article of the present disclosure, the optical material of the present disclosure, and the lens of the present disclosure are shown.

[0343] Reference methods include the following <1A> to <18A>.

[0344] <1A> A polymerizable composition comprising:

[0345] An episulfide compound represented by the following formula (1);

[0346] Polyiso(thio)cyanate compounds;

[0347] Polythiol compounds;

[0348] An epoxy compound (preferably an epoxy compound (X) containing one or more epoxy groups and no episulfide group in one molecule); and

[0349] Organic silicon compounds.

[0350] [Chemical formula 10]

[0351]

[0352] In formula (1), Y represents a substituted or unsubstituted straight-chain 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 alkylene arylene alkylene 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.

[0353] <2A> The polymerizable composition according to <1A>, wherein the organosilicon compound includes a polyether-modified organosilicon compound.

[0354] <3A> The polymerizable composition according to <1A>, wherein the organosilicon compound includes at least one selected from the group consisting of a polyether-modified organosilicon compound represented by the following formula (S1) and a polyether-modified organosilicon compound represented by the following formula (S2).

[0355] [Chemical formula 11]

[0356]

[0357] In formula (S1), m and n each independently represent an integer greater than 1. a and b each independently represent an integer greater than 0 (excluding the case where both a and b are 0). R1 ​​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.

[0358] In the general formula (2), p represents an integer greater than 1, and c, d, e, and f each independently represent an integer greater than 0 (excluding the case where c, d, e, and f are all 0). R2 and R3 each independently represent 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.

[0359] <4A> The polymerizable composition according to any one of <1A> to <3A>, wherein the epoxy compound includes an epoxy compound (X1) having two or more epoxy groups in one molecule.

[0360] <5A> The polymerizable composition according to any one of <1A> to <4A>, wherein the total number of moles of mercapto groups contained in the total amount of the polythiol compounds is denoted by M. S ,

[0361] The total number of moles of iso(thio)cyanate groups in the total amount of the polyiso(thio)cyanate compounds is defined as M. N ,

[0362] The total number of moles of episulfide groups contained in the total amount of episulfide compounds represented by the above formula (1) is defined as M E In the case of

[0363] (M S -M N ) / M E The ratio is greater than 0 and less than 0.20.

[0364] <6A> The polymerizable composition according to any one of <1A> to <5A>, wherein the polythiol compound comprises a compound 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( At least one member selected from the group consisting of mercaptomethyl)-1,4-dithiacyclohexane, bis(mercaptoethyl) sulfide, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiacyclohexane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiacyclohexane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiacyclopentane, and tris(mercaptomethylthio)methane.

[0365] <7A> The polymerizable composition according to any one of <1A> to <6A>, 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(isocyanatemethyl)cyclohexane, bis(isocyanatecyclohexyl)methane, 2,5-bis(isocyanatemethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatemethyl)bicyclo-[2.2.1]-heptane, toluene diisocyanate, 4,4′-diphenylmethane diisocyanate, and phenylene diisocyanate.

[0366] <8A> The polymerizable composition according to any one of <1A> to <7A>, further comprising a compound represented by the following formula (2).

[0367] (R 1 )4Y + X - …(2)

[0368] [In formula (2), the four R 1 Each independently represents a straight-chain 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.

[0369] <9A> The polymerizable composition according to any one of <1A> to <8A>, further comprising a tertiary amine compound.

[0370] <10A> The polymerizable composition according to <9A>, wherein the tertiary amine compound includes at least one of a compound represented by the following formula (3) and a compound represented by the following formula (4).

[0371] [Chemical formula 12]

[0372]

[0373] In formula (3), m R1s each independently represent a straight-chain 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.

[0374] In formula (4), R2, R3, and R4 each independently represent 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. R2 and R3 may be bonded to each other to form a ring.

[0375] <11A> The polymerizable composition according to <10A>, wherein the compound represented by the formula (3) is selected from 2-methylpyrazine, pyridine, α-methylpyridine, β-methylpyridine, γ-methylpyridine, 2,6-lutidine, 3,5-lutidine, 2,4,6-trimethylpyridine, 3

[0376] at least one selected from the group consisting of -chloropyridine, 2-ethylpyridine, and 3-ethylpyridine,

[0377] The compound represented by the formula (4) is at least one selected from the group consisting of triallylamine and trioctylamine.

[0378] <12A> The polymerizable composition according to any one of <1A> to <11A>, further comprising a Lewis acid compound.

[0379] <13A> The polymerizable composition according to <12A>, wherein the Lewis acid compound includes a compound represented by the following formula (5).

[0380] [Chemical formula 13]

[0381] (R4) c -Sn-X 4-c (5)

[0382] In formula (5), R4 represents an alkyl group having 1 to 4 carbon atoms, X represents a fluorine atom, a chlorine atom, a bromine atom, or -OC(=O)-R5, R5 represents an alkyl group having 1 to 11 carbon atoms, and c represents an integer of 1 to 3.

[0383] <14A> The polymerizable composition according to <13A>, wherein the compound represented by the formula (5) is at least one selected from the group consisting of dimethyltin dichloride, dibutyltin dichloride, and dibutyltin dilaurate.

[0384] <15A> Resin, which is <1> A cured product of the polymerizable composition according to any one of <14A> to <14A>.

[0385] <16A> A molded article comprising the resin described in <15A>.

[0386] <17A> An optical material comprising the resin described in <15A>.

[0387] <18A> A lens comprising the resin described in <15A>.

[0388] [Reference polymerizable composition]

[0389] The polymerizable composition of the reference embodiment contains:

[0390] An episulfide compound represented by formula (1);

[0391] Polyiso(thio)cyanate compounds;

[0392] Polythiol compounds;

[0393] An epoxy compound (X) containing one or more epoxy groups and no episulfide group in one molecule; and

[0394] Organic silicon compounds.

[0395] According to the polymerizable composition of the reference embodiment, a resin having reduced haze and excellent appearance can be produced.

[0396] Specifically, since the polymerizable composition containing the episulfide compound represented by formula (1), the polyiso(thio)cyanate compound, the polythiol compound, and the epoxy compound (X) further contains an organosilicon compound, the haze of the obtained resin can be reduced and the appearance can be improved.

[0397] Furthermore, the obtained resin is also excellent in heat resistance.

[0398] The episulfide compound represented by the formula (1) is a component that is a prerequisite for obtaining a resin having a high refractive index.

[0399] The polyiso(thio)cyanate compound, the polythiol compound, and the epoxy compound (X) are components for ensuring the strength of the above-mentioned high refractive index resin.

[0400] In the polymerizable composition of the reference embodiment, the "compound (b) which is at least one selected from the group consisting of an acid (b1) having a pKa of less than 2.0 and an acid anhydride (b2) having a pKa of less than 2.0" described in the section of the polymerizable composition of the present disclosure is an optional component, and the "organic silicon compound" described in the section of the polymerizable composition of the present disclosure is an essential component.

[0401] Except for this point, the polymerizable composition of the reference embodiment is the same as the polymerizable composition of the present disclosure, and the preferred embodiments are also the same.

[0402] Hereinafter, each component that may be contained in the polymerizable composition of the reference embodiment will be described.

[0403] <Episulfide compound represented by formula (1)>

[0404] The polymerizable composition of the reference embodiment contains at least one episulfide compound represented by formula (1).

[0405] The episulfide compound represented by formula (1) in the polymerizable composition of the reference embodiment is the same as the episulfide compound represented by formula (1) in the polymerizable composition of the present disclosure, and the preferred embodiments and preferred contents are also the same.

[0406] <Polyiso(thio)cyanate compounds>

[0407] The polymerizable composition of the reference embodiment contains at least one polyiso(thio)cyanate compound.

[0408] The polyiso(thio)cyanate compound in the polymerizable composition of the reference embodiment is the same as the polyiso(thio)cyanate compound in the polymerizable composition of the present disclosure, and the preferred embodiments and preferred contents are also the same.

[0409] <Polythiol Compound>

[0410] The polymerizable composition of the reference embodiment contains at least one polythiol compound.

[0411] The polythiol compound in the polymerizable composition of the reference embodiment is the same as the polythiol compound in the polymerizable composition of the present disclosure, and the preferred embodiments and preferred contents are also the same.

[0412] <Epoxy Compounds>

[0413] The polymerizable composition of the reference embodiment contains at least one epoxy compound.

[0414] The epoxy compound contained in the polymerizable composition of the reference embodiment is the same as the epoxy compound contained in the polymerizable composition of the present disclosure, and the preferred embodiment and the preferred content are also the same.

[0415] <(M S -M N ) / M E >

[0416] In the polymerizable composition of the reference embodiment (M S -M N ) / M E The preferred range of the ratio is the same as that of the polymerizable composition of the present disclosure (M S -M N ) / M E The preferred range of the ratio is the same.

[0417] <Organic silicon compounds>

[0418] The polymerizable composition of the reference embodiment contains at least one organosilicon compound.

[0419] The organosilicon compound contributes to the effect of improving the appearance of the resin. Specifically, as described above, since the polymerizable composition containing the polyiso(thio)cyanate compound, the polythiol compound, and the epoxy compound (X) further contains the organosilicon compound, the appearance of the obtained resin is improved.

[0420] In addition, the organosilicon compound also functions as a release agent.

[0421] The organosilicon compound in the polymerizable composition of the reference embodiment is the same as the organosilicon compound that may be contained in the polymerizable composition of the present disclosure, and the preferred embodiments and the preferred content are also the same.

[0422] <Compound represented by formula (2)>

[0423] The polymerizable composition of the reference embodiment preferably contains a compound represented by formula (2).

[0424] When the polymerizable composition of the reference embodiment contains the compound represented by formula (2), the compound represented by formula (2) contained may be only one kind or two or more kinds.

[0425] The compound represented by formula (2) that can be contained in the polymerizable composition of the reference embodiment is the same as the compound represented by formula (2) that can be contained in the polymerizable composition of the present disclosure, and the preferred embodiment and the preferred content are also the same.

[0426] <Tertiary amine compound>

[0427] The polymerizable composition of the reference embodiment preferably contains a tertiary amine compound.

[0428] When the polymerizable composition of the reference embodiment contains a tertiary amine compound, the tertiary amine compound contained may be only one kind or two or more kinds.

[0429] The tertiary amine compound that can be contained in the polymerizable composition of the reference embodiment is the same as the tertiary amine compound that can be contained in the polymerizable composition of the present disclosure, and the preferred embodiment and the preferred content are also the same.

[0430] The polymerizable composition of the reference embodiment may contain other compounds other than the compounds represented by the above-mentioned formulae (2) to (4) as a curing catalyst.

[0431] The curing catalyst can be selected from the curing catalysts described in, for example, paragraphs 0029 to 0033 of JP-A-2002-194083.

[0432] <Lewis acid compound>

[0433] The polymerizable composition of the reference embodiment preferably contains a Lewis acid compound.

[0434] Thereby, the pot life of the polymerizable composition can be further improved.

[0435] When the polymerizable composition of the reference embodiment contains a Lewis acid compound, the Lewis acid compound contained may be only one kind or two or more kinds.

[0436] The Lewis acid compound that can be contained in the polymerizable composition of the reference embodiment is the same as the tertiary amine compound that can be contained in the polymerizable composition of the present disclosure, and the preferred embodiments and preferred contents are also the same.

[0437] <Other ingredients>

[0438] The polymerizable composition of the reference embodiment may contain other components in addition to the above-mentioned components.

[0439] Examples of other components include bluing agents, resins (eg, acrylic resins, olefin resins, etc.), crosslinking agents, light stabilizers, ultraviolet absorbers, antioxidants, anti-coloring agents, dyes, fillers, and internal mold release agents.

[0440] As other components, known components can be used.

[0441] Regarding other components, for example, Japanese Patent Application Laid-Open No. 2002-194083 can be appropriately referred to.

[0442] The polymerizable composition of the reference embodiment can be obtained by mixing the above-mentioned respective components (raw materials).

[0443] The order of mixing the components (raw materials) is not particularly limited, and all the raw materials may be put into a container at once and mixed, or the raw materials may be put into a container in multiple portions and mixed.

[0444] In addition, a part of the monomers in the polymerizable composition of the reference embodiment may be polymerized during the mixing to form a prepolymer.

[0445] The monomers in the polymerizable composition of the reference embodiment are at least the episulfide compound, the polyiso(thio)cyanate compound, and the polythiol compound represented by formula (1). In addition to these compounds, the epoxy compound (X) may also function as a monomer.

[0446] 〔Resin, molded article〕

[0447] The resin of the reference embodiment is a cured product of the polymerizable composition of the reference embodiment described above.

[0448] The molded article of the reference embodiment includes the resin of the reference embodiment.

[0449] That is, the resin of the reference embodiment can be produced by curing the polymerizable composition of the reference embodiment described above, specifically, by polymerizing and curing the monomers in the polymerizable composition of the reference embodiment.

[0450] As a method for polymerizing the monomers in the polymerizable composition of the reference embodiment, for example, cast polymerization can be cited. By cast polymerization, a molded article of the present disclosure containing the resin of the reference embodiment (that is, a cured product of the polymerizable composition of the reference embodiment) can be obtained.

[0451] In cast polymerization, first, the polymerizable composition according to one example of the reference embodiment is injected between a pair of molds held by a spacer, a tape, etc. At this time, a degassing treatment, a filtration treatment, etc. may be performed as necessary.

[0452] Next, the monomers in the composition injected into the mold are polymerized, thereby curing the composition in the mold to obtain a cured product. Next, the cured product is removed from the mold to obtain a cured product.

[0453] The polymerization of the monomers can be carried out by heating the polymerizable composition of the reference embodiment. The heating can be carried out, for example, using a heating device having a mechanism for heating a heating object in an oven, water, or the like.

[0454] The polymerization conditions (e.g., polymerization temperature, polymerization time, etc.) for polymerizing the monomers in the polymerizable composition of the reference embodiment can be appropriately set in consideration of the composition composition, the type and amount of the monomers in the composition, the type and amount of the polymerization catalyst in the composition, the shape of the mold, etc.

[0455] Examples of the polymerization temperature include -50°C to 150°C and 10°C to 150°C.

[0456] Examples of the polymerization time include 1 hour to 200 hours and 1 hour to 80 hours.

[0457] The resin of the reference embodiment or a molded article containing the resin may be obtained by subjecting the monomers to polymerization and then subjecting them to treatment such as annealing.

[0458] Examples of the annealing temperature include 50°C to 150°C, 90°C to 140°C, and 100°C to 130°C.

[0459] 〔Optical Materials〕

[0460] The optical material of the reference embodiment includes the resin of the reference embodiment described above.

[0461] The optical material of the reference form can be produced, for example, by the aforementioned cast polymerization.

[0462] The refractive index of the optical material in the reference mode (n e ) is preferably 1.67 to 1.74, more preferably 1.69 to 1.73. e) For example, the refractive index at each wavelength of 546.1 nm (mercury e-line), 480.0 nm (Cd F' line), and 643.9 nm (Cd C' line) can be measured using a Pulfrich refractometer KPR-30 manufactured by Shimadzu Corporation, and the refractive index can be calculated based on these measurement results.

[0463] The optical material of the reference type may be formed of the resin of the reference type, or may include the resin of the reference type and other elements.

[0464] As other elements, other members, coatings provided on the resin of the reference embodiment, and the like can be cited.

[0465] Examples of the optical material of the reference embodiment include lenses (for example, eyeglass lenses, camera lenses, polarizing lenses, etc.), light emitting diodes (LEDs), and the like.

[0466] 〔lens〕

[0467] The reference lens is an example of a reference optical material, and includes the above-mentioned reference resin.

[0468] The lens of the reference type can be produced, for example, by the aforementioned cast polymerization.

[0469] The reference type lens may be formed of the reference type resin, or may include the reference type resin and other elements.

[0470] As other elements, other members, coatings provided on the resin of the reference embodiment, and the like can be cited.

[0471] Examples of the reference lens include eyeglass lenses, camera lenses, and polarizing lenses.

[0472] Hereinafter, a spectacle lens will be described as an example of a reference lens.

[0473] The eyeglass lens includes the resin of the present disclosure molded into a desired lens shape.

[0474] The eyeglass lens preferably further includes a coating layer provided on one or both surfaces of the resin.

[0475] Specific examples of the coating layer include a primer layer, a hard coating layer, an antireflection layer, an antifogging layer, an antifouling layer, a water-repellent layer, etc. These coating layers may be used alone or in a plurality of layers.

[0476] When coating is applied to both surfaces of the cured product, the same coating may be applied to each surface, or different coatings may be applied to each surface.

[0477] The components of the coating layer can be appropriately selected according to the purpose.

[0478] Examples of the coating component 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, antistatic agents, and the like.

[0479] Regarding the eyeglass lenses and coatings, for example, the descriptions of known documents such as Japanese Patent Application Publication No. 2002-194083 and International Publication No. 2017 / 047745 can be appropriately referred to.

[0480] Example

[0481] Hereinafter, examples of the present disclosure are shown, but the present disclosure is not limited to the following examples. It should be noted that, unless otherwise specified, "parts" are based on mass.

[0482] [Example 1]

[0483] <Preparation of polymerizable composition>

[0484] Mix and dissolve the following ingredients at 20°C:

[0485] 25.4 parts by mass of xylylene diisocyanate (hereinafter also referred to as "PI-2") as a polyiso(thio)cyanate compound,

[0486] 0.010 parts by mass of (±)-10-camphorsulfonic acid (hereinafter also referred to as "CSA") as compound (b),

[0487] 1.5 parts by mass of bisphenol A diglycidyl ether (hereinafter also referred to as "BGPP") as the epoxy compound (X),

[0488] 0.04 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)),

[0489] 0.005 parts by mass of "KF-615A" (trade name; KF-615A manufactured by Shin-Etsu Silicone Co., Ltd.) as an organic silicon compound, and

[0490] 1.000 parts by mass of "Tinuvin PS" (manufactured by BASF Japan Ltd.) as an ultraviolet absorber.

[0491] For the obtained solution,

[0492] After 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) was charged,

[0493] A mixture of 32.0 parts by mass of a polythiol composition (hereinafter also referred to as "PT-1") containing 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 as main components and 0.03 parts by mass of 3,5-lutidine as a curing catalyst, which is a compound represented by formula (3), was charged and mixed at 5 to 10° C. to obtain a polymerizable composition.

[0494] 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.

[0495] <Production of Resin Molded Body>

[0496] The polymerizable composition obtained above was fully degassed under a reduced pressure condition of 600 Pa until foaming was no longer observed.

[0497] The degassed polymerizable composition was filtered using a 1 μm PTFE (polytetrafluoroethylene) filter and then injected between a pair of glass molds fixed with tape. Next, the pair of glass molds injected with the polymerizable composition were placed in an oven, and the temperature in the oven was slowly raised from 20° C. to 120° C. over 23 hours. Through the above process, the monomers in the degassed polymerizable composition (i.e., the episulfide compound, polyiso(thio)cyanate compound, polythiol composition, etc. represented by formula (1)) were polymerized to form a resin molded body (i.e., a molded body of a resin that is a cured product of the polymerizable composition) between the pair of glass molds.

[0498] Next, the oven was cooled, and after cooling, the pair of glass molds were taken out of the oven, and then the resin molded body was taken out from the pair of glass molds to obtain a resin molded body. The obtained resin molded body was annealed at 120° C. for 1 hour to obtain a lens containing resin.

[0499] <Evaluation>

[0500] The polymerizable composition or the resin molded article was subjected to the following evaluations.

[0501] The results are shown in Table 1.

[0502] ·Viscosity of polymerizable composition

[0503] The polymerizable composition was stirred at 10° C. for 1 hour, and the viscosity was measured using a Brookfield Company B-type viscometer (spindle No. 62).

[0504] The smaller the numerical value of the viscosity is, the more excellent the length of pot life is.

[0505] Heat resistance

[0506] 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 operation as in the above-mentioned <Production of Resin Molded Article> except that the shape and size of the pair of glass molds were appropriately selected.

[0507] The glass transition temperature Tg of the sample was measured using a thermomechanical analyzer TMA-60 manufactured by Shimadzu Corporation by the TMA penetration method (50 g load, needle tip 0.5 mmφ, heating rate 10°C / min) as an indicator of heat resistance.

[0508] The higher the glass transition temperature Tg, the better the heat resistance.

[0509] Mold release

[0510] In the production of the resin molded body, after the resin molded body was formed, the releasability when the resin molded body was removed from the pair of glass molds was confirmed, and the releasability was evaluated according to the following evaluation criteria.

[0511] In the following evaluation criteria, the grade with the best mold release property was A.

[0512] -Evaluation criteria for mold release properties-

[0513] A: The resin molded body was naturally released from the pair of glass molds by cooling the oven in which the resin molded body was formed to room temperature.

[0514] B: Even when the oven in which the resin molded body was formed was cooled to room temperature, the resin molded body was not naturally released from the pair of glass molds, but the resin molded body could be released from the mold by applying force.

[0515] C: Even after the oven in which the resin molded body was formed was cooled to room temperature, the resin molded body was not naturally released from the pair of glass molds, and the resin molded body could be released by inserting a wedge at the edge of the resin molded body.

[0516] D: Even after the oven in which the resin molded body was formed was cooled to room temperature, the resin molded body was not naturally released from the pair of glass molds, and even when a wedge was placed at the edge of the resin molded body, the resin molded body could not be released from the mold.

[0517] YI (Yellow Index; Yellowness)

[0518] The shape and size of a pair of glass molds were appropriately selected, and the same operation as in the above-mentioned <Production of Resin Molded Body> was performed to obtain a disc-shaped test piece having a thickness of 2.5 mm and a diameter of 75 mm. The YI (yellowness index; yellowness) was obtained using a spectrophotometer CM-5 manufactured by Konica Minolta, Inc. for the obtained test piece.

[0519] The smaller the YI value is, the better the hue of the lens is.

[0520] ·Fog

[0521] The shape and size of a pair of glass molds were appropriately selected, and the same operation as the above-mentioned <Production of Resin Molded Body> was performed to obtain a disc-shaped test piece with a thickness of 2.5 mm and a diameter of 75 mm. The haze value of the resin was measured using a haze meter (model: NDH 2000) manufactured by Nippon Denshoku Industries Co., Ltd. for the obtained test piece.

[0522] The smaller the haze value is, the better the transparency of the lens is.

[0523] Appearance

[0524] The test piece (resin molded article) used for the measurement of the above-mentioned YI and the like was visually observed, and the appearance of the test piece (resin molded article) was evaluated according to the following evaluation criteria.

[0525] In the following evaluation criteria, the most excellent grade in appearance is A.

[0526] - Evaluation criteria for appearance -

[0527] A: No pattern is visible at all, and the appearance is good.

[0528] B: Although stripe-like or spot-like patterns are visible when observed from the closest distance, no patterns are visible when observed from a distance of 50 cm.

[0529] C: The pattern is observed when observed from a position 50 cm away.

[0530] Wave tendons

[0531] As a pair of glass molds, a glass mold with a base curve of 6 was used. In addition, the same operation as the above-mentioned <Production of Resin Molded Body> was performed to produce a semi-finished lens with a thickness of 10 mm (hereinafter also referred to as "lens"). The obtained lens was visually observed for ribs using a high-pressure mercury lamp (manufactured by USHIO INC., Optical ModuleX).

[0532] Based on the results of visual observation, striae in the lens were evaluated according to the following evaluation criteria.

[0533] In the following evaluation criteria, the level in which ribs are most suppressed is A.

[0534] -Evaluation criteria for ribs-

[0535] A: Even with a high-pressure mercury lamp, no ribs can be observed.

[0536] B: By using a high-pressure mercury lamp, ribs were observed, and ribs were observed only within a range of 10 mm from the end surface portion of the lens toward the center.

[0537] C: By using a high-pressure mercury lamp, ribs were observed, and ribs were observed within a range of 30 mm from the end surface portion of the lens toward the center.

[0538] D: Even without using a high-pressure mercury lamp, ribs are observed.

[0539] [Examples 2 to 4]

[0540] Except for changing the kind and / or amount of compound (b) as shown in Table 1, the same operation as in Example 1 was carried out.

[0541] The results are shown in Table 1.

[0542] The compounds (b) in Examples 1 to 4 are as follows.

[0543] ·CSA: (±)-10-Camphorsulfonic acid

[0544] MSA: Methanesulfonic acid

[0545] PTSA: p-Toluenesulfonic anhydride

[0546] [Comparative Example 1]

[0547] The same operation as in Example 1 was carried out except that the compound (b) was not used.

[0548] The results are shown in Table 1.

[0549] In Table 1, “-” means that the corresponding component is not contained.

[0550] [Table 1]

[0551]

[0552] As shown in Table 1, in Examples 1 to 4 using a polymerizable composition containing an episulfide compound represented by formula (1), a polyiso(thio)cyanate compound, a polythiol compound, an epoxy compound (X) containing one or more epoxy groups in one molecule and no episulfide group, and at least one compound (b) selected from the group consisting of an acid (b1) having a pKa of less than 2.0 and an acid anhydride (b2) having a pKa of less than 2.0, it is possible to produce a resin molded product in which striae are suppressed, as compared with Comparative Example 1.

[0553] The resin molded bodies obtained in Examples 1 to 4 were also superior in heat resistance and had reduced haze compared to the resin molded body obtained in Comparative Example 1.

[0554] In addition, compared with the polymerizable composition obtained in Comparative Example 1, the viscosity of the polymerizable compositions obtained in Examples 1 to 4 was reduced.

[0555] [Comparative Example 2]

[0556] A polymerizable composition of Comparative Example 2 having a composition obtained by removing the polyiso(thio)cyanate compound and the epoxy compound (X) from the composition of the polymerizable composition of Example 1 was prepared, and a resin molded body was prepared using the obtained polymerizable composition in the same manner as the preparation of the resin molded body in Example 1. The obtained resin molded body tended to be insufficient in strength compared with the resin molded body obtained in Example 1.

[0557] Next, a specific example of the polymerizable composition of the aforementioned reference embodiment (i.e., a polymerizable composition containing an episulfide compound represented by formula (1), a polyiso(thio)cyanate compound, a polythiol compound, an epoxy compound (X) containing one or more epoxy groups in one molecule and no episulfide group, and an organosilicon compound) is shown as a "reference example", and a comparative example for the "reference example" is shown as a "reference comparative example".

[0558] 〔Reference Example 1〕

[0559] <Preparation of polymerizable composition>

[0560] Mix and dissolve the following ingredients at 20°C:

[0561] 25.4 parts by mass of xylylene diisocyanate (hereinafter also referred to as "PI-2") as a polyiso(thio)cyanate compound,

[0562] 1.5 parts by mass of bisphenol A diglycidyl ether (hereinafter also referred to as "BGPP") as the epoxy compound (X),

[0563] 0.04 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)),

[0564] 0.005 parts by mass of "KF-615A" (trade name; KF-615A manufactured by Shin-Etsu Silicone Co., Ltd.) as an organic silicon compound, and

[0565] 1.000 parts by mass of "Tinuvin PS" (manufactured by BASF Japan Ltd.) as an ultraviolet absorber.

[0566] For the obtained solution,

[0567] After 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) was charged,

[0568] A mixture of 32.0 parts by mass of a polythiol composition (hereinafter also referred to as "PT-1") containing 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 as main components and 0.03 parts by mass of 3,5-lutidine as a curing catalyst, which is a compound represented by formula (3), was charged and mixed at 5 to 10° C. to obtain a polymerizable composition.

[0569] <Production of Resin Molded Body>

[0570] The polymerizable composition obtained above was fully degassed under a reduced pressure condition of 600 Pa until foaming was no longer observed.

[0571] The degassed polymerizable composition was filtered using a 1 μm PTFE (polytetrafluoroethylene) filter and then injected between a pair of glass molds fixed with tape. Next, the pair of glass molds injected with the polymerizable composition were placed in an oven, and the temperature in the oven was slowly raised from 20° C. to 120° C. over 23 hours. Through the above process, the monomers in the degassed polymerizable composition (i.e., the episulfide compound, polyiso(thio)cyanate compound, polythiol composition, etc. represented by formula (1)) were polymerized to form a resin molded body (i.e., a molded body of a resin that is a cured product of the polymerizable composition) between the pair of glass molds.

[0572] Next, the oven was cooled, and after cooling, the pair of glass molds were taken out of the oven, and then the resin molded body was taken out from the pair of glass molds to obtain a resin molded body. The obtained resin molded body was annealed at 120° C. for 1 hour to obtain a lens containing resin.

[0573] <Evaluation>

[0574] The polymerizable composition or the resin molded article was subjected to the following evaluations.

[0575] The results are shown in Table 2.

[0576] Heat resistance

[0577] 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 operation as in the above-mentioned <Production of Resin Molded Article> except that the shape and size of the pair of glass molds were appropriately selected.

[0578] The glass transition temperature Tg of the sample was measured using a thermomechanical analyzer TMA-60 manufactured by Shimadzu Corporation by the TMA penetration method (50 g load, needle tip 0.5 mmφ, heating rate 10°C / min) as an indicator of heat resistance.

[0579] The higher the glass transition temperature Tg, the better the heat resistance.

[0580] Mold release

[0581] In the production of the resin molded body, after the resin molded body was formed, the releasability when the resin molded body was removed from the pair of glass molds was confirmed, and the releasability was evaluated according to the following evaluation criteria.

[0582] In the following evaluation criteria, the grade with the best mold release property was A.

[0583] -Evaluation criteria for mold release properties-

[0584] A: The resin molded body was naturally released from the pair of glass molds by cooling the oven in which the resin molded body was formed to room temperature.

[0585] B: Even when the oven in which the resin molded body was formed was cooled to room temperature, the resin molded body was not naturally released from the pair of glass molds, but the resin molded body could be released from the mold by applying force.

[0586] C: Even after the oven in which the resin molded body was formed was cooled to room temperature, the resin molded body was not naturally released from the pair of glass molds, and the resin molded body could be released by inserting a wedge at the edge of the resin molded body.

[0587] D: Even after the oven in which the resin molded body was formed was cooled to room temperature, the resin molded body was not naturally released from the pair of glass molds, and even when a wedge was placed at the edge of the resin molded body, the resin molded body could not be released from the mold.

[0588] YI (yellowness index; yellowness)

[0589] The shape and size of a pair of glass molds were appropriately selected, and the same operation as in the above-mentioned <Production of Resin Molded Body> was performed to obtain a disc-shaped test piece having a thickness of 2.5 mm and a diameter of 75 mm. The YI (yellowness index; yellowness) was obtained using a spectrophotometer CM-5 manufactured by Konica Minolta, Inc. for the obtained test piece.

[0590] The smaller the YI value is, the better the hue of the lens is.

[0591] ·Fog

[0592] The shape and size of a pair of glass molds were appropriately selected, and the same operation as the above-mentioned <Production of Resin Molded Body> was performed to obtain a disc-shaped test piece with a thickness of 2.5 mm and a diameter of 75 mm. The haze value of the resin was measured using a haze meter (model: NDH 2000) manufactured by Nippon Denshoku Industries Co., Ltd. for the obtained test piece.

[0593] The smaller the haze value is, the better the transparency of the lens is.

[0594] Appearance

[0595] The test piece (resin molded article) used for the measurement of the above-mentioned YI and the like was visually observed, and the appearance of the test piece (resin molded article) was evaluated according to the following evaluation criteria.

[0596] In the following evaluation criteria, the most excellent grade in appearance is A.

[0597] - Evaluation criteria for appearance -

[0598] A: No pattern is visible at all, and the appearance is good.

[0599] B: Although stripe-like or spot-like patterns are visible when observed from the closest distance, no patterns are visible when observed from a distance of 50 cm.

[0600] C: The pattern is observed when observed from a position 50 cm away.

[0601] <Viscosity of Polymerizable Composition>

[0602] The polymerizable composition was stirred at 10° C. for 1 hour, and the viscosity was measured using a Brookfield Company B-type viscometer (spindle No. 62).

[0603] The smaller the numerical value of the viscosity is, the more excellent the length of pot life is.

[0604] [Reference Examples 2 to 4]

[0605] Except for changing the kind of the organosilicon compound as shown in Table 2, the same operation as in Reference Example 1 was carried out.

[0606] The results are shown in Table 2.

[0607] In Table 2, “-” means that the corresponding component is not contained.

[0608] The organosilicon compounds in Reference Examples 1 to 4 are as follows.

[0609] · KF-615A ... manufactured by Shin-Etsu Silicone Co., Ltd. Corresponding to compound (S1). The molar fraction of the silicone unit [i.e., (m+n) / (m+n+a+b)] was 0.16, and the molar fraction of the polyether unit [i.e., (a+b) / (a+b+m+n)] was 0.84.

[0610] · KF-351A ... manufactured by Shin-Etsu Silicone Co., Ltd. Corresponding to compound (S1). The molar fraction of the silicone unit [i.e., (m+n) / (m+n+a+b)] was 0.18, and the molar fraction of the polyether unit [i.e., (a+b) / (a+b+m+n)] was 0.82.

[0611] SH-3773M ... manufactured by Shin-Etsu Silicone Co., Ltd. Corresponding to a mixture of compound (S1) and compound (S2). The molar fraction of the silicone unit [i.e., (m+n+p) / (m+n+p+a+b+c+d+e+f)] is 0.44, and the molar fraction of the polyether unit [i.e., (a+b+c+d+e+f) / (a+b+c+d+e+f+m+n+p)] is 0.56.

[0612] ·KF-96 ... manufactured by Shin-Etsu Silicone Co., Ltd. Dimethyl silicone oil (unmodified dimethyl polysiloxane).

[0613] [Reference Comparative Example 1]

[0614] The same operation as in Reference Example 1 was carried out except that “KF-615A” (0.005 parts by mass) as the organosilicon compound was replaced with “ZELEC UN” (trade name; acidic phosphate release agent manufactured by Stepan) (0.03 parts by mass).

[0615] The results are shown in Table 2.

[0616] [Table 2]

[0617]

[0618] As shown in Table 2, in Reference Examples 1 to 4 using a polymerizable composition containing an episulfide compound represented by formula (1), a polyiso(thio)cyanate compound, a polythiol compound, an epoxy compound, and an organosilicon compound, a resin molded body having an excellent appearance and reduced haze can be produced as compared with Reference Comparative Example 1.

[0619] The resin molded bodies obtained in Reference Examples 1 to 4 also have excellent heat resistance compared to the resin molded body obtained in Reference Comparative Example 1.

[0620] Among Reference Examples 1 to 4, Reference Examples 1 to 3 using a polyether-modified silicone compound were more excellent in mold release properties when producing a resin molded article than Reference Example 4 using an unmodified silicone compound (dimethylpolysiloxane).

[0621] [Reference Comparative Example 2]

[0622] A polymerizable composition of Reference Comparative Example 2 having a composition obtained by removing a polyiso(thio)cyanate compound and an epoxy compound (X) from the composition of the polymerizable composition of Reference Example 1 was prepared, and a resin molded body was prepared using the obtained polymerizable composition in the same manner as in the preparation of the resin molded body in Reference Example 1. The obtained resin molded body tended to have insufficient strength compared to the resin molded body obtained in Reference Example 1.

[0623] The entire disclosure of Japanese Patent Applications No. 2022-121963 and No. 2022-121964 filed on July 29, 2022 is incorporated into this specification by reference.

[0624] All documents, patent applications, and technical standards described in this specification are incorporated into this specification by reference to the same extent as if each document, patent application, and technical standard was specifically and individually described.

Claims

1. A polymerizable composition comprising: An episulfide compound represented by the following formula (1); Polyiso(thio)cyanate compounds; Polythiol compounds; Epoxides; and at least one compound (b) selected from the group consisting of an acid (b1) having a pKa of less than 2.0 and an acid anhydride (b2) having a pKa of less than 2.0, [Chemical formula 1] In formula (1), Y represents a substituted or unsubstituted straight-chain 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 alkylene arylene alkylene 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 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.

3. The polymerizable composition according to claim 1, wherein The acid (b1) comprises at least one selected from the group consisting of 10-camphorsulfonic acid, methanesulfonic acid, and p-toluenesulfonic acid, The acid anhydride (b2) includes at least one selected from the group consisting of 10-camphorsulfonic anhydride, methanesulfonic anhydride, and p-toluenesulfonic anhydride.

4. The polymerizable composition according to claim 1, wherein The epoxy compound includes an epoxy compound (X) having one or more epoxy groups and no episulfide group in one molecule.

5. The polymerizable composition according to claim 1, wherein The epoxy compound includes an epoxy compound (X1) having two or more epoxy groups in one molecule.

6. The polymerizable composition according to claim 1, wherein The total number of moles of mercapto groups contained in the total amount of the polythiol compound is defined as M S , The total number of moles of iso(thio)cyanate groups in the total amount of the polyiso(thio)cyanate compounds is defined as M. N , The total number of moles of episulfide groups contained in the total amount of episulfide compounds represented by the formula (1) is defined as M E In the case of (M S -M N ) / M E The ratio is greater than 0 and less than 0.

20.

7. The polymerizable composition according to claim 1, wherein The polythiol compound comprises 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-dithiacyclohexane, At least one selected from the group consisting of oxadiazine, 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-dithiane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, and tris(mercaptomethylthio)methane.

8. The polymerizable composition according to claim 1, 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(isocyanate methyl)cyclohexane, bis(isocyanate cyclohexyl)methane, 2,5-bis(isocyanate methyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanate methyl)bicyclo-[2.2.1]-heptane, toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenylene diisocyanate.

9. The polymerizable composition according to claim 1, further comprising a tertiary amine compound.

10. The polymerizable composition according to claim 9, wherein The tertiary amine compound includes at least one of a compound represented by the following formula (3) and a compound represented by the following formula (4), [Chemical formula 2] In formula (3), m R1s each independently represent 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), R2, R3, and R4 each independently represent a straight-chain 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; R2 and R3 may be bonded to each other to form a ring.

11. The polymerizable composition according to claim 10, wherein The compound represented by the formula (3) is at least one selected from the group consisting of 2-methylpyrazine, pyridine, α-methylpyridine, β-methylpyridine, γ-methylpyridine, 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. 12 . The polymerizable composition according to claim 1 , further comprising a Lewis acid compound.

13. The polymerizable composition according to claim 12, wherein The Lewis acid compound includes a compound represented by the following formula (5): [Chemical formula 3] (R4) c —Sn—X 4-c (5) In formula (5), R4 represents an alkyl group having 1 to 4 carbon atoms, X represents a fluorine atom, a chlorine atom, a bromine atom, or -OC(=O)-R5, R5 represents an alkyl group having 1 to 11 carbon atoms, and c represents an integer of 1 to 3.

14. The polymerizable composition according to claim 13, wherein The compound represented by the formula (5) is at least one selected from the group consisting of dimethyltin dichloride, dibutyltin dichloride, and dibutyltin dilaurate.

15. The polymerizable composition according to claim 1, further comprising an organosilicon compound.

16. A resin which is a cured product of the polymerizable composition according to any one of claims 1 to 15.

17. A molded article comprising the resin according to claim 16.

18. An optical material comprising the resin according to claim 16.

19. A lens comprising the resin according to claim 16.

Images