Polymer compositions, resins, molded articles, optical materials, and lenses

Abstract

A polymerizable composition comprising a cyclic sulfur compound, a polyisocyanate compound, a polythiol compound, and an epoxy compound (X) containing one or more epoxy groups and not containing cyclic sulfur groups in one molecule, as represented by formula (1). In formula (1), Y represents a substituted or unsubstituted linear hydrocarbon group having 1 to 4 carbon atoms, a substituted or unsubstituted branched hydrocarbon group having 2 to 4 carbon atoms, a substituted or unsubstituted cyclic hydrocarbon group having 3 to 6 carbon atoms, a substituted or unsubstituted 1,4-dithionecyclohexyl group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted arylene group, m represents an integer from 0 to 2, and n represents an integer from 0 to 3.

Description

Technical Field

[0001] This disclosure relates to polymeric compositions, resins, molded articles, optical materials, and lenses. Background Technology

[0002] Compared to inorganic lenses, plastic lenses are lighter and less prone to breakage, and can be stained. As a result, they have become increasingly popular in recent years for applications such as eyeglass lenses and camera lenses.

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

[0004] For example, in Patent Document 1, a method for adjusting the polymerization rate and improving the heat resistance of a resin optical material with a sufficiently high refractive index and a good Abbe number is disclosed. The resin composition comprises a compound having a specific thiohexacyclopropane ring (i.e., a specific cyclic sulfur compound), a compound having one or more epoxy groups in one molecule, and a polymerization catalyst.

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

[0006] The problem that the invention aims to solve

[0007] However, for resins obtained using compositions containing cyclic sulfur compounds (hereinafter also referred to as "polymeric compositions"), it is sometimes required to further increase the strength while maintaining a high refractive index.

[0008] One aim of this disclosure is to provide polymerizable compositions capable of manufacturing resins with high refractive index and excellent strength, as well as resins with high refractive index and excellent strength, molded articles, optical materials, and lenses.

[0009] Methods for solving problems

[0010] The means to solve the above problems include the following methods.

[0011] <1> Polymerizable composition comprising:

[0012] The cyclic sulfur compound represented by the following formula (1),

[0013] Polyisocyanate compounds,

[0014] Polythiol compounds, and

[0015] An epoxy compound (X) containing one or more epoxy groups and no cyclic sulfide groups in one molecule.

[0016] [Chemical Formula 1]

[0017]

[0018] In formula (1), Y represents a substituted or unsubstituted straight-chain hydrocarbon group with 1 to 4 carbon atoms, a substituted or unsubstituted branched hydrocarbon group with 2 to 4 carbon atoms, a substituted or unsubstituted cyclic hydrocarbon group with 3 to 6 carbon atoms, a substituted or unsubstituted 1,4-dithionecyclohexyl group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted arylene group, m represents an integer from 0 to 2, and n represents an integer from 0 to 3.

[0019] <2> like <1> The polymeric composition wherein the aforementioned epoxy compound (X) comprises an epoxy compound (X1) containing two or more epoxy groups in one molecule.

[0020] <3> like <1> or <2> The polymerizable composition, wherein the total molar number of thiol groups contained in the total amount of the aforementioned polythiol compounds is set as M. S ,

[0021] Let M be the total number of moles of isocyanate groups in the total amount of the aforementioned polyisocyanate compounds. N ,

[0022] Let M be the total number of moles of cyclic sulfide groups contained in the total amount of the cyclic sulfide compound represented by the aforementioned formula (1). E In this case,

[0023] (M S -M N ) / M E The ratio is greater than 0 and less than 0.20.

[0024] <4> like <1> ~ <3> The polymerizable composition described in any one of the above-mentioned polythiol compounds comprises a compound selected from 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, and 2,5-bis(mercaptomethyl)-1 At least one of the following groups: 4-dithiacyclohexane, bis(mercaptoethyl) sulfide, 1,1,3,3-tetra(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiacyclohexane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiacyclobutane, 1,1,2,2-tetra(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, and tri(mercaptomethylthio)methane.

[0025] <5> like <1> ~ <4> The polymerizable composition according to any one of the above-mentioned polyisocyanate compounds comprises at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, phenylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenyl diisocyanate.

[0026] <6> like <1> ~ <5> The polymeric composition described in any one of the following methods further comprises a compound represented by formula (2).

[0027] (R 1 )4Y + X - …(2)

[0028] In equation (2), there are 4 R's. 1 Each group independently represents a straight-chain hydrocarbon group with 1 to 10 carbon atoms or a branched hydrocarbon group with 3 to 10 carbon atoms; X represents a halogen atom, and Y represents a nitrogen atom or a phosphorus atom.

[0029] <7> like <1> ~ <6> The polymeric composition described in any one of the above statements further contains a tertiary amine compound.

[0030] <8> like <7> The polymeric composition further comprises at least one of the compounds represented by formula (3) and formula (4).

[0031] [Chemical Formula 2]

[0032]

[0033] In formula (3), each of the m R1s independently represents a straight-chain alkyl group with 1 to 20 carbon atoms, a branched alkyl group with 3 to 20 carbon atoms, a cycloalkyl group with 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 from 0 to 5.

[0034] In formula (4), R2, R3, and R4 each independently represent a straight-chain alkyl group with 3 to 20 carbon atoms, a branched alkyl group with 3 to 20 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, or an allyl group. R2 and R3 can bond together to form a ring.

[0035] <9> like <8> The polymerizable composition wherein the compound represented by the aforementioned formula (3) is at least one selected from the group consisting of 2-methylpyrazine, pyridine, α-methylpyridine, β-methylpyridine, γ-methylpyridine, 2,6-dimethylpyridine, 3,5-dimethylpyridine, 2,4,6-trimethylpyridine, 3-chloropyridine, 2-ethylpyridine, and 3-ethylpyridine.

[0036] The compound represented by the aforementioned formula (4) is selected from at least one of the groups consisting of triallylamine and trioctylamine.

[0037] <10> like <1> ~ <9> The polymeric composition described in any one of the following statements further contains a Lewis acid compound.

[0038] <11> like <10> The polymeric composition wherein the aforementioned Lewis acid compound comprises a compound represented by the following formula (5).

[0039] [Chemical Formula 3]

[0040] (R4) c -Sn-X 4-c (5)

[0041] In formula (5), R4 represents an alkyl group with 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 with 1 to 11 carbon atoms, and c represents an integer from 1 to 3.

[0042] <12> like <11> The polymeric composition wherein the compound represented by the aforementioned formula (5) is at least one selected from the group consisting of dimethyltin dichloride, dibutyltin dichloride, and dibutyltin dilaurate.

[0043] <13> Resin, which is <1> ~ <12> The cured product of the polymeric composition described in any one of the above statements.

[0044] <14> Molded body, which includes <13> The aforementioned resin.

[0045] <15> Optical materials, which include <13> The aforementioned resin.

[0046] <16> Lens, which includes <13> The aforementioned resin.

[0047] Invention Effects

[0048] According to one aspect of this disclosure, polymerizable compositions capable of manufacturing resins with high refractive index and excellent strength, as well as resins with high refractive index and excellent strength, molded articles, optical materials, and lenses, can be provided. Detailed Implementation

[0049] In this public document, the range of values ​​indicated by “~” refers to the range of values ​​recorded before and after “~” as the lower and upper limits.

[0050] In this disclosure, the amount of each component in the composition, unless otherwise specified, refers to the total amount of the various substances present in the composition when multiple substances belonging to each component are present in the composition.

[0051] In the numerical ranges described in this disclosure, the upper or lower limit of one numerical range can be replaced with the upper or lower limit of another numerical range described in other stages. Furthermore, the upper or lower limit of a numerical range described in this disclosure can be replaced with the values ​​shown in the embodiments.

[0052] [Polymerizable Composition]

[0053] The polymeric compositions disclosed herein contain:

[0054] The cyclic sulfur compound represented by formula (1) described later,

[0055] Polyisocyanate compounds,

[0056] Polythiol compounds, and

[0057] An epoxy compound (X) containing one or more epoxy groups and no cyclic sulfide groups in one molecule.

[0058] According to the polymerizable composition disclosed herein, it is possible to manufacture a resin with high refractive index and excellent strength.

[0059] Here, it is assumed that the high refractive index of the resin is due to the effect of the cyclic sulfur compound (1) represented by formula (1) described later.

[0060] The strength of the resin is believed to be due to the effects of polyisocyanate compounds, polythiols, and epoxy compounds (X).

[0061] The following describes the components that may be contained in the polymeric compositions of this disclosure.

[0062] <Equation (1) represents cyclic sulfur compounds>

[0063] The polymeric compositions disclosed herein contain at least one cyclic sulfur compound represented by formula (1) below.

[0064] [Chemical Formula 4]

[0065]

[0066] In formula (1), Y represents a substituted or unsubstituted straight-chain hydrocarbon group with 1 to 4 carbon atoms, a substituted or unsubstituted branched hydrocarbon group with 2 to 4 carbon atoms, a substituted or unsubstituted cyclic hydrocarbon group with 3 to 6 carbon atoms, a substituted or unsubstituted 1,4-dithionecyclohexyl group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted arylene group, m represents an integer from 0 to 2, and n represents an integer from 0 to 3.

[0067] Examples of hydrocarbon groups represented by Y, which are straight-chain hydrocarbon groups with 1 to 4 carbon atoms that are substituted or unsubstituted, and branched hydrocarbon groups with 2 to 4 carbon atoms that are substituted or unsubstituted, include unsubstituted alkylene groups such as methylene, ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, and 1,4-butylene, as well as groups formed by substituting the aforementioned unsubstituted alkylene groups with substituents such as alkyl, hydroxyl, mercapto, carbonyl, and thiocarbonyl groups.

[0068] Examples of unsubstituted cyclic alkylene groups with 3 to 6 carbon atoms, represented by Y, include cyclopropylene, 1,2-cyclobutylene, 1,3-cyclobutylene, 1,2-cyclopentylene, 1,3-cyclopentylene, 1,2-cyclohexylene, 1,3-cyclohexylene, and 1,4-cyclohexylene, as well as groups formed by substituting the aforementioned unsubstituted cyclic alkylene groups with substituents such as alkyl, hydroxyl, mercapto, carbonyl, and thiocarbonyl groups.

[0069] As Y represents substituted or unsubstituted 1,4-dithiocyclohexane, examples include unsubstituted 1,4-dithiocyclohexanes represented by the following formula, and groups formed by substituting the above unsubstituted 1,4-dithiocyclohexanes with substituents such as alkyl or hydroxyl groups.

[0070] In the following formulas, * represents the bonding position.

[0071] [Chemical Formula 5]

[0072]

[0073] Examples of substituted or unsubstituted arylene groups represented by Y include unsubstituted arylene groups such as phenylene and naphthylene, as well as groups formed by substituting the aforementioned unsubstituted arylene groups with substituents such as alkyl, hydroxyl, mercapto, carbonyl, and thiocarbonyl groups.

[0074] Examples of substituted or unsubstituted arylene alkyl groups represented by Y include unsubstituted arylene alkyl groups such as benzylene and phenethylene, as well as groups formed by substituting the aforementioned unsubstituted arylene alkyl groups with substituents such as alkyl, hydroxyl, mercapto, carbonyl, and thiocarbonyl groups.

[0075] In equation (1), m represents an integer from 0 to 2.

[0076] m is preferably 0 or 1, more preferably 0.

[0077] In equation (1), n ​​represents an integer from 0 to 3.

[0078] n is preferably 0 or 1.

[0079] Regarding the cyclic sulfur compounds represented by formula (1), for example, reference may be made to paragraphs 0025 to 0038 of Japanese Patent Application Publication No. 2005-272778.

[0080] As a cyclic sulfur compound represented by formula (1), it preferably contains selected from

[0081] bis(2,3-cyclothiopropyl) sulfide,

[0082] bis(2,3-cyclothiopropylthio)methane,

[0083] bis(2,3-cyclothiopropylthio)ethane,

[0084] 3,8-bis(2,3-cyclothiopropylthio)-3,6-dithiaoctane, and

[0085] At least one of the groups consisting of bis(2,3-cyclothiopropyl)disulfides (hereinafter also referred to as "cyclic sulfur compounds (E1)").

[0086] More preferably, it comprises at least one of bis(2,3-cyclothiopropyl) sulfide and bis(2,3-cyclothiopropyl) disulfide (hereinafter also referred to as "cyclic sulfur compound (E2)").

[0087] In the polymerizable composition, the proportion of the cyclic sulfur compound (E1) in the total amount of the cyclic sulfur compound represented by 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.

[0088] In the polymerizable composition, the preferred range of the proportion of cyclic sulfur compound (E2) in the total amount of cyclic sulfur compound represented by formula (1) is the same as the preferred range of the proportion of cyclic sulfur compound (E1) in the total amount of cyclic sulfur compound represented by formula (1).

[0089] From the viewpoint of obtaining a resin with a superior refractive index, the content of the cyclic sulfur compound represented by formula (1) relative to the total amount of the polymerizable composition of this disclosure is preferably 30% by mass or more, and more preferably 40% by mass or more.

[0090] From the viewpoint of further improving the strength and hue of the obtained resin, the content of the cyclic sulfur compound represented by formula (1) relative to the total amount of the polymerizable composition of this disclosure is preferably 85% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.

[0091] A preferred range for the content of the cyclic sulfur compound represented by formula (1) relative to the total amount of the polymeric composition of this disclosure is, for example, 30% by mass to 85% by mass.

[0092] <Polyisocyanate compounds>

[0093] The polymeric compositions disclosed herein contain at least one polyisocyanate compound.

[0094] In this publication, a polyisocyanate compound is defined as a compound containing two or more isocyanate groups in one molecule.

[0095] In this publication, the term "isocyanate group" refers to isocyanate group or isothiocyanate group.

[0096] Regarding polyisocyanate compounds, for example, reference may be made to paragraphs 0049 to 0051 of Japanese Patent Application Publication No. 2005-272778.

[0097] The polyisocyanate compound in the polymerizable compositions of this disclosure is particularly preferably composed of at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, phenylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenyl diisocyanate (hereinafter referred to as "polyisocyanate compound N1").

[0098] In the polymerizable composition, the proportion of polyisocyanate compound N1 in the total amount of polyisocyanate compound is preferably 50% to 100% by mass, more preferably 60% to 100% by mass, and even more preferably 80% to 100% by mass.

[0099] From the viewpoint of further improving the Abbe number, hue, and strength of the obtained resin, the content of the polyisocyanate compound relative to the total amount of the polymerizable composition of this disclosure is preferably 2% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more.

[0100] From the viewpoint of obtaining a resin with a superior refractive index, the content of the polyisocyanate compound relative to the total amount of the polymerizable composition of this disclosure is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.

[0101] Preferred ranges for the content of polyisocyanate compounds relative to the total amount of the polymeric composition of this disclosure include, for example, 2% by mass to 50% by mass.

[0102] <Polythiol compounds>

[0103] The polymeric compositions disclosed herein contain at least one polythiol compound.

[0104] In this publication, a polythiol compound is defined as a compound containing two or more thiol groups (i.e., thiol groups) in one molecule.

[0105] In this publication, two or more polythiol compounds are sometimes referred to as a “polythiol composition”.

[0106] Regarding polythiol compounds, for example, reference may be made to paragraphs 0039 to 0048 of Japanese Patent Application Publication No. 2005-272778.

[0107] The polythiol compound in the polymerizable compositions of this disclosure preferably comprises selected from 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 following groups (hereinafter also referred to as "polythiol compound S1"): bis(mercaptoethyl) sulfide, 1,1,3,3-tetra(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiacyclohexane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiacyclobutane, 1,1,2,2-tetra(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, and tri(mercaptomethylthio)methane.

[0108] In the polymerizable composition, the proportion of polythiol compound S1 in the total amount of polythiol compounds (i.e., the proportion of the total content of the two or more compounds when polythiol compound S1 is composed of two or more compounds) is preferably 50% to 100% by mass, more preferably 60% to 100% by mass, and even more preferably 80% to 100% by mass.

[0109] From the viewpoint of further improving the hue and strength of the obtained resin, the content of polythiol compounds relative to the total amount of the polymerizable composition of this disclosure is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more.

[0110] From the viewpoint of obtaining a resin with superior refractive index and heat resistance, the content of polythiol compounds relative to the total amount of the polymerizable composition of this disclosure is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less.

[0111] Preferred ranges for the content of polythiol compounds relative to the total amount of the polymeric composition of this disclosure include, for example, 5% by mass to 60% by mass.

[0112] <Epoxy Compound (X)>

[0113] The polymeric compositions disclosed herein contain at least one epoxy compound (X).

[0114] The epoxy compound (X) in this disclosure is a compound containing one or more epoxy groups in a molecule and without cyclic sulfide groups.

[0115] The epoxy compound (X) preferably includes the epoxy compound (X1).

[0116] Here, the so-called epoxy compound (X1) is a compound containing two or more (preferably two to four, more preferably two or three, and even more preferably two) epoxy groups in one molecule.

[0117] The proportion of epoxy compound (X1) in the total amount of epoxy compound (X) is preferably 50% to 100% by mass, more preferably 60% to 100% by mass, and even more preferably 80% to 100% by mass.

[0118] As a specific example of an epoxy compound (X), for example:

[0119] Phenolic epoxy compounds are condensations of aromatic hydroxyl compounds such as phenol, cresol, xylenol, naphthol, hydroquinone, catechol, resorcinol, bisphenol A, bisphenol F, bisphenol sulfone, bisphenol ether, bisphenol sulfide, bisphenol sulfide, halogenated bisphenol A, and Novolac resin with glycidyl ether.

[0120] Alcoholic epoxides are condensates of 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 trimethacrylate, pentaerythritol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,3-cyclohexanediethanol, 1,4-cyclohexanediethanol, hydrogenated bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, and other alcoholic compounds with glycidyl ether.

[0121] Glycidyl esters are epoxy compounds that are condensations of carboxylic acid compounds such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, isovaleric acid, benzoic acid, benzoylacetic acid, naphtholic 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, benzoyltetracarboxylic acid, benzophenone tetracarboxylic acid, naphtholic acid, and diphenyldicarboxylic acid with glycidyl esters.

[0122] The following substances are used: 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-diaminocyclohexane. Primary amines such as 1,3- or 1,4-diaminomethylcyclohexane, 1,3- or 1,4-diaminoethylcyclohexane, 1,3- or 1,4-diaminopropylcyclohexane, hydrogenated 4,4'-diaminodiphenylmethane, isophorone diamine, 1,4-diaminopropylpiperazine, meta- or p-phenylenediamine, 2,4- or 2,6-diaminotoluene, meta- or p-phenylenediamine, 1,5- or 2,6-naphthylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, and 2,2-(4,4'-diaminodiphenyl)propane, etc.

[0123] Dimethylamine, diethylamine, dibutylamine, methylethylamine, methylpropylamine, methylbutylamine, methylpentylamine, methylhexylamine, ethylpropylamine, ethylbutylamine, ethylpentylamine, 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-diaminoheptane, N,N'- Amine-based epoxy compounds are produced by reacting secondary amines such as 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, 1,1-di-(4-piperidinyl)methane, 1,2-di-(4-piperidinyl)ethane, 1,3-di-(4-piperidinyl)propane, and 1,4-di-(4-piperidinyl)butane with epihaloalcohols.

[0124] Alicyclic epoxy compounds such as cyclohexane oxide, 3,4-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexyl ester, vinylcyclohexane dioxide, 1,2:8,9-diepoxylimonene, 2-(3,4-epoxycyclohexyl)-5,5-spiro-3,4-epoxycyclohexane-m-dioxane, and bis(3,4-epoxycyclohexyl) adipic acid ester;

[0125] Epoxy compounds are produced by epoxidation of unsaturated compounds such as styrene oxide, cyclopentadiene epoxide, epoxidized soybean oil, epoxidized polybutadiene, and vinylcyclohexene epoxide.

[0126] Carbamate-based epoxy compounds are made from polyols or phenolic compounds, diisocyanates, and glycidyl ether.

[0127] etc.

[0128] From the viewpoint of further improving the heat resistance of the obtained resin, the epoxy compound (X) (such as the epoxy compound (X1) mentioned above, the same below) preferably contains an aromatic ring, more preferably contains an aromatic ring and a glycidyl group, and even more preferably contains an aromatic ring and two or more (preferably two to four, more preferably two or three, and even more preferably two) glycidyl groups.

[0129] From the viewpoint of further improving the heat resistance of the obtained resin, the molecular weight of the epoxy compound (X) is preferably 1000 or less, more preferably 500 or less, and even more preferably 400 or less.

[0130] The lower limit of the molecular weight of the epoxy compound (X) is preferably 100, and more preferably 200.

[0131] The epoxy compound (X) preferably comprises 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).

[0132] In this case, the total proportion of bisphenol A diglycidyl ether and resorcinol diglycidyl ether in the total amount of epoxide (X) is preferably 50% to 100% by mass, more preferably 60% to 100% by mass, and even more preferably 80% to 100% by mass.

[0133] From the viewpoint of further improving the hue of the obtained resin, the content of epoxy compound (X) relative to the total amount of the polymerizable composition of this 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.

[0134] From the viewpoint of obtaining a resin with superior strength, the content of epoxy compound (X) relative to the total amount of the polymerizable composition of this disclosure is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 3% by mass or less.

[0135] A preferred range for the content of epoxy compound (X) relative to the total amount of the polymeric composition of this disclosure is, for example, 0.05% by mass to 20% by mass.

[0136] <(M S -M N ) / M E Comparison >

[0137] In the polymeric composition disclosed herein,

[0138] Let M be the total number of moles of thiol groups contained in the total amount of polythiol compounds.S ,

[0139] Let M be the total number of moles of isocyanate groups in the total amount of polyisocyanate compounds. N ,

[0140] Let M be the total number of moles of cyclic sulfide groups contained in the total amount of cyclic sulfide compounds represented by equation (1). E In this case,

[0141] (M S -M N ) / M E The preferred value is greater than 0 and less than 0.20, and the more preferred value is greater than 0 and less than 0.15.

[0142] (M S -M N ) / M E When the ratio is greater than 0, the strength of the obtained resin is further improved.

[0143] (M S -M N ) / M E When the ratio is below 0.20, the heat resistance of the obtained resin is further improved.

[0144] <Compound represented by formula (2)>

[0145] The polymeric compositions disclosed herein preferably contain compounds represented by the following formula (2).

[0146] The compound represented by the following formula (2) can function as a curing catalyst.

[0147] When the polymeric composition disclosed herein contains a compound represented by the following formula (2), the strength of the resulting resin can be further improved.

[0148] When the polymeric composition disclosed herein contains a compound represented by formula (2) below, the compound represented by formula (2) may be only one or more.

[0149] (R 1 )4Y + X - …(2)

[0150] In equation (2), there are 4 R's. 1 Each group independently represents a straight-chain hydrocarbon group with 1 to 10 carbon atoms or a branched hydrocarbon group with 3 to 10 carbon atoms. X represents a halogen atom, and Y represents a nitrogen atom or a phosphorus atom.

[0151] In equation (2), R is used as 1The term "a straight-chain hydrocarbon group having 1 to 10 carbon atoms or a branched hydrocarbon group having 3 to 10 carbon atoms" is preferred to be a straight-chain alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms.

[0152] From the perspective of achieving a better appearance of the obtained resin, as R 1 The term "a straight-chain hydrocarbon group having 1 to 10 carbon atoms or a branched hydrocarbon group having 3 to 10 carbon atoms" is more preferably a straight-chain alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms, and even more preferably a straight-chain alkyl group having 1 to 6 carbon atoms.

[0153] In formula (2), the halogen atom represented by X is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom, a chlorine atom, or a bromine atom, and even more preferably a chlorine atom or a bromine atom.

[0154] From the viewpoint of making the obtained resin have a better appearance, the halogen atom represented by X is particularly preferred to be a bromine atom.

[0155] In equation (2), Y can be a nitrogen atom or a phosphorus atom, but is preferably a nitrogen atom.

[0156] The compound represented by formula (2) is preferably tetra-n-butylammonium bromide (TBAB) or tri-n-octylmethylammonium chloride (TOMAC).

[0157] Tetra-n-butylammonium bromide (TBAB) is the four Rs in formula (2). 1 A compound in which each is a n-butyl atom, Y is a nitrogen atom, and X is a bromine atom.

[0158] The content of the compound represented by formula (2) in the polymerizable composition is preferably 0.01% 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 cyclic sulfur compound, polyisocyanate compound, and polythiol compound represented by formula (1).

[0159] <Tertiary amine compounds>

[0160] The polymerizable compositions disclosed herein preferably contain tertiary amine compounds.

[0161] Tertiary amine compounds can function as curing catalysts.

[0162] When the polymerizable composition of this disclosure contains a tertiary amine compound, the resulting resin can have a better appearance.

[0163] When the polymeric composition disclosed herein contains a tertiary amine compound, the tertiary amine compound may be only one type or may be two or more types.

[0164] The polymeric compositions disclosed herein may also contain both a compound represented by formula (2) and a tertiary amine compound (e.g., at least one of the compounds represented by formula (3) and formula (4)).

[0165] The tertiary amine compound preferably comprises at least one of the compounds represented by formula (3) below and the compounds represented by formula (4) below.

[0166] (The compound represented by formula (3))

[0167] When the polymeric composition disclosed herein contains a compound represented by formula (3) below, the compound represented by formula (3) may be only one or more.

[0168] [Chemical Formula 6]

[0169]

[0170] In formula (3), each of the m R1s independently represents a straight-chain alkyl group with 1 to 20 carbon atoms, a branched alkyl group with 3 to 20 carbon atoms, a cycloalkyl group with 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 from 0 to 5.

[0171] In equation (3), m is preferably an integer from 0 to 3, and more preferably an integer from 1 to 3.

[0172] In formula (3), the straight-chain alkyl group with 1 to 20 carbon atoms represented by R1 can be methyl, ethyl, n-propyl, n-butyl, pentyl, hexyl, heptyl, n-octyl, nonyl, decyl, dodecyl, etc.

[0173] In formula (3), branched alkyl groups with 3 to 20 carbon atoms represented by R1 can be represented by isopropyl, isobutyl, tert-butyl, isopentyl, isooctyl, 2-ethylhexyl, 2-propylpentyl, isodecyl, etc.

[0174] In formula (3), cycloalkyl groups with 3 to 20 carbon atoms represented by R1 can be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.

[0175] In formula (3), R1 is preferably a straight-chain alkyl or halogen atom with 1 to 20 carbon atoms, and more preferably a straight-chain alkyl or chlorine atom with 1 to 3 carbon atoms.

[0176] The compound represented by formula (3) is preferably selected from at least one of the group consisting of 2-methylpyrazine, pyridine, α-methylpyridine, β-methylpyridine, γ-methylpyridine, 2,6-dimethylpyridine, 3,5-dimethylpyridine, 2,4,6-trimethylpyridine, 3-chloropyridine, 2-ethylpyridine, and 3-ethylpyridine.

[0177] (The compound represented by formula (4))

[0178] When the polymeric composition disclosed herein contains a compound represented by formula (4) below, the compound represented by formula (4) may be only one or more.

[0179] [Chemical Formula 7]

[0180]

[0181] In formula (4), R2, R3, and R4 each independently represent a straight-chain alkyl group with 3 to 20 carbon atoms, a branched alkyl group with 3 to 20 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, or an allyl group. R2 and R3 can bond together to form a ring.

[0182] In formula (4), R2, R3, and R4 are each preferably straight-chain alkyl with 3 to 20 carbon atoms, more preferably straight-chain alkyl with 3 to 10 carbon atoms, and particularly preferably straight-chain alkyl with 5 to 10 carbon atoms.

[0183] Examples of straight-chain alkyl groups with 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.

[0184] R2 and R3 can bond together to form a ring.

[0185] That is, the compound represented by formula (4) can also be a cyclic amine compound with R2 and R3 bonded to each other to form a ring.

[0186] Examples of the aforementioned cyclic amine compounds include 1-propylpiperidine, 1-butylpiperidine, 1-cyclohexylpiperidine, 1-butylpyrrolidine, and 1-cyclohexylpyrrolidine.

[0187] The compound represented by formula (4) is preferably at least one selected from the group consisting of triallylamine and trioctylamine.

[0188] The content of tertiary amine compounds in the polymerizable composition (e.g., the total content of compounds represented by formula (3) and formula (4)) is preferably 0.01% to 1% by mass, more preferably 0.01% to 0.5% by mass, and even more preferably 0.01% to 0.5% by mass, relative to the total amount of cyclic sulfur compounds, polyisocyanate compounds, and polythiols represented by formula (1).

[0189] The total content of the compound represented by formula (2) and the tertiary amine compound (e.g., the total content of the compound represented by formula (2) to formula (4)) in the polymerizable composition is preferably 0.01% to 1% by mass, more preferably 0.01% to 0.5% by mass, and even more preferably 0.01% to 0.5% by mass, relative to the total amount of the cyclic sulfur compound, polyisocyanate compound, and polythiol compound represented by formula (1).

[0190] The polymeric compositions disclosed herein may also contain other compounds besides those represented by formulas (2) to (4) above as curing catalysts.

[0191] The curing catalyst can be selected from the curing catalysts described, for example, in sections 0029 to 0033 of Japanese Patent Application Publication No. 2002-194083.

[0192] Lewis acid compounds

[0193] The polymerizable compositions disclosed herein preferably contain Lewis acid compounds.

[0194] This allows for a further improvement in the pot life of polymeric compositions.

[0195] When the polymeric composition disclosed herein contains a Lewis acid compound, the Lewis acid compound may be only one type or may be two or more types.

[0196] There are no particular limitations on Lewis acid compounds; for example, organotin compounds, zinc chloride, zinc acetylacetonate, aluminum chloride, aluminum fluoride, triphenylaluminum, tetrachlorotitanium, calcium acetate, etc. can be cited.

[0197] Regarding Lewis acid compounds, reference may be made, for example, to known publications such as Japanese Patent Application Publication No. 2000-256435 (especially paragraphs 0059-0060), Japanese Patent Application Publication No. 2005-272778 (especially paragraph 0058), and Japanese Patent Application Publication No. 2001-131257 (especially paragraph 0027).

[0198] As organotin compounds, there are no particular limitations; for example, the following can be cited:

[0199] Dialkyltin halides such as dibutyltin dichloride and dimethyltin dichloride; dialkyltin dicarboxylic acids such as dimethyltin diacetate, dibutyltin dioctanoate, and dibutyltin dilaurate;

[0200] Tin tetrachloride;

[0201] Dibutyltin oxide;

[0202] etc.

[0203] Dialkyl tin halides can also include monoalkyl tin halides and trialkyl tin halides.

[0204] Dicarboxylic acid dialkyltin compounds can also include tricarboxylic acid monoalkyltin compounds and carboxylic acid trialkyltin compounds.

[0205] From the viewpoint of further improving the pot life of the polymerizable composition, the Lewis acid compound preferably includes a compound represented by the following formula (5) as a specific organotin compound.

[0206] [Chemical Formula 8]

[0207] (R4) c -Sn-X 4-c (5)

[0208] In formula (5), R4 represents an alkyl group with 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 with 1 to 11 carbon atoms, and c represents an integer from 1 to 3.

[0209] The compound represented by formula (5) is preferably selected from at least one of the group consisting of dimethyltin dichloride, dibutyltin dichloride, and dibutyltin dilaurate.

[0210] The content of Lewis acid compounds (e.g., organotin compounds such as those represented by formula (5)) is preferably 100 ppm to 500 ppm by mass, more preferably 200 ppm to 400 ppm by mass, relative to the total amount of the polymerizable composition.

[0211] <Other Ingredients>

[0212] The polymeric compositions disclosed herein may also contain other components besides those described above.

[0213] Other components include bluing agents, thiol organic acids, resins (e.g., acrylic resins, olefin resins, etc.), crosslinking agents, light stabilizers, ultraviolet absorbers, antioxidants, anti-coloring agents, dyes, fillers, and internal release agents.

[0214] Other ingredients may be known ingredients.

[0215] For other components, for example, Japanese Patent Application Publication No. 2002-194083 may be appropriately referred to.

[0216] The polymeric composition disclosed herein can be obtained by mixing the above-described components (raw materials).

[0217] There are no particular restrictions on the order in which the ingredients (raw materials) are mixed. All raw materials can be added to the container at once for mixing, or they can be added to the container in multiple batches for mixing.

[0218] Alternatively, a portion of the monomers in the polymerizable composition of this disclosure can be polymerized during the mixing process to form a prepolymer.

[0219] The monomers in the polymerizable compositions disclosed herein refer at least to cyclic sulfur compounds, polyisocyanate compounds, and polythiols represented by formula (1). In addition to these compounds, epoxides (X) may also function as monomers.

[0220] [Resin, Molded Body]

[0221] The resin in this disclosure is a cured product of the polymeric composition described above.

[0222] The molded body of this disclosure contains the resin of this disclosure.

[0223] That is, the resin of this disclosure can be manufactured by curing the polymeric composition of this disclosure described above, specifically by polymerizing and curing the monomers in the polymeric composition of this disclosure.

[0224] As a method for polymerizing monomers in the polymerizable composition of this disclosure, casting polymerization can be cited as an example. By casting polymerization, a molded body of this disclosure containing the resin of this disclosure (i.e., a cured polymerizable composition of this disclosure) can be obtained.

[0225] In casting polymerization, firstly, the polymerizable composition, as exemplified in this disclosure, is injected between a pair of molding dies held by gaskets or tapes. At this point, degassing, filtration, etc., may be performed as needed.

[0226] Next, the monomers in the composition injected into the molding die are polymerized, thereby curing the composition in the molding die to obtain a cured product. Then, the cured product is removed from the molding die to obtain the cured product.

[0227] The polymerization of the aforementioned monomers can be carried out by heating the polymerizable composition of this disclosure. This heating can be carried out, for example, using a heating device equipped with a mechanism for heating the object in an oven, water, or similar medium.

[0228] The polymerization conditions (e.g., polymerization temperature, polymerization time, etc.) used to polymerize the monomers in the polymerizable compositions of this disclosure can be suitably set taking into account the composition of the composition, the type and amount of monomers in the composition, the type and amount of polymerization catalyst in the composition, the shape of the mold, etc.

[0229] Examples of polymerization temperatures include -50℃ to 150℃ and 10℃ to 150℃.

[0230] Examples of aggregation times include 1 hour to 200 hours, 1 hour to 80 hours, etc.

[0231] The resin or molded body containing the resin in this disclosure may also be obtained by annealing or other treatments after polymerization of the monomer.

[0232] Examples of annealing temperatures include 50℃~150℃, 90℃~140℃, and 100℃~130℃.

[0233] [Optical Materials]

[0234] The optical material of this disclosure includes the resin described above.

[0235] The optical materials disclosed herein can be manufactured, for example, by the aforementioned casting polymerization.

[0236] The optical material of this disclosure may be formed from the resin of this disclosure, or may contain the resin of this disclosure and other elements.

[0237] Other elements include other components, coatings provided for the resin used in this disclosure, etc.

[0238] Examples of optical materials used in this disclosure include lenses (e.g., spectacle lenses, camera lenses, polarizing lenses, etc.) and light-emitting diodes (LEDs).

[0239] 〔lens〕

[0240] The lens in this disclosure is an example of the optical material of this disclosure, including the resin described above.

[0241] The lens of this disclosure can be manufactured, for example, by the aforementioned casting polymerization.

[0242] The lens of this disclosure may be formed from the resin of this disclosure, or may contain the resin of this disclosure and other elements.

[0243] Other elements include other components, coatings provided for the resin used in this disclosure, etc.

[0244] Examples of lenses used in this disclosure include eyeglass lenses, camera lenses, and polarizing lenses.

[0245] The following description, as an example of a lens used in this disclosure, illustrates an eyeglass lens.

[0246] The eyeglass lens comprises resin formed into the desired lens shape as described in this disclosure.

[0247] The eyeglass lens preferably also includes a coating disposed on one or both sides of the resin.

[0248] As a coating, examples include primers, hard coatings, anti-reflective layers, anti-fog coatings, anti-fog layers, and waterproof layers. These coatings can be used individually or in multiple layers.

[0249] When applying a coating to both sides of a cured material, the same coating can be applied to each side, or different coatings can be applied.

[0250] The composition of the coating can be appropriately selected according to the purpose.

[0251] As components of the coating, examples 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, etc.

[0252] Regarding eyeglass lenses and coatings, for example, reference may be made to known documents such as Japanese Patent Application Publication No. 2002-194083 and International Publication No. 2017 / 047745.

[0253] Example

[0254] The following are embodiments of this disclosure, but this disclosure is not limited to these embodiments. It should be noted that, unless otherwise specified, "parts" are based on mass.

[0255] [Example 1]

[0256] <Preparation of Polymer Compositions>

[0257] Mix and dissolve the following components at 20°C:

[0258] A mixture of 2,5-bis(isocyanate methyl)bicyclo[2.2.1]heptane and 2,6-bis(isocyanate methyl)bicyclo[2.2.1]heptane (hereinafter also referred to as "PI-1") as a polyisocyanate compound, 26.5 parts by mass.

[0259] 0.68 parts by weight of bisphenol A diglycidyl ether (hereinafter also referred to as "BGPP") as epoxy compound (X),

[0260] 0.067 parts by mass of tetrabutylammonium bromide (hereinafter also referred to as "TBAB") as a curing catalyst (which is a compound represented by formula (2)).

[0261] 0.050 parts by weight of "ZELEC UN" (trade name; Stepan's acidic phosphate ester-based release agent) as a release agent, and

[0262] 0.088 parts by weight of "TinuvinPS" (manufactured by BASF Japan Ltd.) as a UV absorber.

[0263] The following components are sequentially added to and mixed with the obtained solution to obtain a polymerizable composition:

[0264] 45.4 parts by mass of bis(2,3-cyclothiopropyl) disulfide (hereinafter also referred to as "EPS-1"), representing the cyclic sulfur compound of formula (1), and

[0265] 28.1 parts by weight of a polythiol composition (hereinafter also referred to as "PT-1") mainly composed of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane.

[0266] Table 1 shows the types and amounts of each component contained in the polymeric composition.

[0267] In Table 1, a "-" indicates that the corresponding ingredient is not present.

[0268] Table 1 also shows the (M) in the polymerizable compositions. S -M N ) / M E Compare.

[0269] Here, (M) S -M N ) / M E The ratio is defined as the total number of moles of thiol groups contained in the total amount of polythiol compounds, denoted as M. SLet M be the total number of moles of isocyanate groups in the total amount of polyisocyanate compounds. N Let M be the total number of moles of cyclic sulfide groups contained in the total amount of cyclic sulfide compounds represented by equation (1). E In the case of (M) S -M N ) / M E Compared to (roughly speaking), the excess thiol groups (M) S -M N ) and cyclic sulfide (M E (ratio).

[0270] <Preparation of Resin Molded Entities>

[0271] The polymeric composition obtained above was filtered through a 3μm TEFLON (registered trademark) filter and then degassed under reduced pressure of 600Pa until no foaming was observed.

[0272] The degassed polymeric composition is injected between a pair of glass molds fixed with tape. Next, the pair of glass molds containing the polymeric composition are placed in an oven, and the temperature inside the oven is slowly increased from 30°C to 120°C over 15 hours. Through the above process, the monomers in the degassed polymeric composition (i.e., cyclic sulfur compounds, polyisocyanate compounds, polythiols, etc. represented by formula (1)) are polymerized to form a resin molded body (i.e., a molded body of resin as a cured product of the polymeric composition) between the pair of glass molds.

[0273] Next, the oven is cooled. After cooling, a pair of glass molds are removed from the oven, and then the resin molded body is removed from the pair of glass molds to obtain the resin molded body. The obtained resin molded body is annealed at 120°C for 1 hour to obtain a lens containing resin.

[0274] <Evaluation>

[0275] The above polymeric composition or resin molded article was evaluated as follows.

[0276] The results are shown in Table 1.

[0277] Optical properties (refractive index (n) e ) and Abbe number (ν e ))

[0278] Using a Pulverchi refractometer KPR-30 manufactured by Shimadzu Corporation, the refractive index at wavelengths of 546.1 nm (mercury e-line), 480.0 nm (Cd F'-line), and 643.9 nm (Cd C'-line) was measured. Based on these measurements, the refractive index (n) was calculated. e) and Abbe number (ν e ).

[0279] Heat resistance

[0280] In addition to appropriately selecting the shape and size of a pair of glass molds, a test piece with a length of 10 mm, a width of 10 mm, and a thickness of 2.5 mm was obtained by performing the same operation as described above in the <Preparation of Resin Molded Body>.

[0281] The glass transition temperature (Tg) of the above samples was determined using a Shimadzu TMA-60 thermomechanical analyzer and the TMA penetration method (50g load, 0.5mm φ needle tip, heating rate of 10℃ / min) as an indicator of heat resistance.

[0282] The higher the glass transition temperature (Tg), the better the heat resistance.

[0283] • Bending strength (bending modulus of elasticity)

[0284] In addition to appropriately selecting the shape and size of a pair of glass molds, a rectangular plate-shaped test piece with a length of 65 mm, a width of 25 mm, and a thickness of 2.5 mm is obtained by performing the same operation as described above for the <Preparation of Resin Molded Body>.

[0285] For the obtained test pieces, a three-point bending test was carried out using the AUTOGRAPH AGS-J manufactured by Shimadzu Corporation. Based on the range of 20N to 30N of force applied to the sample, the bending modulus of the sample was determined.

[0286] · Perforation tensile strength

[0287] In addition to appropriately selecting the shape and size of a pair of glass molds, a circular plate-shaped molded body with S = -2.00D and a diameter of 45mm is obtained by performing the same operations as described above in the <Preparation of Resin Molded Body>.

[0288] Two holes with a diameter of 1.6 mm were made at two locations 5 mm off-center from both ends of the obtained circular plate-shaped molded body to prepare test pieces. Using an AUTOGRAPH AGS-J manufactured by Shimadzu Corporation, pins were inserted into the holes at the two locations to measure the test results. The yield point was determined as 0.5% permanent strain, and the result was used as an indicator of the perforation strength.

[0289] • YI (Yellow Index; yellowness), a ＊ and b ＊

[0290] Besides appropriately selecting the shape and size of a pair of glass molds, a circular plate-shaped test piece with a thickness of 2.5 mm and a diameter of 75 mm was obtained by performing the same operations as described above in the <Preparation of Resin Molded Body> procedure. For the obtained test piece, a Konica Minolt a, Inc. spectrophotometer CM-5 was used to determine YI (yellow index; yellowness) and a. ＊ and b ＊ .

[0291] The smaller the value of YI, the better the hue of the lens.

[0292] • Appearance

[0293] The appearance of the test pieces (resin molded bodies) used in the above-mentioned determination of YI, etc., is evaluated by visual observation according to the following evaluation criteria.

[0294] -Appearance Evaluation Criteria-

[0295] A: The pattern is not visible at all; the appearance is good.

[0296] B: Although striped or spotted patterns are visible when viewed at close range, they are not visible when viewed from a distance of 50cm. The appearance is within the acceptable range for practical use.

[0297] C: The pattern is visible when viewed from a distance of 50cm, and its appearance exceeds the acceptable range for practical use.

[0298] [Example 2]

[0299] Except for changing the composition of the polymerizable composition as shown in Table 1, the same operation as in Example 1 was performed.

[0300] The results are shown in Table 1.

[0301] In Table 1, PT-2 is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane.

[0302] [Example 3]

[0303] Except for the following aspects, the same operation as in Example 1 shall be performed.

[0304] The results are shown in Table 1.

[0305] -Changes compared to Example 1-

[0306] • The composition of the polymerizable composition may be changed as shown in Table 1.

[0307] In Table 1, PI-2 is phenylene diisocyanate, and TOMAC is tri-n-octylmethylammonium chloride.

[0308] • After mixing all the ingredients, stir at 20°C for 1 hour to obtain a polymerizable composition.

[0309] • The filtering process in the <Preparation of Resin Molded Entities> has been omitted.

[0310] [Example 4]

[0311] Except for changing the type and amount of the curing catalyst as shown in Table 1, the same operation as in Example 3 was performed.

[0312] The results are shown in Table 1.

[0313] -Changes compared to Example 1-

[0314] • The composition of the polymerizable composition may be changed as shown in Table 1.

[0315] • 3,5-Dimethylpyridine is dissolved in a polythiol composition mainly composed of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane.

[0316] [Comparative Example 1]

[0317] The polymeric composition and resin molded articles shown below were prepared, and the resulting polymeric composition and resin molded articles were evaluated in the same manner as in Example 1.

[0318] The results are shown in Table 1.

[0319] <Preparation of Polymer Compositions>

[0320] At 20°C, the following components were sequentially mixed and dissolved in 90.9 parts by mass of bis(2,3-cyclothiopropyl) disulfide (EPS-1), which is a cyclic sulfur compound represented by formula (1):

[0321] 1 part by weight of "TinuvinPS" (manufactured by BASF Japan Ltd.) as a UV absorber.

[0322] A polythiol composition (PT-1) with 8.2 parts by weight of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane as the main components, and

[0323] 0.091 parts by mass of N,N-dicyclohexylmethylamine (hereinafter also referred to as "DCH") as a curing catalyst.

[0324] The obtained solution was mixed with 0.018 parts by mass of N,N-dimethylcyclohexylamine (hereinafter also referred to as "DCA") as a curing catalyst and 0.9 parts by mass of a polythiol composition (PT-1) mainly composed of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and the mixture was mixed at 20°C to obtain a polymerizable composition.

[0325] <Preparation of Resin Molded Entities>

[0326] The polymeric composition obtained above was filtered through a 1μm TEFLON (registered trademark) filter and then degassed under reduced pressure of 600Pa until no foaming was observed.

[0327] The degassed polymeric composition is injected between a pair of glass molds fixed with tape. Next, the pair of glass molds containing the polymeric composition are placed in an oven, and the temperature inside the oven is slowly increased from 30°C to 80°C over 21 hours. Through the above process, the monomers in the degassed polymeric composition (i.e., the cyclic sulfur compound polythiol composition, etc. represented by formula (1)) are polymerized, forming a resin molded body (i.e., a molded body of resin as a cured product of the polymeric composition) between the pair of glass molds.

[0328] Next, the oven is cooled. After cooling, a pair of glass molds are removed from the oven, and then the resin molded body is removed from the pair of glass molds to obtain the resin molded body. The obtained resin molded body is annealed at 120°C for 3 hours to obtain a lens containing resin.

[0329] [Table 1]

[0330]

[0331] As shown in Table 1, resin molded articles with high refractive index and excellent strength (especially strength in puncture tensile tests) can be manufactured according to the polymerizable compositions of Examples 1 to 4 containing cyclic sulfur compounds, polyisocyanate compounds, polythiols, and epoxy compounds (X) containing one or more epoxy groups and no cyclic sulfur groups in one molecule.

[0332] In contrast, the resin molded articles obtained using the resin composition of Comparative Example 1 have a high refractive index, but poor strength (especially in the piercing tensile test).

[0333] [Example 101]

[0334] <Preparation of Polymer Compositions>

[0335] Mix and dissolve the following components at 20°C:

[0336] 25.4 parts by weight of PI-2 (i.e., phenylene diisocyanate), a polyisocyanate compound.

[0337] 1.00 parts by weight of BGPP (i.e., bisphenol A diglycidyl ether) as epoxy compound (X)

[0338] 0.04 parts by mass of dimethyltin dichloride (hereinafter also referred to as "DMC") as a Lewis acid compound (specifically, the compound represented by formula (5)).

[0339] 0.03 parts by weight of "ZELEC UN" (trade name; Stepan's acidic phosphate ester-based release agent) as a release agent, and

[0340] 0.088 parts by weight of "TinuvinPS" (manufactured by BASF Japan Ltd.) as a UV absorber.

[0341] Regarding the obtained solution,

[0342] After loading 42.6 parts by mass of EPS-1 (i.e., bis(2,3-cyclothiopropyl) disulfide), which is a cyclic sulfur compound represented by formula (1),

[0343] A mixture of 32.0 parts by weight of PT-1 (i.e., a polythiol composition mainly composed of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane) and 0.03 parts by weight of 3,5-dimethylpyridine as a curing catalyst (which is a compound represented by formula (3)) was mixed at 5 to 10 °C to obtain a polymerizable composition.

[0344] <Preparation of Resin Molded Entities>

[0345] The polymeric composition obtained above was degassed thoroughly under reduced pressure of 600 Pa until no foaming was observed.

[0346] The degassed polymeric composition is injected between a pair of glass molds fixed with tape. Next, the pair of glass molds containing the polymeric composition are placed in an oven, and the temperature inside the oven is slowly increased from 20°C to 120°C over 23 hours. Through the above process, the monomers in the degassed polymeric composition (i.e., cyclic sulfur compounds, polyisocyanate compounds, polythiols, etc. represented by formula (1)) are polymerized to form a resin molded body (i.e., a molded body of resin as a cured product of the polymeric composition) between the pair of glass molds.

[0347] Next, the oven is cooled. After cooling, a pair of glass molds are removed from the oven, and then the resin molded body is removed from the pair of glass molds to obtain the resin molded body. The obtained resin molded body is annealed at 120°C for 1 hour to obtain a lens containing resin.

[0348] <Evaluation>

[0349] The above polymeric composition or resin molded article was evaluated as follows.

[0350] The results are shown in Table 2.

[0351] • Viscosity of polymeric compositions

[0352] The above polymeric composition was stirred at 10°C for 1 hour, and the viscosity was measured using a Brookfield Company Type B viscometer (spindle No. 62).

[0353] The lower the viscosity value, the better the pot life.

[0354] • Heat resistance, YI (yellowness index; yellowness)

[0355] The same procedure was followed as in Example 1, and the heat resistance and YI (yellow index; yellowness) of the resin molded articles were evaluated respectively.

[0356] [Examples 102-106]

[0357] Except for changing the composition of the polymerizable composition as shown in Table 2, the same operation as in Example 101 was performed.

[0358] The results are shown in Table 2.

[0359] In Table 2, DBC refers to dibutyltin dichloride as a Lewis acid compound (specifically, a compound represented by formula (5)).

[0360] In addition, in Table 2, the "-" in the column "Lewis acid compound (compound represented by formula (5))" of Example 106 indicates that Lewis acid compound is not used.

[0361] [Table 2]

[0362]

[0363] As shown in Table 2, it was confirmed that among Examples 101 to 106, regarding Examples 101 to 105 where the polymeric composition contains a Lewis acid compound, the viscosity of the polymeric composition was reduced and the pot life of the polymeric composition was superior compared to Example 106 where the polymeric composition does not contain a Lewis acid compound.

[0364] The full disclosures of Japanese Patent Application No. 2021-017406, filed on February 5, 2021, and Japanese Patent Application No. 2021-124416, filed on July 29, 2021, are incorporated herein by reference.

[0365] All documents, patent applications and technical standards described in this specification are incorporated herein by reference to the extent that each document, patent application and technical standard is incorporated by reference to the extent that it is specifically and separately described.

Claims

1. A polymeric composition comprising: The cyclic sulfur compound represented by the following formula (1), Polyisocyanate compounds and / or polyisothiocyanate compounds, Polythiol compounds, An epoxy compound (X) containing one or more epoxy groups and no cyclic sulfide groups in one molecule. Tertiary amine compounds, and Lewis acid compounds; [Chemical Formula 1] In formula (1), Y represents a substituted or unsubstituted straight-chain hydrocarbon group with 1 to 4 carbon atoms, a substituted or unsubstituted branched hydrocarbon group with 2 to 4 carbon atoms, a substituted or unsubstituted cyclic hydrocarbon group with 3 to 6 carbon atoms, a substituted or unsubstituted 1,4-dithionecyclohexyl group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted arylene group, m represents an integer from 0 to 2, and n represents an integer from 0 to 3.

2. The polymerizable composition of claim 1, wherein, The epoxy compound (X) includes an epoxy compound (X1) containing two or more epoxy groups in one molecule.

3. The polymeric composition according to claim 1 or claim 2, wherein, Let M be the total number of moles of thiol groups contained in the total amount of the polythiol compound. S , Let M be the total number of moles of isocyanate groups and / or isothiocyanate groups in the total amount of the polyisocyanate compound and / or polyisothiocyanate compound. N , Let M be the total number of moles of cyclic sulfide groups contained in the total amount of the cyclic sulfide compound represented by formula (1). E In this case, (M) S -M N ) / M E The ratio is greater than 0 and less than 0.

20.

4. The polymeric composition according to claim 1 or claim 2, wherein, The polythiols compound comprises, selected from 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, and 2,5-bis(mercaptomethyl)-1,4-dithiacyclohexane. At least one of the following groups: alkyl, bis(mercaptoethyl) sulfide, 1,1,3,3-tetra(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiacyclohexane, 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiacyclobutane, 1,1,2,2-tetra(mercaptomethylthio)ethane, 3-mercaptomethyl-1,5-dimercapto-2,4-dithiapentane, and tri(mercaptomethylthio)methane.

5. The polymeric composition according to claim 1 or claim 2, wherein, The polyisocyanate compound comprises at least one selected from the group consisting of pentamethylene diisocyanate, hexamethylene diisocyanate, phenylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and phenyl diisocyanate.

6. The polymeric composition of claim 1 or claim 2, further comprising a compound represented by formula (2) below, (R 1 )4Y + X - …(2) In equation (2), there are 4 R's. 1 Each group independently represents a straight-chain hydrocarbon group with 1 to 10 carbon atoms or a branched hydrocarbon group with 3 to 10 carbon atoms. X represents a halogen atom, and Y represents a nitrogen atom or a phosphorus atom.

7. The polymeric composition according to claim 1 or claim 2, wherein, The tertiary amine compound comprises at least one of the compounds represented by formula (3) and the compounds represented by formula (4). [Chemical Formula 2] In formula (3), each of the m R1s independently represents a straight-chain alkyl group with 1 to 20 carbon atoms, a branched alkyl group with 3 to 20 carbon atoms, a cycloalkyl group with 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 from 0 to 5. In formula (4), R2, R3, and R4 each independently represent a straight-chain alkyl group with 3 to 20 carbon atoms, a branched alkyl group with 3 to 20 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, or an allyl group; R2 and R3 can bond to each other to form a ring.

8. The polymerizable composition of claim 7, wherein, The compound represented by formula (3) is at least one selected from the group consisting of 2-methylpyrazine, pyridine, α-methylpyridine, β-methylpyridine, γ-methylpyridine, 2,6-dimethylpyridine, 3,5-dimethylpyridine, 2,4,6-trimethylpyridine, 3-chloropyridine, 2-ethylpyridine, and 3-ethylpyridine. The compound represented by formula (4) is selected from at least one of the groups consisting of triallylamine and trioctylamine.

9. The polymeric composition according to claim 1 or claim 2, wherein, The Lewis acid compound comprises a compound represented by the following formula (5), [Chemical Formula 3] In formula (5), R4 represents an alkyl group with 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 with 1 to 11 carbon atoms, and c represents an integer from 1 to 3.

10. The polymerizable composition of claim 9, wherein, The compound represented by formula (5) is selected from at least one of the group consisting of dimethyltin dichloride, dibutyltin dichloride, and dibutyltin dilaurate.

11. A resin, which is a cured product of the polymeric composition according to any one of claims 1 to 10.

12. A molded article comprising the resin of claim 11.

13. An optical material comprising the resin of claim 11.

14. A lens comprising the resin of claim 11.

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