Resins, molded articles, optical materials, lenses, 2,5-bis(isocyanatomethyl)furan and polymerizable compositions

Abstract

This resin is a cured product of a polymerizable composition containing a compound represented by general formula (1) and a thiol compound having one or more mercapto groups, and the resin has a biomass degree of 15% or greater. In general formula (I), R1 and R2 each independently represent a hydrogen atom or a methyl group. n represents an integer of 0 or 1.

Description

[Technical Field] 【0001】 This disclosure relates to resins, molded articles, optical materials, lenses, 2,5-bis(isocyanatomethyl)furan, and polymerizable compositions. [Background technology] 【0002】 Plastic lenses, which contain resin, are lighter, less prone to breakage, and can be dyed compared to inorganic lenses, and have therefore become rapidly popular in recent years for applications such as eyeglass lenses and camera lenses. 【0003】 For example, studies have been conducted on lenses containing thiourethane resin. Patent Document 1 proposes a polymerizable composition for optical materials, comprising a polyisocyanate (a) containing an aliphatic polyisocyanate (a1) and a modified aliphatic polyisocyanate (a2), and a polythiol (b) having two or more mercapto groups, wherein the modified aisocyanate (a2) is contained in the polyisocyanate (a) in an amount of 60% by weight or less, as well as a molded article and a plastic spectacle lens using a thiourethane resin obtained by polymerizing and curing this composition. [Patent Document 1] International Publication No. 2015 / 119220 [Overview of the project] [Problems that the invention aims to solve] 【0004】 Patent Document 1 describes a thiourethane resin obtained by polymerizing and curing a polymerizable composition for optical materials, in which the biomass content is 25% or more. Considering the impact on the global environment, it is desirable to obtain resins using biomass raw materials, even for thiourethane resins other than those described in Patent Document 1. Furthermore, for thiourethane resins with a refractive index exceeding 1.65, there is room for improvement in terms of achieving both a high refractive index and a high biomass content, as well as in terms of productivity. 【0005】 An object of the present disclosure is to provide a resin obtained using a compound derived from a biomass raw material, a molded body containing this resin, an optical material and a lens, and 2,5-bis(isocyanatomethyl)furan derived from a biomass raw material and a polymerizable composition containing the same. 【Means for Solving the Problems】 【0006】 The means for solving the above problems include the following aspects. <1> A cured product of a polymerizable composition containing a compound represented by the following general formula (1) and a thiol compound having one or more mercapto groups, A resin having a biomass content of 15% or more. 【0007】 【Chemical formula】 【0008】 (In general formula (1), R1 and R2 each independently represent a hydrogen atom or a methyl group. n represents an integer of 0 or 1.) <2> The resin according to <1>, wherein the compound represented by the general formula (1) is 2,5-bis(isocyanatomethyl)furan represented by the following formula (2). 【0009】 【Chemical formula】 【0010】 <3> The resin according to <1> or <2>, having a biomass content of 35% or more. <4> The thiol compound is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 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, Includes at least one selected from the group consisting of, <1> ~ <3> The resin described in any one of the following. <5> The polymerizable composition further comprises an episulfide compound having one or more episulfide groups. <1> ~ <4> The resin described in any one of the following. <6> The refractive index ne is 1.650 or higher. <1> ~ <5> The resin described in any one of the following. <7> <1> ~ <6> A molded article containing the resin described in any one of the following. <8> <7> Optical materials including the molded articles described above. <9> <7> A lens containing the molded body described above. <10> 2,5-bis(isocyanatomethyl)furan with a biomass content of 50% or more. <11> 2,5-bis(isocyanatomethyl)furan derived from 2,5-bis(aminomethyl)furan obtained from biomass raw materials. <12> <10> or <11> A polymerizable composition containing 2,5-bis(isocyanatomethyl)furan as described above. <13> Further comprising a thiol compound having one or more mercapto groups, <12> The polymerizable composition described above. <14> Further comprising an episulfide compound having one or more episulfide groups, <12> or <13> The polymerizable composition described above. [Effects of the Invention] 【0011】 According to this disclosure, it is possible to provide a resin obtained using a compound derived from biomass raw materials, a molded article containing this resin, an optical material and a lens, and 2,5-bis(isocyanatomethyl)furan derived from biomass raw materials and a polymerizable composition containing the same. [Modes for carrying out the invention] 【0012】 In this disclosure, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. In this disclosure, the amount of each component contained in the composition means the total amount of any multiple substances that constitute each component in the composition, unless otherwise specified. In numerical ranges described in stages within this disclosure, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in numerical ranges described within this disclosure, the upper or lower limit of that range may be replaced with the values ​​shown in the examples. 【0013】 <Resin> The resin of this disclosure is a cured product of a polymerizable composition containing a compound represented by the following general formula (1) and a thiol compound having one or more mercapto groups (hereinafter also referred to as "thiol compound"), and is a resin with a biomass content of 15% or more. 【0014】 [ka] 【0015】 In general formula (1), R1 and R2 each independently represent a hydrogen atom or a methyl group. n represents an integer of 0 or 1. 【0016】 The resin disclosed herein is a cured product of a polymerizable composition containing a compound represented by general formula (1) and a thiol compound, and is a resin with a biomass content of 15% or more. Therefore, at least one of the compound represented by general formula (1) and the thiol compound is derived from biomass raw materials. By using a resin obtained from a compound derived from biomass raw materials, it is possible to manufacture molded articles, optical materials, lenses, etc. that contribute to the preservation of the global environment and are in harmony with the global environment. Cured products of polymerizable compositions containing a compound represented by general formula (1) and a thiol compound tend to have a higher refractive index compared to cured polyurethane resins. 【0017】 In general formula (1), R1 and R2 may be hydrogen atoms or methyl groups. The compound represented by general formula (1) may be a single compound or a mixture of two or more compounds. 【0018】 From the viewpoint of ease of operation during distillation purification in compound manufacturing and the heat resistance of the resulting resin, the compound represented by general formula (1) is preferably 2,5-bis(isocyanatomethyl)furan represented by the following formula (2). 2,5-bis(isocyanatomethyl)furan corresponds to the compound n=0 in general formula (1). Furthermore, using 2,5-bis(isocyanatomethyl)furan represented by the following formula (2) tends to result in a higher refractive index of the resulting resin. 【0019】 [ka] 【0020】 The biomass content of the compound represented by general formula (1), preferably 2,5-bis(isocyanatomethyl)furan, is preferably 50% or more, and more preferably 60% or more. From the viewpoint of availability, the biomass content of the compound represented by general formula (1), preferably 2,5-bis(isocyanatomethyl)furan, may be 80% or less. 【0021】 In this disclosure, biomass percentage (%) is expressed in accordance with ASTM D6866-21, δ 13 This represents the biomass content of the sample calculated using C-corrected pMC. The atmospheric correction factor REF(pMC) was calculated using REF(pMC)=100, assuming the biomass material was produced between 2019 and 2021. Measurement method Based on a tandem accelerator 14 Using a dedicated C-AMS device (manufactured by NEC Corporation), 14 The count of C, 13 C concentration ( 13 C / 12 C) and 14 C concentration ( 14 C / 12 The measurement of (C) was carried out. In the measurement, oxalic acid (HOxII) provided by the National Institute of Standards and Technology (NIST) of the United States was used as the standard sample. δ 13 C is the 13 C concentration ([[]] 13 C / 12 C) was measured and expressed as the deviation per thousand (‰) from the reference sample. pMC (percent Modern Carbon) is the 14 ratio of the C concentration of the sample carbon to the standard modern carbon. δ 14 C is the 14 deviation of the C concentration of the sample carbon from the standard modern carbon, expressed as the deviation per thousand (‰), and the value corrected by this δ 13 C is Δ 14 C. 【0022】 Hereinafter, an example of a method for producing a compound represented by the general formula (1) will be described. Note that the method for producing the compound represented by the general formula (1) may be any method as long as it can produce the compound represented by the general formula (1) using a biomass raw material, and is not limited to the production method described below. 【0023】 (Production Method 1 of the Compound Represented by the General Formula (1)) First, an example of a method for producing 2,5-bis(isocyanatomethyl)furan, which is a kind of the compound represented by the general formula (1), using a biomass raw material will be described. As the biomass raw material, saccharides are prepared. The saccharides are not particularly limited, and examples thereof include monosaccharides such as glucose and fructose, disaccharides such as sucrose and maltose, and polysaccharides such as cellulose and starch. 【0024】 Using the prepared sugars, 5-hydroxymethylfurfural, the compound shown in formula (3) below, is obtained through dehydration reactions, etc. For example, polysaccharides such as cellulose and starch, or disaccharides such as sucrose and maltose may be broken down into glucose by the action of enzymes, and 5-hydroxymethylfurfural may be obtained by dehydration reactions of the broken-down glucose. When synthesizing 5-hydroxymethylfurfural from glucose, fructose may be used as an intermediate. 【0025】 Other methods for synthesizing 5-hydroxymethylfurfural from sugars include, for example, the method described in Japanese Patent No. 6328990, which involves synthesizing 5-hydroxymethylfurfural from sugars such as cellulose, oligosaccharides, and monosaccharides. 【0026】 [ka] 【0027】 The aldehyde group in 5-hydroxymethylfurfural represented by formula (3) may be reduced using a reducing agent to obtain 2,5-bis(hydroxymethyl)furan, which is the compound shown in formula (5). Alternatively, 2,5-bis(hydroxymethyl)furan may be obtained by reacting ammonia with 2,5-bis(hydroxymethyl)furan in the presence of a catalyst, as shown in the following reaction equation, to obtain 2,5-bis(aminomethyl)furan, which is the compound shown in formula (4). As a method for synthesizing the compound shown in formula (4) from the compound shown in formula (5), the synthesis method described in "Chemical Science, 2020, 11, 9884-9890" may be used. 【0028】 [ka] 【0029】 Next, the amino group in 2,5-bis(aminomethyl)furan is phosgenated to obtain 2,5-bis(isocyanatomethyl)furan. Methods for obtaining 2,5-bis(isocyanatomethyl)furan include the reaction of at least one of 2,5-bis(aminomethyl)furan and its hydrochloride salt with phosgene. For reactions in which an amino group or amine hydrochloride salt is converted to an isocyanate group by reacting with phosgene, known methods for producing isocyanate compounds can be appropriately referenced. 【0030】 The reaction temperature for phosgenating amine hydrochloride is preferably 170°C or lower, and more preferably 150°C or lower, from the viewpoint of suppressing side reactions due to the dissociation of amine hydrochloride. 【0031】 (Method for producing compounds represented by general formula (1) 2) First, we will explain another example of a method for producing a compound represented by general formula (6), which is a type of compound represented by general formula (1), using biomass raw materials. 【0032】 [ka] 【0033】 It is preferable to prepare furfural derived from biomass raw materials as a raw material for the compound represented by general formula (6). For example, sugars such as xylose and hemicellulose are prepared as biomass raw materials. Hemicellulose may be decomposed into xylose by the action of an enzyme. Furfural is obtained by dehydration of xylose. Then, as shown in the following reaction equation, furfurylamine is obtained from furfural by conventionally known methods using a catalyst. After furfurylamine is converted to a hydrochloride salt, it is reacted with a carbonyl compound such as acetone, and the amino group derived from furfurylamine is phosgenated by conventionally known methods to obtain the compound represented by general formula (6). 【0034】 [ka] 【0035】 The polymerizable composition contains a compound represented by general formula (1) along with one or more thiol compounds having mercapto groups. 【0036】 Examples of thiol compounds include polythiol compounds having two or more mercapto groups, and hydroxythiol compounds having one or more mercapto groups and one or more hydroxyl groups. Among these, polythiol compounds having two or more mercapto groups and hydroxythiol compounds having one or more mercapto groups and one or more hydroxyl groups are preferred. As the thiol compound, oligomers of the thiol compound having one or more mercapto groups, halogen-substituted derivatives of the thiol compound having one or more mercapto groups (e.g., chlorine-substituted derivatives, bromine-substituted derivatives, etc.) may be used. Furthermore, thiol compounds may be used individually or in mixtures of two or more types. The thiol compound may or may not be derived from biomass raw materials. 【0037】 (Polythiol compounds having two or more mercapto groups) Examples of polythiol compounds having two or more mercapto groups (hereinafter also referred to as "polythiol compounds") include the compounds exemplified in International Publication No. 2016 / 125736. Examples of polythiol compounds include 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and pentaerythritol tetrakiss( Examples include 3-mercaptopropionate, bis(mercaptoethyl) sulfide, pentaerythritol tetrakis(2-mercaptoacetate), 2,5-bis(mercaptomethyl)-1,4-dithiane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, and 2-(2,2-bis(mercaptomethylthio)ethyl)-1,3-dithiane. 【0038】 Polythiol compounds are 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 4,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Tritiaundecane, and 5,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, Preferably, it includes at least one selected from the group consisting of the following: 【0039】 (Hydroxythiol compounds having one or more mercapto groups and one or more hydroxyl groups) Examples of hydroxythiol compounds having one or more mercapto groups and one or more hydroxyl groups include 2-mercaptoethanol, 3-mercapto-1,2-propanediol, and Ri Examples include serinebis(mercaptoacetate), 4-mercaptophenol, 2,3-dimercapto-1-propanol, pentaerythritol tris(3-mercaptopropionate), and pentaerythritol tris(thioglycolate). 【0040】 The polymerizable composition may further contain a composition comprising other active hydrogen compounds other than compounds having one or more mercapto groups. Examples of other active hydrogen compounds include polyol compounds having two or more hydroxyl groups, amine compounds, and the like. 【0041】 (Polyol compounds having two or more hydroxyl groups) Examples of polyol compounds having two or more hydroxyl groups include one or more aliphatic or alicyclic alcohols. Specifically, these include linear or branched aliphatic alcohols, alicyclic alcohols, and alcohols obtained by adding at least one selected from the group consisting of ethylene oxide, propylene oxide, and ε-caprolactone to these alcohols. More specifically, examples include the compounds exemplified in International Publication No. 2016 / 125736. 【0042】 Examples of polyol compounds having two or more hydroxyl groups include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, and 1,4-cyclohexanediol. 【0043】 (Amine compounds) Examples of amine compounds include ethylenediamine, 1,2- or 1,3-diaminopropane, 1,2-, 1,3- or 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,10-diaminodecane, 1,2-, 1,3- or 1,4-diaminocyclohexane, o-, m- or p-diaminobenzene, 3,4- or 4,4'-diaminobenzophenone, 3,4- or 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3' -or 4,4'-diaminodiphenylsulfone, 2,7-diaminofluorene, 1,5-, 1,8- or 2,3-diaminonaphthalene, 2,3-, 2,6- or 3,4-diaminopyridine, 2,4- or 2,6-diaminotoluene, m- or p-xylylenediamine, isophoronediamine, bis(aminomethyl)bi C Primary polyamine compounds such as chloroheptane, 1,3- or 1,4-bis(aminomethyl)cyclohexane, 2- or 4-aminopiperidine, 2- or 4-aminomethylpiperidine, 2- or 4-aminoethylpiperidine, N-aminoethylmorpholine, and N-aminopropylmorpholine; Monofunctional secondary amine compounds such as diethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine, diisobutylamine, di-n-pentylamine, di-3-pentylamine, dihexylamine, dioctylamine, di(2-ethylhexyl)amine, methylhexylamine, diallylamine, N-methylallylamine, piperidine, pyrrolidine, diphenylamine, N-methylamine, N-ethylamine, dibenzylamine, N-methylbenzylamine, N-ethylbenzylamine, dicyclohexylamine, N-methylaniline, N-ethylaniline, dinaphthylamine, 1-methylpiperazine, and morpholine; N,N'-dimethylethylenediamine, N,N'-dimethyl-1,2-diaminopropane, N,N'-dimethyl-1,3-diaminopropane, N,N'-dimethyl-1,2-diaminobutane, N,N'-dimethyl-1,3-diaminobutane, N,N'-dimethyl-1,4-diaminobutane, N,N'-dimethyl-1,5-diaminopentane, N,N'-dimethyl-1,6-diaminohexane, N,N'-dimethyl-1,7-diaminoheptane, N,N'-diethylethylenediamine, N,N'-diethyl-1,2-diaminopropane, N,N'-diethyl-1,3-diaminopropane, N,N'-diethyl-1,2-diamino Examples include secondary polyamine compounds such as nobutane, N,N'-diethyl-1,3-diaminobutane, N,N'-diethyl-1,4-diaminobutane, N,N'-diethyl-1,5-diaminopentane, N,N'-diethyl-1,6-diaminohexane, N,N'-diethyl-1,7-diaminoheptane, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 2,6-dimethylpiperazine, homopiperazine, 1,1-di-(4-piperidyl)methane, 1,2-di-(4-piperidyl)ethane, 1,3-di-(4-piperidyl)propane, 1,4-di-(4-piperidyl)butane, and tetramethylguanidine. 【0044】 The polymerizable composition may further contain an episulfide compound having one or more episulfide groups. 【0045】 Examples of episulfide compounds include epithioethylthio compounds, linear aliphatic 2,3-epithiopropylthio compounds, cyclic aliphatic 2,3-epithiopropylthio compounds, aromatic 2,3-epithiopropylthio compounds, linear aliphatic 2,3-epithiopropyloxy compounds, cyclic aliphatic 2,3-epithiopropyloxy compounds, and aromatic 2,3-epithiopropyloxy compounds. Episulfide compounds may be used individually or in combination of two or more types. 【0046】 Examples of episulfide compounds include those described in International Publication No. 2015 / 137401, International Publication No. 2017 / 159839, and Japanese Patent Publication No. 2018-154690, as well as thioepoxy compounds described in Japanese Patent Publication No. 2002-194083 and novel tetrathiaspiro compounds described in Japanese Patent Publication No. 2019-1785. 【0047】 The polymerizable composition may contain isocyanate compounds other than the compound represented by general formula (1) derived from biomass raw materials (hereinafter also referred to as other isocyanate compounds). Examples of other isocyanate compounds include the compound represented by general formula (1) that is not derived from biomass raw materials, pentamethylene diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, phenylene diisocyanate, and the like. Other isocyanate compounds may be used individually or in combination of two or more. Other isocyanate compounds (excluding compounds represented by general formula (1) that are not derived from biomass raw materials) may or may not be derived from biomass raw materials. 【0048】 In the polymerizable composition, the content of the compound represented by general formula (1) derived from biomass raw materials may be 50% to 100% by mass, 70% to 100% by mass, or 90% to 100% by mass, relative to the total amount of isocyanate compounds. 【0049】 The mixing ratio of the isocyanate compound containing the compound represented by general formula (1) to the thiol compound, and the mixing ratio of the isocyanate compound or thiol compound to the active hydrogen compound which may be included in the polymerizable composition as needed, are not particularly limited. For example, the ratio of the mass of the thiol compound to the mass of the isocyanate compound (i.e., mass [thiol compound / isocyanate compound]) is preferably 0.10 to 10.0, more preferably 0.20 to 5.00, even more preferably 0.50 to 1.50, and particularly preferably 0.70 to 1.30. For example, the molar ratio (mercapto group / isocyanato group) of the mercapto group in the thiol compound to the isocyanate group in the isocyanate compound is preferably 0.5 to 3.0, more preferably 0.6 to 2.0, and even more preferably 0.8 to 1.3. 【0050】 The total mass of the thiol compound and the isocyanate compound is not particularly limited. For example, the total mass is preferably 60% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, based on the total amount of the polymerizable composition. 【0051】 The polymerizable composition may contain components other than the aforementioned compounds (hereinafter also referred to as "other components"). Examples of other components include polymerization catalysts, internal release agents, resin modifiers, chain extenders, crosslinking agents, radical scavengers, light stabilizers, UV absorbers, antioxidants, oil-soluble dyes, fillers, adhesion enhancers, antibacterial agents, antistatic agents, dyes, fluorescent whitening agents, fluorescent pigments, inorganic pigments, and the like. 【0052】 Examples of polymerization catalysts include tertiary amine compounds, their inorganic or organic salts, metal compounds, quaternary ammonium salts, and organic sulfonic acids. 【0053】 As internal release agents, acidic phosphate esters, silicone compounds, etc., can be used. Examples of acidic phosphate esters include phosphate monoesters and phosphate diesters, which can be used individually or in combination of two or more types. 【0054】 For example, ZelecUN from STEPAN, internal release agent for MR from Mitsui Chemicals, JP series from Johoku Chemical Industry, Phosphanol® series from Toho Chemical Industry, AP and DP series from Daihachi Chemical Industry, etc. can be used. As silicone compounds, polyether-modified silicone compounds and the like can be used. 【0055】 Examples of resin modifiers include episulfide compounds, alcohol compounds, amine compounds, epoxy compounds, organic acids, anhydrides of organic acids, and olefin compounds including (meth)acrylate compounds. Here, (meth)acrylate compounds mean at least one of acrylate compounds and methacrylate compounds. 【0056】 The mixing of the above-mentioned components can be carried out according to conventional methods, and the method of mixing is not particularly limited. 【0057】 A cured product, which is the resin of this disclosure, is obtained by curing the polymerizable composition. The polymerizable composition described above can be cured by polymerizing the monomers in the polymerizable composition (e.g., isocyanate compounds, thiol compounds, and optionally active hydrogen compounds). As a pretreatment for polymerization, the polymerizable composition may be subjected to treatments such as filtration and degassing. The method for curing the polymerizable composition may be either thermal curing or photocuring, or a combination of thermal curing and photocuring. The polymerization conditions (e.g., polymerization temperature, polymerization time, etc.) for polymerizing the monomers in the above polymerizable composition are set appropriately, taking into consideration the composition of the composition, the type and amount of monomers used in the composition, the type and amount of polymerization catalyst used in the composition, and, if a mold described later is used, the properties of the mold. For example, when curing a polymerizable composition by thermosetting, the polymerization temperature can be, for example, 0°C to 150°C or 20°C to 130°C. Examples of polymerization times include 1 to 200 hours, 1 to 80 hours, and 1 to 48 hours. 【0058】 Polymers obtained by monomer polymerization may be subjected to treatments such as annealing. Typical annealing temperatures include 50°C to 150°C, 90°C to 140°C, and 100°C to 130°C. 【0059】 The biomass content of the resin disclosed herein is preferably 35% or more, and more preferably 50% or more. The biomass content of the resin may be 85% or less, or 70% or less. 【0060】 In the resin of this disclosure, the refractive index ne is preferably 1.650 or higher, more preferably 1.652 or higher, and even more preferably 1.654 or higher. In the resin of this disclosure, the refractive index ne may be 1.750 or less. The refractive index can be measured by the method described in the following examples. 【0061】 <2,5-Bis(isocyanatomethyl)furan> The 2,5-bis(isocyanatomethyl)furan of this disclosure is derived from 2,5-bis(aminomethyl)furan obtained from biomass raw materials. Examples of biomass raw materials include the aforementioned sugars. The preferred form of the 2,5-bis(isocyanatomethyl)furan of this disclosure is the same as the preferred form of 2,5-bis(isocyanatomethyl)furan described in the <Resin> section above. 【0062】 <Polymerizable composition> The polymerizable composition of this disclosure preferably contains 2,5-bis(isocyanatomethyl)furan as described in the <Resin> section above, or 2,5-bis(isocyanatomethyl)furan derived from biomass raw materials of this disclosure. 【0063】 The polymerizable compositions of this disclosure may contain one or more thiol compounds having mercapto groups or other active hydrogen compounds, and may also contain the other components mentioned above. Preferred forms of the polymerizable compositions are the same as preferred forms of polymerizable compositions described in the <Resins> section above. 【0064】 From the viewpoint of the refractive index of the resulting resin, the polymerizable composition of this disclosure preferably contains 2,5-bis(isocyanatomethyl)furan or 2,5-bis(isocyanatomethyl)furan derived from biomass raw materials of this disclosure, as described in the <Resin> section above, and a thiol compound having one or more mercapto groups. Furthermore, as the thiol compound, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 4,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Tritiaundecane, and 5,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, It is more preferable to include at least one selected from the group consisting of the following: 【0065】 <Molded body> The molded articles of this disclosure include the resin of this disclosure as described above. The molded articles of this disclosure may be manufactured, for example, by casting polymerization. 【0066】 In casting polymerization, the polymerizable composition is first injected between a pair of molding molds held together by a gasket, tape, etc. Degassing and filtration treatments may be performed as needed. Next, the monomers in the polymerizable composition injected between the molding molds are polymerized, causing the polymerizable composition to harden between the molding molds and obtain a cured product. Then, the cured product is removed from the molding molds to obtain the hardened product. This results in a molded body, which is a molded hardened product. 【0067】 <Optical materials> The optical materials of this disclosure include the molded articles of this disclosure described above. The optical materials of this disclosure can be manufactured, for example, by the casting polymerization described above. 【0068】 The optical materials of this disclosure may consist of a molded body of this disclosure, or may include a molded body of this disclosure and other elements. Other elements include other components, a coating layer applied to the molded article of this disclosure, and so on. 【0069】 Examples of optical materials in this disclosure include lenses (e.g., eyeglass lenses, camera lenses, polarizing lenses, etc.), light-emitting diodes (LEDs), and the like. 【0070】 <Lens> The lenses of this disclosure are examples of the optical materials of this disclosure and include the molded articles of this disclosure described above. The lenses of this disclosure may be manufactured, for example, by the casting polymerization described above. 【0071】 Examples of lenses in this disclosure include eyeglass lenses, camera lenses, polarized lenses, and the like. Below, we will describe eyeglass lenses as an example of the lenses described herein. The eyeglass lens includes a molded body of the present disclosure that is molded into a desired lens shape. The spectacle lens preferably further includes a coating layer provided on one or both sides of the molded body. 【0072】 Examples of coating layers include primer layers, hard coat layers, anti-reflective layers, anti-fogging layers, anti-stain layers, and water-repellent layers. These coating layers can be used individually or in multiple layers. When applying coating layers to both sides of a molded body, the same coating layer may be applied to each side, or different coating layers may be applied to each side. 【0073】 The components of the coating layer can be selected as appropriate depending on the purpose. The components of the coating layer include, for example, resins (e.g., urethane resin, epoxy resin, polyester resin, melamine resin, polyvinyl acetal resin, etc.), infrared absorbers, light stabilizers, antioxidants, photochromic compounds, dyes, pigments, antistatic agents, and the like. 【0074】 For eyeglass lenses and coating layers, you can refer to the descriptions in publicly available documents such as Japanese Patent Publication No. 2002-194083 and International Publication No. 2017 / 047745 as appropriate. [Examples] 【0075】 The following are examples of the embodiments of this disclosure, but this disclosure is not limited to the following embodiments. In the following, "room temperature" refers to 25°C unless otherwise specified. First, the evaluation method in the embodiments of this disclosure is shown below. 【0076】 <Evaluation Method> • Refractive index (ne), Abbe number (νe) Using a Shimadzu KPR-30 Pulfrich refractometer, the refractive indices (ne, nF', nC') were measured at wavelengths of 546.1 nm (mercury e line), 480.0 nm (Cd F' line), and 643.9 nm (Cd C' line), respectively, and the refractive index (ne) and Abbe number (νe) of the molded material were determined. ·Heat resistance Using a Shimadzu TMA-60 thermomechanical analyzer, the glass transition temperature (Tg) of the molded body was measured using the TMA penetration method (50g load, 0.5mmφ pin tip, heating rate 10℃ / min) and used as an indicator of heat resistance. • Specific gravity: Measured by the Archimedes method. · Hayes A haze meter (NDH 2000, manufactured by Nippon Denshoku Industries Co., Ltd.) was used to measure the haze value of a flat molded plate (thickness: 2.5 mm). Furthermore, if the haze value is less than 0.5, the lens can be used without any problems. pMC Measurement method Based on a tandem accelerator 14 Using a dedicated C-AMS device (manufactured by NEC Corporation), 14 The count of C, 13 C concentration ( 13 C / 12 C), and 14 C concentration ( 14 C / 12 Measurement C) was performed. For the measurement, oxalic acid (HOxII) provided by the U.S. National Institute of Standards (NIST) was used. This was used as a standard sample. Measurements of this standard sample and the background sample were also performed simultaneously. Calculation method (1)δ 13 C is the carbon of the sample 13 C concentration ( 13 C / 12 C) is measured and expressed as a deviation of 1000 parts (‰) from the reference sample. 14 Measurement values ​​obtained using a C-AMS device were used. (2) pMC is the carbon in the sample relative to standard modern carbon. 14 This is the percentage of C concentration. δ 13 The values ​​corrected by C are shown. 【0077】 [Experimental Example 1] Synthesis of 2,5-bis(aminomethyl)furan hydrochloride 48.0 g of 2,5-bis(aminomethyl)furan was added to 218.8 g of orthodichlorobenzene and stirred to prepare an orthodichlorobenzene solution containing 18.0% by mass of 2,5-bis(aminomethyl)furan. 298.2 g of orthodichlorobenzene was added to a 1 L five-necked flask and stirred, then the internal temperature was raised to 93°C. After raising the temperature to 93°C, hydrogen chloride gas was blown into the orthodichlorobenzene at a rate of 0.27 g / min. Next, the prepared 18.0 mass% orthodichlorobenzene solution of 2,5-bis(aminomethyl)furan was introduced into the orthodichlorobenzene at a rate of 1.16 g / min to start the reaction. The internal temperature was controlled between 93°C and 96°C during the reaction. After delivering the entire 18.0% by mass solution of 2,5-bis(aminomethyl)furan orthodichlorobenzene over a period of 3 hours and 50 minutes, hydrogen chloride gas was blown in for an additional 30 minutes. Subsequently, the bubbling of hydrogen chloride gas into the orthodichlorobenzene was stopped, and nitrogen gas was bubbling into the orthodichlorobenzene to degas the hydrogen chloride gas for 30 minutes. Finally, the reaction solution was returned to room temperature to obtain 617.3 g of 2,5-bis(aminomethyl)furan hydrochloride solution in orthodichlorobenzene. 【0078】 Synthesis of 2,5-bis(isocyanatomethyl)furan 328.2 g of the above-prepared 2,5-bis(aminomethyl)furan hydrochloride orthodichlorobenzene solution and 41.7 g of orthodichlorobenzene were added to a 500 mL five-necked flask and stirred, and the internal temperature was raised to 165°C. After raising the temperature, phosgene gas was blown into the solution at a rate of 43.5 g / hour for 4 hours. The internal temperature during the reaction was controlled between 161°C and 168°C. After blowing in the phosgene gas, the internal temperature was controlled between 155°C and 161°C, and nitrogen gas was blown into the reaction solution to degas the phosgene gas for 2 hours. The reaction solution was allowed to return to room temperature, yielding 363.7 g of 2,5-bis(isocyanatomethyl)furan solution. After filtering the obtained 2,5-bis(isocyanatomethyl)furan solution, it was purified by distillation to obtain 17.8 g of 2,5-bis(isocyanatomethyl)furan. 【0079】 [Experimental Example 2] Synthesis of 2,5-bis(isocyanatomethyl)furan 253.4 g of the orthodichlorobenzene solution of 2,5-bis(aminomethyl)furan hydrochloride prepared in Experimental Example 1 and 51.6 g of orthodichlorobenzene were added to a 500 mL five-necked flask and stirred, and the internal temperature was raised to 60°C. After raising the temperature, phosgene gas was blown into the solution at a rate of 45.5 g / hour for 4 hours. During the reaction, the internal temperature reached 145°C 40 minutes after the start of phosgene gas blowing and was controlled between 145°C and 150°C for 3 hours. Thereafter, the internal temperature gradually decreased, reaching 108°C after 4 hours. After phosgene gas blowing, nitrogen gas was blown into the reaction solution while controlling the internal temperature from 108°C to 150°C to degas the phosgene gas for 2 hours. The reaction solution was allowed to return to room temperature to obtain 300.1 g of 2,5-bis(isocyanatomethyl)furan solution. The obtained 2,5-bis(isocyanatomethyl)furan solution was filtered and then purified by distillation to obtain 19.3 g of 2,5-bis(isocyanatomethyl)furan. The carbon in the obtained 2,5-bis(isocyanatomethyl)furan 14 C concentration ratio (pMC, δ 13 (with C correction) was 62.99±0.22%, and the biomass content was 63%. 【0080】 [Example 1] A catalyst master solution was prepared by mixing 10.0 parts by mass of 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, which were synthesized according to the method described in International Publication No. 2021 / 010392, with 0.01 parts by mass of dibutyltin dichloride as a curing catalyst and epichlorohydrin derived from biomass raw materials. The carbon of the aforementioned polythiol composition 14 C concentration ratio (pMC, δ 13(with C correction) was 59.87±0.22%, and the biomass content was 60%. A solution was obtained by mixing and dissolving 0.0052 parts by mass of an internal release agent for MR (manufactured by Mitsui Chemicals, Inc.), 0.079 parts by mass of Biosorb 583 (manufactured by Kyodo Pharmaceutical Co., Ltd., 2-(2-hydroxy-5-tert-butyl-octylphenyl)benzotriazole), and 2.50 parts by mass of 2,5-bis(isocyanatomethyl)furan. To the obtained solution, 0.54 parts by mass of catalyst master solution and 2.24 parts by mass of 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, synthesized according to the method described in International Publication No. 2021 / 010392 using epichlorohydrin derived from biomass raw materials, with the same biomass content (60%) as above, were added and mixed to obtain a homogeneous solution. Next, the solution was filtered through a 3 μm filter, degassed at 400 Pa for 30 minutes, and the homogeneous solution was injected into a molding mold. Subsequently, the molding mold into which the homogeneous solution was injected was placed in a polymerization oven, and the temperature was gradually increased from 25°C to 120°C, allowing polymerization and curing to occur over 20 hours. After polymerization was complete, the cured material was removed from the oven and released from the molding mold, and then annealed at 120°C for 2 hours to obtain the molded body. The resulting molded body has a refractive index of 1.655 (e-line), an Abbe number of 33, a Tg of 88.4°C, a specific gravity of 1.409, and the carbon content in the molded body is 14 C concentration ratio (pMC, δ 13 (with C correction) was 60.07±0.19%, and the biomass content of the resin constituting the molded body was 60%. 【0081】 [Example 2] A catalyst master solution was prepared by mixing 10.0 parts by mass of 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, which were synthesized according to the method described in International Publication No. 2021 / 010392, with 0.01 parts by mass of dibutyltin dichloride as a curing catalyst and epichlorohydrin derived from non-biomass raw materials. The carbon of the aforementioned polythiol composition 14 C concentration ratio (pMC, δ 13 (with C correction) was <0.13%, and the biomass content was 0%. A solution was obtained by mixing and dissolving 0.0046 parts by mass of an internal release agent for MR (manufactured by Mitsui Chemicals, Inc.), 0.069 parts by mass of Biosorb 583 (manufactured by Kyodo Pharmaceutical Co., Ltd., 2-(2-hydroxy-5-tert-butyl-octylphenyl)benzotriazole), and 2.20 parts by mass of 2,5-bis(isocyanatomethyl)furan. To the obtained solution, 0.46 parts by mass of catalyst master solution and 1.95 parts by mass of 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, synthesized according to the method described in International Publication No. 2021 / 010392 using epichlorohydrin derived from non-biomass raw materials, with the same biomass content (0%) as above, were added and mixed to obtain a homogeneous solution. Next, the solution was filtered through a 3 μm filter, degassed at 400 Pa for 30 minutes, and the homogeneous solution was injected into a molding mold. Subsequently, the molding mold into which the homogeneous solution was injected was placed in a polymerization oven, and the temperature was gradually increased from 25°C to 120°C, allowing polymerization and curing to occur over 20 hours. After polymerization was complete, the cured material was removed from the oven and released from the molding mold, and then annealed at 120°C for 2 hours to obtain the molded body. The resulting molded body has a refractive index of 1.655 (e-line) and an Abbe number of 32. Tg 88.9℃, specific gravity 1.396, carbon in the molded body 14 C concentration ratio (pMC, δ 13 (with C correction) was 36.29±0.16%, and the biomass content of the resin constituting the molded body was 36%. 【0082】 [Example 3] A molded article was obtained in the same manner as in Example 1, except that a mixture of biomass and non-biomass raw materials was used as epichlorohydrin. The resulting molded body has a refractive index of 1.655 (e-line), an Abbe number of 32, a Tg of 85.8°C, a specific gravity of 1.406, and the carbon content in the molded body is 14 C concentration ratio (pMC, δ 13 The biomass content (with C correction) was 40.19 ± 0.16%, indicating that the biomass content of the resin constituting the molded body was 40%. Furthermore, the haze of the 2.5 mm thick molded body was 0.34, demonstrating high transparency. 【0083】 Furthermore, in Examples 1 to 3, molded articles with high transparency were obtained without special preparation methods such as reacting the polymerizable composition for more than one hour beforehand. 【0084】 On the other hand, in the comparative examples (e.g., Comparative Examples B9b to B11b) described in the aforementioned Patent Document 1 (International Publication No. 2015 / 119220), a 90-minute reaction operation is required in advance to prevent the lens clouding that occurs in other comparative examples (e.g., Comparative Examples B9 and B10). However, operations requiring a prior reaction may reduce the productivity of cured products such as lenses, and the increase in viscosity due to the reaction may make it difficult to inject the composition into the mold. As shown in Examples 1-3, this disclosure makes it possible to produce highly transparent cured products such as lenses without prior reaction operations, and offers excellent productivity of cured products. 【0085】 In particular, when the polymerizable composition contains a compound represented by general formula (1) which is 2,5-bis(isocyanatomethyl)furan represented by formula (2), and the thiol compound contains at least one selected from the group consisting of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 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, the production of cured products with excellent transparency tends to be excellent. Furthermore, cured products obtained using this polymerizable composition have a high biomass content, a high refractive index, and high heat resistance. 【0086】 The disclosure of Japanese Patent Application No. 2022-031204, filed on March 1, 2022, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference.

Claims

[Claim 1] A cured product of a polymerizable composition comprising a compound represented by the following general formula (1) and a thiol compound having one or more mercapto groups, The biomass content is 15% or more. The thiol compound is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 4,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Tritiaundecane, and 5,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Tritiaundecane, A resin comprising at least one selected from the group consisting of the following. 【Chemistry 1】 (In general formula (1), R １ and R ２ Each of these independently represents either a hydrogen atom or a methyl group. n represents an integer of 0 or 1. [Claim 2] The resin according to claim 1, wherein the compound represented by the general formula (1) is 2,5-bis(isocyanatomethyl)furan represented by the following formula (2). 【Chemistry 2】 [Claim 3] The resin according to claim 1, wherein the biomass content is 35% or more. [Claim 4] The polymerizable composition further comprises an episulfide compound having one or more episulfide groups, as described in claim 1. [Claim 5] The resin according to claim 1, wherein the refractive index ne is 1.650 or higher. [Claim 6] A molded article comprising the resin according to any one of claims 1 to 5. [Claim 7] An optical material comprising the molded article described in claim 6. [Claim 8] A lens comprising the molded body described in claim 6. [Claim 9] The product comprises 2,5-bis(isocyanatomethyl)furan having a biomass content of 50% or more, or 2,5-bis(aminomethyl)furan derived from biomass raw materials, and a thiol compound having one or more mercapto groups. The thiol compound is 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 4,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Tritiaundecane, and 5,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Tritiaundecane, A polymerizable composition comprising at least one selected from the group consisting of the following. [Claim 10] The polymerizable composition according to claim 9, further comprising an episulfide compound having one or more episulfide groups.

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