Compound having sulfur-containing aromatic heterocycle, polymerizable composition, and polymer

Abstract

To provide a compound that is easy to polymerize and makes it possible to produce a polymer with a sufficiently high refractive index.SOLUTION: The present invention relates to a compound represented by a formula (1), where A3 and A4 independently represent a (meth)acryloyl group, Cy1 and Cy2 independently represent an optionally substituted benzothiazole ring, Q1, Q2, Q3, and Q4 independently represent a C1-6 alkylene group, X1, X2, X3, and X4 independently represent a nitrogen atom optionally linked with an oxygen atom, a sulfur atom, or an organic group, Z1, Z2, Z3, and Z4 independently represent a divalent organic group, and n1, n2, n3, and n4 each represent 0.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a compound having a sulfur-containing aromatic heterocycle, a polymerizable composition containing the compound, and a polymer of the polymerizable composition. [Background technology]

[0002] Conventionally, glass has been widely used as an optical material. For example, in the case of optical lenses, even if the lenses have the same focal length, if they are manufactured using a material with a high refractive index, the lenses can be made thinner, which has the advantages of reducing weight and improving the degree of freedom in designing the optical path. In addition, high refractive index optical lenses are also effective in reducing the size, increasing the resolution, and increasing the angle of view of optical imaging devices. In recent years, highly transparent plastics have been attracting attention as an alternative optical material to glass. Compared to glass, plastic materials have the advantages of being lighter, easier to improve mechanical strength, and easier to process and mold. Patent Documents 1 and 2 relate to optical materials used, for example, in holographic recording media, and examples thereof describe a compound in which three of four molecular chains bonded to a quaternary carbon atom of a pentaerythritol skeleton have a sulfur atom and an aromatic ring, and one has a polymerizable group. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2016-222566 A [Patent Document 2] JP 2017-014213 A Summary of the Invention [Problem to be solved by the invention]

[0004] In recent years, with the development of peripheral technologies, there has been an increasing demand for improved performance of plastic optical materials. For example, materials for optical lenses are required to be easy to polymerize (easy polymerization), have good curing properties, and have a high refractive index after polymerization (high refractive index), but conventional compounds are not necessarily sufficient. An object of the present invention is to provide a compound which has good curability and can be used to produce a polymer having an excellent high refractive index, a polymerizable composition containing the compound, and a polymer of the polymerizable composition. [Means for solving the problem]

[0005] <1> A compound represented by the following formula (1A): [ka] [In the formula, A 3 , A 4 each independently represents a (meth)acryloyl group, Cy 1 , Cy 2 each independently represents a benzothiazole ring which may have a substituent; Q 1 , Q 2 , Q 3 , Q 4 each independently represents an alkylene group having 1 to 6 carbon atoms; X 1 , X 2 , X 3 , X 4 each independently represents an oxygen atom, a sulfur atom, or a nitrogen atom to which an organic group may be bonded; Z 1 , Z 2 , Z 3 , Z 4 each independently represents a divalent organic group, and n1, n2, n3, and n4 are all 0. <2> The above <1> and a polymerization initiator. <3> For use as a component constituting all or part of a transparent optical component; <2> The polymerizable composition according to claim 1. <4> For use as a component constituting part or all of a lens; <3> The polymerizable composition according to claim 1. <5> The above <2> ~ <4> A polymerizable product of the polymerizable composition according to any one of claims 1 to 4. The present invention also has the following aspects. [1] A compound represented by the following formula (1):

[0006] [ka]

[0007] [In the formula, A 1 , A 2 each independently represents a polymerizable group; Cy 1 , Cy 2 each independently represents a sulfur-containing aromatic heterocycle which may have a substituent; Q 1 , Q 2 , Q 3 , Q 4 each independently represents an alkylene group having 1 to 6 carbon atoms; X 1 , X 2 , X 3 , X 4 each independently represents an oxygen atom, a sulfur atom, or a nitrogen atom to which an organic group may be bonded; Z 1 , Z 2 , Z 3 , Z 4 each independently represents a divalent organic group, and n1, n2, n3, and n4 each independently represent 0 or an integer of 1 to 3.] [2] A. 1 , A 2 each independently represents a (meth)acryloyl group, 1 , Cy 2 each independently represents a benzothiazole ring which may have a substituent, a dibenzothiophene ring which may have a substituent, or a benzothiophene ring which may have a substituent. [3] A polymerizable composition comprising the compound of [1] or [2] above and a polymerization initiator. [4] A polymer of the polymerizable composition according to [3] above. [5] A compound represented by the following formula (2):

[0008] [ka]

[0009] [In the formula, Cy 1 , Cy 2 each independently represents a sulfur-containing aromatic heterocycle which may have a substituent; Q 1 , Q 2 , Q 3 , Q 4 each independently represents an alkylene group having 1 to 6 carbon atoms; X 1 , X 2 , X 3 , X 4 each independently represents an oxygen atom, a sulfur atom, or a nitrogen atom to which an organic group may be bonded; Z 1 , Z 2 , Z 3 , Z 4 each independently represents a divalent organic group, and n1, n2, n3, and n4 each independently represent 0 or an integer of 1 to 3.] [6] Cy 1 , Cy 2 each independently represents a benzothiazole ring which may have a substituent, a dibenzothiophene ring which may have a substituent, or a benzothiophene ring which may have a substituent. [7] A polymerizable composition comprising the compound according to [5] or [6] above, a dicarboxylic acid compound, a diester compound, or a carbonate ester compound, and a polymerization catalyst. [8] A polymer of the polymerizable composition according to [7]. [9] A method for producing a compound, comprising reacting a compound represented by the following formula (2) with a (meth)acrylate agent to obtain a compound represented by the following formula (1A):

[0010] [ka]

[0011] [In the formula, Cy 1 , Cy 2 each independently represents a sulfur-containing aromatic heterocycle which may have a substituent; Q 1 , Q 2 , Q3 , Q 4 each independently represents an alkylene group having 1 to 6 carbon atoms; X 1 , X 2 , X 3 , X 4 each independently represents an oxygen atom, a sulfur atom, or a nitrogen atom to which an organic group may be bonded; Z 1 , Z 2 , Z 3 , Z 4 each independently represents a divalent organic group, and n1, n2, n3, and n4 each independently represent 0 or an integer of 1 to 3.]

[0012] [ka]

[0013] [In the formula, A 3 , A 4 each independently represents a (meth)acryloyl group, Q 1 , Q 2 , Q 3 , Q 4 , Cy 1 , Cy 2 , X 1 , X 2 , X 3 , X 4 , Z 1 , Z 2 , Z 3 , Z 4 , n1, n2, n3, and n4 are the same as in formula (2).

[10] The method according to [9], wherein the reaction product of the compound represented by the formula (2) and the (meth)acrylate agent is purified by a recrystallization method. Effect of the Invention

[0014] The compound of the present invention is easily polymerizable, and can produce a polymer having a high refractive index. The polymerizable composition containing the compound of the present invention is easily polymerized, and can produce a polymer having an excellent high refractive index. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] In this specification, "(meth)acrylic" is a general term for acrylic and methacrylic. "(meth)acrylate" is a general term for acrylate and methacrylate. "(meth)acryloyl group" is a general term for acryloyl group and methacryloyl group, and is a group represented by CH2=C(R)-C(=O)- (R represents a hydrogen atom or a methyl group). In this specification, the compound represented by formula (1) will be referred to as compound (1). Compounds represented by other formulas will be similarly referred to.

[0016] <Compound (1)> The compound (1) of this embodiment is represented by the following formula (1).

[0017] [ka]

[0018] In equation (1), Q 1 , Q 2 , Q 3 , Q 4 Each independently represents an alkylene group having 1 to 6 carbon atoms. It may be linear or branched. The number of carbon atoms is preferably 1 to 4. A methylene group, an ethylene group, a methylmethylene group, or an ethylmethylene group is more preferred, a methylene group or an ethylene group is even more preferred, and a methylene group is particularly preferred. Q in one molecule 1 , Q 2 , Q 3 , Q 4 may be the same as or different from each other. Q is advantageous in that raw materials are easily available and the stereoisomers of the products can be easily controlled. 1 , Q 2 , Q 3 , Q 4 are preferably the same as each other.

[0019] In formula (1), A 1 , A 2each independently represents a polymerizable group. The polymerizable group is preferably a group containing a polymerizable carbon-carbon double bond or a group containing an alicyclic ether bond. Specific examples of the group containing a polymerizable carbon-carbon double bond include a (meth)acryloyl group, a vinyl group, a vinyl-substituted phenyl group, an isopropenyl-substituted phenyl group, a vinyl-substituted naphthyl group, and an isopropenyl-substituted naphthyl group. Specific examples of the group containing an alicyclic ether bond include an oxiranyl group, a 2-methyloxiranyl group, and an oxetanyl group. The (meth)acryloyl group is preferred because it is easy to obtain high transparency. 1 and A 2 may be the same as or different from each other.

[0020] In formula (1), Cy 1 , Cy 2 Each independently represents a sulfur-containing aromatic heterocycle which may have a substituent. The sulfur-containing aromatic heterocycle contributes to a high refractive index. The sulfur-containing aromatic heterocycle may have a substituent. 1 and Cy 2 may be the same as or different from each other. In terms of facilitating raw material acquisition and synthesis, Cy 1 and Cy 2 It is preferable that Cy be the same as Cy. 1 and Cy 2 are preferably different. The sulfur-containing aromatic heterocycle has at least a sulfur atom as a heteroatom constituting the aromatic heterocycle. In addition to the sulfur atom, the heteroatom may have an oxygen atom, a nitrogen atom, or an oxygen atom and a nitrogen atom. From the viewpoint of avoiding coloration and ensuring solubility, the number of heteroatoms constituting the sulfur-containing aromatic heterocycle is preferably 1 to 3, more preferably 1 to 2.

[0021] Specific examples of sulfur-containing aromatic heterocycles include aromatic heterocycles containing one sulfur atom, such as a thiophene ring, a benzothiophene ring, a dibenzothiophene ring, a thiopyran ring, a naphthothiophene ring, a dinaphthothiophene ring, and a dibenzothiopyran ring; aromatic heterocycles containing two or more sulfur atoms, such as a thianthrene ring; and aromatic heterocycles containing two or more heteroatoms, such as a thiazole ring, an isothiazole ring, a benzothiazole ring, a naphthothiazole ring, a phenothiazine ring, a thiazoloimidazole ring, a thiazolopyridine ring, a thiazolopyridazine ring, a thiazolopyrimidine ring, a dioxazolopyrazine ring, a thiazolopyrazine ring, a thiazolooxazole ring, a dibenzobenzothiophene ring, a thienoxazole ring, a thienothiadiazole ring, and a thiazolothiadiazole ring. The sulfur-containing aromatic heterocycle may be a single ring or a condensed ring. A condensed ring is preferable from the viewpoint of increasing the refractive index. The number of rings constituting the condensed ring is preferably 2 to 5, more preferably 2 to 4, and particularly preferably 2 to 3 from the viewpoint of facilitating the availability of raw materials and synthesis. In particular, a benzothiazole ring, a dibenzothiophene ring, and a benzothiophene ring are preferred in terms of increasing the refractive index and reducing coloration.

[0022] Cy 1 , Cy 2 The linking group (-S-) that is bonded to Cy 1 , Cy 2 may be bonded to any position of the ring structure. Cy 1 , Cy 2 may have a substituent. The substituent is preferably an alkyl group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, an alkoxyalkoxy group, or an alkanoyloxy group, in terms of easiness in improving solubility. Preferably, the substituent is an aryl group, an alkylthio group, an alkylthioalkyl group, an aryloxy group, an arylalkoxyl group, or a halogen atom, in terms of easiness in increasing the refractive index. In order to achieve economical synthesis, non-substitution is preferred. The alkyl group may be linear or branched and preferably has 1 to 8 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, an n-hexyl group, and a 2-ethylhexyl group. The carbon number of the alkoxy group is preferably 1 to 4. Specific examples include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an s-butoxy group, and a t-butoxy group. The carbon number of the alkoxyalkyl group is preferably 2 to 6. Specific examples include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, a methoxyethyl group, an ethoxyethyl group, a propoxyethyl group, and a butoxyethyl group. The carbon number of the alkoxycarbonyl group is preferably 2 to 5. Specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and a butoxycarbonyl group. The carbon number of the alkoxyalkoxy group is preferably 3 to 6. Specific examples include a methoxyethoxy group, an ethoxyethoxy group, a propoxyethoxy group, and a butoxyethoxy group. The carbon number of the alkanoyloxy group is preferably 2 to 5. Specific examples include an acetoxy group, a propionoxy group, a butyloxy group, and a valeroxy group. The ring structure of the aryl group may be a single ring or a condensed ring. The number of carbon atoms in the aryl group is preferably 6 to 14. Specific examples include a phenyl group, a tolyl group, a mesityl group, a naphthyl group, and an anthranyl group. The carbon number of the alkylthio group is preferably 2 to 4. Specific examples include a methylthio group, an ethylthio group, an n-propylthio group, and an isopropylthio group. The carbon number of the alkylthioalkyl group is preferably 2 to 4. Specific examples include a methylthiomethyl group, a methylthioethyl group, an ethylthiomethyl group, and an ethylthioethyl group. The ring structure of the aryloxy group may be a single ring or a condensed ring. The number of carbon atoms in the aryloxy group is preferably 6 to 14. Specific examples include a phenoxy group. The ring structure of the arylalkoxy group may be a single ring or a condensed ring. The number of carbon atoms in the arylalkoxy group is preferably 7 to 15. A specific example is a benzyloxy group. The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

[0023] In formula (1), X 1 , X 2 , X 3 , X 4 each independently represents an oxygen atom, a sulfur atom, or a nitrogen atom which may have an organic group bonded thereto. The organic group that may be bonded to the nitrogen atom is not particularly limited, but examples thereof include alkyl groups having 1 to 8 carbon atoms (e.g., methyl group, ethyl group), and aromatic hydrocarbon groups having 6 to 15 carbon atoms (e.g., phenyl group, naphthyl group), and it is preferable that such an organic group is bonded to the nitrogen atom. X 1 , X 2 From the viewpoints of facilitating synthesis and reducing viscosity, an oxygen atom or a sulfur atom is preferred. From the viewpoint of availability of raw materials, an oxygen atom is more preferred, and from the viewpoint of refractive index, a sulfur atom is more preferred. Among these, an oxygen atom is particularly preferred. 1 and X 2 are preferably the same. X 3 , X 4 In terms of the ease of keeping the water absorption rate low, an oxygen atom or a sulfur atom is preferred. In terms of availability of raw materials, an oxygen atom is more preferred, and in terms of refractive index, a sulfur atom is more preferred. Among these, an oxygen atom is particularly preferred. 3 and X 4 are preferably the same.

[0024] In formula (1), Z 1 , Z 2 , Z 3 , Z 4 Each independently represents a divalent organic group. 1 and Z 2 are preferably the same in terms of ease of synthesis. 3 and Z 4are preferably the same in terms of ease of synthesis. The divalent organic group may be linear, branched, or cyclic. A hydrocarbon group which may have a substituent is preferred. The number of carbon atoms in the hydrocarbon group (not including the number of carbon atoms in the substituent) is preferably 1 to 8. If the number of carbon atoms is 8 or less, the refractive index is unlikely to decrease, the viscosity is likely to decrease due to the small molecular weight, and processability is likely to improve. Specific examples include methylene, ethylene, 1,3-propylene, 1,2-propylene, butylene, 2-hydroxypropylene, oxopropylene, oxobutylene, oxohexylene, oxoheptylene, 3-oxapentylene, cyclohexylene, phenylene, xylylene, -CH2CH2NHC(O)-, -CH2CH2OCH2CH2NHC(O)-, etc. Methylene, ethylene, 1,3-propylene, 1,2-propylene, 2-hydroxypropylene, and -CH2CH2NHC(O)- are preferred. Examples of the substituent include a halogen atom (a chlorine atom, a bromine atom, an iodine atom), a hydroxyl group, a mercapto group, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a mesityl group, a tolyl group, a naphthyl group, a cyano group, an acetyloxy group, an alkylcarbonyloxy group having 2 to 9 carbon atoms, an alkoxycarbonyl group having 2 to 9 carbon atoms, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, an alkylcarbonyl group having 2 to 9 carbon atoms, a phenethyl group, a hydroxyethyl group, an acetylamide group, a dialkylaminoethyl group having an alkyl group having 1 to 4 carbon atoms bonded thereto, a trifluoromethyl group, an alkylthio group having 1 to 8 carbon atoms, and a nitro group. Among these, alkyl groups having 1 to 8 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, cyano groups, acetyloxy groups, alkylcarboxyl groups having 2 to 8 carbon atoms, sulfamoyl groups, alkylsulfamoyl groups having 2 to 9 carbon atoms, and nitro groups are preferred.

[0025] In formula (1), n1, n2, n3, and n4 each independently represent 0 or an integer of 1 to 3. When n1, n2, n3, and n4 are small, the refractive index tends to be high. When n1, n2, n3, and n4 are small, the compound tends to be solid at room temperature (23°C). When the compound is solid at room temperature, it is possible to purify the compound by a recrystallization method, and a compound (1) that is nearly colorless and transparent (low coloring) can be obtained. By producing a polymer using the compound (1) that is low coloring, it becomes easy to obtain a polymer with low coloring. A polymer that is nearly colorless and transparent (low coloring) is particularly suitable for optical materials. In this specification, being solid at room temperature means having a melting point at or above room temperature, and when a sample is measured with a differential scanning calorimeter while increasing the temperature, an endothermic peak can be observed upon dissolution, or a melting point can be observed at or above room temperature with a melting point measuring device. On the other hand, when n1, n2, n3, and n4 are large, the material is easily liquefied and good processability is easily obtained. An embodiment in which n1, n2, n3 and n4 are all 0 is more preferable, in that a compact structure makes it easier to increase the aromatic ring density and thus the refractive index, and a compound with low coloration can be obtained. In terms of ease of improving processability by lowering the melting point of the compound or liquefying it, an embodiment in which n1, n2, n3, and n4 are each independently an integer of 1 to 3 is preferred.

[0026] Preferred embodiments of compound (1) include the following. Mode (1): A 1 , A 2 are each independently a (meth)acryloyl group, and Cy 1 , Cy 2 are each independently a benzothiazole ring which may have a substituent, a dibenzothiophene ring which may have a substituent, or a benzothiophene ring which may have a substituent. Mode (2): Mode (1), in which n1, n2, n3, and n4 are all 0. Aspect (3): In aspect (1), Q 1 , Q 2 , Q 3 , Q 4 are all methylene groups. Mode (4): In mode (1), n1, n2, n3, and n4 are all 0, and Q 1 , Q 2 , Q 3 , Q 4 are all methylene groups. Specific examples of the embodiment (4) include the following compounds (1A-1) to (1A-18).

[0027] [ka]

[0028] [ka]

[0029] The compound (1) of the present embodiment is easily polymerized since it has two polymerizable groups per molecule, and also has two molecular chains containing a sulfur-containing aromatic heterocycle per molecule, which makes it easy to obtain a high refractive index. In formula (1), compounds that are solid at room temperature are preferred from the viewpoint of ease of purification. Compounds that are liquid at room temperature are preferred because they are easily processable. Compound (1) that is liquid at room temperature is easy to mix in any ratio when synthesizing a polymer using compound (1). The refractive index of compound (1), measured at 23°C with helium lamp d-line (587.6 nm), is preferably 1.60 or more, more preferably 1.63 or more, and even more preferably 1.65 or more. If the refractive index of compound (1) is 1.60 or more, when it is applied to a transparent optical component, various optical designs become possible, and it can be applied to various uses. The refractive index is a value measured by the method described below.

[0030] <Method for producing compound (1)> Compound (1) is prepared by converting the active hydrogens (H) of the two hydroxyl groups into polymerizable groups (A 1 , A 2 ) can be used to produce the product. For example, the compound (1A) represented by the following formula (1A) is 1 , A 2 are each independently a (meth)acryloyl group. Compound (1A) can be produced by a method of reacting compound (2) with a (meth)acrylate agent.

[0031] [ka]

[0032] [ka]

[0033] In equation (2), Q 1 , Q 2 , Q 3 , Q 4 , Cy 1 , Cy 2 , X 1 , X 2 , X 3 , X 4 , Z 1 , Z 2 , Z 3 , Z 4 , n1, n2, n3, and n4 are the same as in formula (1), including preferred embodiments. In formula (1A), A 3 , A 4 each independently represents a (meth)acryloyl group, Q 1 , Q 2 , Q 3 , Q 4 , Cy 1 , Cy 2 , X 1 , X 2 , X 3 , X 4 , Z 1 , Z 2 , Z 3 , Z 4 , n1, n2, n3, and n4 are the same as in equation (2). In formula (1A), A 3 , A 4each independently represents a (meth)acryloyl group, Q 1 , Q 2 , Q 3 , Q 4 , Cy 1 , Cy 2 , X 1 , X 2 , X 3 , X 4 , Z 1 , Z 2 , Z 3 , Z 4 , n1, n2, n3, and n4 are the same as in equation (2). Formula (1A') is Cy of formula (1A). 1 , Cy 2 Limited to the benzothiazole ring, Cy 11 , Cy 12 where n1, n2, n3, and n4 are limited to zero.

[0034] The (meth)acrylating agent may be any compound having a (meth)acryloyl group or a group convertible to a (meth)acryloyl group and capable of reacting with active hydrogen, such as (meth)acrylic acid chloride, (meth)acrylic acid anhydride, (meth)acrylic acid ester, 3-chloropropionic acid chloride, 2-acryloyloxyethyl isocyanate, and 2-methacryloyloxyethyl isocyanate. The reaction of the active hydrogen of the compound (2) with a (meth)acrylate agent can be carried out by a known method. For example, the compound (1A) can be obtained by reacting the compound (2) with a (meth)acrylate agent in the presence of a basic compound. The basic compound may be one or more organic basic compounds (e.g., triethylamine, pyridine, imidazole), one or more inorganic basic compounds (e.g., sodium carbonate, potassium carbonate), or a combination of one or more organic basic compounds and one or more inorganic basic compounds. It is preferable to use an organic solvent in the reaction between compound (2) and a (meth)acrylate agent. Examples of the organic solvent include dimethoxyethane, dichloromethane, tetrahydrofuran (THF), toluene, and N,N-dimethylformamide (DMF). One type of organic solvent may be used, or two or more types may be used in combination.

[0035] The reaction between compound (2) and the (meth)acrylate agent is preferably carried out in a reaction system that does not contain moisture. Specifically, the reaction is preferably carried out in an inert gas (argon gas, nitrogen gas) atmosphere. The organic solvent is preferably a dehydrated, dry organic solvent. The amount of the (meth)acrylate agent used is preferably 1.0 mol or more, more preferably 1.5 mol or more, and even more preferably 2.0 mol or more per mol of compound (2) because purification becomes difficult if the reaction is not completed and raw materials remain. Also, from the viewpoint of suppressing side reactions and the load on the post-reaction treatment process, the amount of the (meth)acrylate agent used is preferably 8 mol or less, more preferably 6 mol or less, and even more preferably 5 mol or less per mol of compound (2). The amount of the basic compound used is preferably 1.0 mol or more, more preferably 1.5 mol or more, and even more preferably 2.0 mol or more per mol of compound (2) because purification becomes difficult if the reaction is not completed and raw materials remain. Also, from the viewpoint of suppressing side reactions and the load on the post-reaction treatment process, the amount of the basic compound used is preferably 8 mol or less, more preferably 6 mol or less, and even more preferably 5 mol or less per mol of compound (2).

[0036] In the production of compound (1), it is preferable to purify the reaction product (crude product) obtained in the synthesis reaction. By purifying and removing impurities, low coloration can be achieved. As the purification method, a known method can be applied. For example, purification can be performed by means of extraction, column chromatography, recrystallization, distillation, etc. These purification methods may be performed by one method or in combination. When compound (1) is a solid at room temperature, it is preferable to use a recrystallization method, since colored substances can be easily removed to a high degree. Examples of the recrystallization solvent include aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane, alicyclic hydrocarbons such as cyclopentane and cyclohexane, aromatic hydrocarbons such as toluene, ethylbenzene, xylene, and mesitylene, halogenated hydrocarbons such as methylene chloride, chloroform, and 1,2-dichloroethane, ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, t-butyl methyl ether, and 1,4-dioxane, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, esters such as ethyl acetate, n-butyl acetate, and propylene glycol monomethyl ether acetate, nitriles such as acetonitrile and propionitrile, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, t-butanol, 2-methoxyethanol, 2-butoxyethanol, and propylene glycol monomethyl ether, glycols such as ethylene glycol and diethylene glycol, and water. These solvents may be used alone or in combination of two or more. In that the amount of impurities can be easily reduced with only one solvent, an alcohol-based solvent is preferred, and ethanol is more preferred.

[0037] <Curable resin raw material composition containing compound (1)> A first embodiment of the polymerizable composition is a curable resin raw material composition containing compound (1). In this specification, the polymer of the curable resin raw material composition is also referred to as a curable resin. Compound (1) is suitable as a raw material for curable resins such as poly(meth)acrylate resins. The curable resin raw material composition of the present embodiment contains a compound (1) and a polymerization initiator. A polymer is obtained by polymerizing the polymerizable group of the compound (1). The compound (1) may be used alone or in combination of two or more kinds. The curable resin raw material composition of the present embodiment may contain, in addition to the compound (1), other polymerizable compounds copolymerizable with the compound (1). It may also contain other components not having a polymerizable group. It may also contain a solvent, if necessary.

[0038] [Polymerization initiator] The polymerization initiator may be any one that initiates the polymerization reaction of the polymerizable group of the compound (1). Known polymerization initiators may be appropriately used depending on the polymerization method. The polymerization initiator may be used alone or in combination of two or more kinds. For example, a radical polymerization initiator can be used, such as a photopolymerization initiator, a thermal polymerization initiator, or a peroxide used in redox polymerization.

[0039] The photopolymerization initiator is a radical polymerization initiator used in photopolymerization. Specific examples of the photopolymerization initiator include benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, 4-phenylbenzophenone, and other benzophenone-type compounds; t-butylanthraquinone, 2-ethylanthraquinone, and other anthraquinone-type compounds; 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone}, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl ether, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-hydroxy-1-{4-[4-(2- alkylphenone type compounds such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, diethylthioxanthone, isopropylthioxanthone, and the like; acylphosphine oxide type compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and the like; and phenylglyoxylate type compounds such as phenylglyoxylic acid methyl ester, and the like. Among these, alkylphenone type compounds are preferred in terms of suppressing coloration of the polymer, and 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1-hydroxycyclohexyl phenyl ketone are more preferred. Acylphosphine oxide type compounds are preferred in terms of facilitating sufficient polymerization into the interior of the polymer, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide is more preferred in terms of suppressing coloration of the polymer. These photopolymerization initiators may be used alone or in combination of two or more.

[0040] The thermal polymerization initiator is a radical polymerization initiator used in thermal polymerization, and examples of the thermal polymerization initiator include organic peroxides and azo compounds. Specific examples of organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide; peroxyketals such as 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, and 1,1-di(t-butylperoxy)cyclohexane; hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, and p-menthane hydroperoxide; dicumyl peroxide, and di-t-butyl peroxide. diacyl peroxides such as dilauroyl peroxide and dibenzoyl peroxide; peroxydicarbonates such as di(4-t-butylcyclohexyl)peroxydicarbonate and di(2-ethylhexyl)peroxydicarbonate; and peroxy esters such as t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxybenzoate, and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate. Specific examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1'-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2'-azobisisobutyrate, 4,4'-azobis-4-cyanovaleric acid, and 2,2'-azobis-(2-amidinopropane) dihydrochloride. These thermal polymerization initiators may be used alone or in combination of two or more.

[0041] As the thermal polymerization initiator, an organic peroxide is preferred because it is less likely to cause bubbles in the polymer. Considering the balance between the curing time and pot life of the curable resin raw material composition, the 10-hour half-life temperature of the organic peroxide is preferably 35 to 80°C, more preferably 40 to 75°C, and even more preferably 45 to 70°C. If the 10-hour half-life temperature is 35°C or higher, the curable resin raw material composition is less likely to gel at room temperature, and the pot life is good. On the other hand, if the 10-hour half-life temperature is 80°C or lower, the curing time of the curable resin raw material composition can be shortened. Examples of such organic peroxides include 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, and di(4-t-butylcyclohexyl)peroxydicarbonate. Commercially available products of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate include, for example, Perocta O (trade name, manufactured by NOF Corp., 10-hour half-life temperature: 65.3°C). Commercially available products of t-butylperoxy-2-ethylhexanoate include, for example, Perbutyl O (trade name, manufactured by NOF Corp., 10-hour half-life temperature: 72.1°C). Commercially available products of di(4-t-butylcyclohexyl)peroxydicarbonate include, for example, Peroyl TCP (trade name, manufactured by NOF Corp., 10-hour half-life temperature: 40.8°C).

[0042] Examples of peroxides used in redox polymerization include dibenzoyl peroxide, hydroperoxide, etc. These peroxides may be used alone or in combination of two or more kinds. In addition, a redox polymerization initiator is usually used for redox polymerization. The redox polymerization initiator is a polymerization initiator in which a peroxide and a reducing agent are used in combination. When the above-mentioned peroxide is used as a redox polymerization initiator, an example of the combination with the reducing agent is as follows. (1) A combination of dibenzoyl peroxide (peroxide) and an aromatic tertiary amine (reducing agent) such as N,N-dimethylaniline, N,N-dimethyl-p-toluidine, or N,N-bis(2-hydroxypropyl)-p-toluidine. (2) A combination of hydroperoxides (peroxides) and metal soaps (reducing agents). (3) A combination of hydroperoxides (peroxides) and thioureas (reducing agents).

[0043] [Other polymerizable compounds] Examples of other polymerizable compounds (excluding compound (1)) include monofunctional (meth)acrylic monomers, polyfunctional (meth)acrylic monomers, vinyl group-containing monomers other than (meth)acrylic monomers, silsesquioxane compounds having a radical polymerizable group, etc. The polyfunctional (meth)acrylic monomer preferably has 2 to 6 (meth)acryloyl groups.

[0044] Specific examples of the monofunctional (meth)acrylate compound include (meth)acrylates containing a carboxyl group, such as (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl maleate, 2-(meth)acryloyloxyethyl phthalate, and 2-(meth)acryloyloxyethyl hexahydrophthalate; (Meth)acrylates having a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate; methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, heptyl (meth)acrylate, (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate and other alkyl (meth)acrylates; cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, 2-dicyclopentenoxyethyl (meth)acrylate, iso Bornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, phenoxypolypropylene glycol (meth)acrylate, phenylphenyl (meth)acrylate, phenylphenoxy (meth)acrylates containing a cyclic structure, such as methoxyethyl (meth)acrylate, phenoxybenzyl (meth)acrylate, phenylbenzyl (meth)acrylate, naphthyl (meth)acrylate, (1-naphthyl)methyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, and (meth)acryloylmorpholine; alkoxy (meth)acrylates, such as methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, and butoxyethyl (meth)acrylate; Examples of the silane derivatives include 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 2-(meth)acryloyloxyethyl acid phosphate, trifluoroethyl (meth)acrylate, heptadecafluorodecyl (meth)acrylate, and 2-(meth)acryloyloxyethyl isocyanate.

[0045] Specific examples of polyfunctional (meth)acrylate compounds include alkylene glycol di(meth)acrylates such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,9-nonanediol di(meth)acrylate; polyalkylene glycol di(meth)acrylates such as polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polybutylene glycol di(meth)acrylate; neopentyl glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, polycarbonate diol di(meth)acrylate, polyester diol di(meth)acrylate, and ethoxy Examples of the polyfunctional monomer include bifunctional (meth)acrylates such as propoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, 9,9-bis(4-acryloyloxyethoxyphenyl)fluorene, and polyurethane di(meth)acrylate; trifunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, and ε-caprolactone-modified tris((meth)acryloxyethyl)isocyanurate; tetrafunctional (meth)acrylates such as ditrimethylolpropane tetra(meth)acrylate; pentafunctional (meth)acrylates such as dipentaerythritol penta(meth)acrylate; and hexafunctional (meth)acrylates such as dipentaerythritol hexa(meth)acrylate.

[0046] Examples of vinyl group-containing monomers other than (meth)acrylic monomers include aromatic vinyl monomers (styrene, α-methylstyrene, etc.), vinyl cyanide monomers (acrylonitrile, etc.), and vinyl ester monomers (vinyl acetate, etc.). A silsesquioxane compound having a radically polymerizable group can be obtained, for example, by subjecting an alkoxysilane compound containing a trialkoxysilane compound having one radically polymerizable group in the molecule (e.g., 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, etc.). The other polymerizable compounds may be used alone or in combination of two or more kinds. As the other polymerizable compound, a compound having a (meth)acryloyl group is preferable since high transparency can be easily obtained.

[0047] [Other ingredients] Examples of other components include acrylic polymers, rubber, titanium oxide (IV), chromium oxide (III), zinc sulfide, aluminum oxide, barium sulfate, barium titanate, antimony trioxide, iron oxide (III), cadmium sulfide, cerium oxide (IV), lead chloride (II), cadmium oxide, tungsten oxide (VI), indium oxide (III), lead oxide (II), tantalum oxide (V), zirconium oxide (IV), and other highly refractive inorganic compounds, silica particles, plasticizers, antioxidants, ultraviolet absorbers, defoamers, thixotropic agents, polymerization inhibitors, release agents, fillers, fluorescent materials, pigments, and the like. The above-mentioned other components may be added when a high refractive index or light resistance is required, but may not be added when transparency is required. When added, one type may be used alone, or two or more types may be used in combination.

[0048] An acrylic polymer may be added to the curable resin raw material composition of the present embodiment for the purpose of increasing viscosity and reducing cure shrinkage. Specific examples of the acrylic polymer include the following: PMMA, a copolymer of methyl methacrylate and n-butyl methacrylate, a copolymer of methyl methacrylate and n-butyl acrylate, etc.

[0049] In order to improve the strength of the polymer, rubber may be added to the curable resin raw material composition of the present embodiment. Specific examples of rubber include the following: (meth)acrylic acid ester-butadiene copolymer, (meth)acrylic acid ester-butadiene-styrene copolymer, polybutadiene rubber, chloroprene rubber, acrylonitrile butadiene rubber, etc.

[0050] An antioxidant may be added to the curable resin raw material composition of this embodiment in order to prevent the polymer from being oxidized and deteriorated. Specific examples of the antioxidant include the following: phenol-based antioxidants such as n-octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate, tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, triethylene glycol bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], and 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]; phosphorus-based antioxidants such as tris(2,4-di-t-butylphenyl)phosphite, trisisodecylphosphite, tristridecylphosphite, tris(2,4-di-t-butylphenyl)phosphite, etc.; sulfur-based antioxidants such as dihexyl sulfide, dilauryl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distereyl-3,3'-thiodipropionate, pentaerythritol tetrakis(β-laurylthiopropionate), etc.

[0051] A plasticizer may be added to the curable resin raw material composition of the present embodiment in order to adjust the hardness of the polymer. Specific examples of the plasticizer include the following: phthalates such as dibutyl phthalate, di-2-ethylhexyl phthalate, and diisodecyl phthalate; adipic esters such as di-2-ethylhexyl adipate and octyl adipate; sebacic esters such as dibutyl sebacate and di-2-ethylhexyl sebacate; azelaic esters such as di-2-ethylhexyl azelate and octyl azelate; and dibasic fatty acid esters; paraffins such as chlorinated paraffin.

[0052] In order to suppress photodegradation of the polymer, an ultraviolet absorber may be added to the curable resin raw material composition of this embodiment. Specific examples of ultraviolet absorbers include the following: 2-hydroxybenzophenone derivatives such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-octyloxybenzophenone, 2-hydroxy-4-decyloxybenzophenone, 2-hydroxy-4,4'-dimethoxybenzophenone, and 2-hydroxy-4,4'-dibutoxybenzophenone, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-ditertiarybutylphenyl)benzotriazole, or halides thereof, phenyl salicylate, p-tertiarybutylphenyl salicylate, and the like.

[0053] A defoaming agent may be added to the curable resin raw material composition of the present embodiment to remove bubbles. Specific examples of the defoaming agent include an acrylic defoaming agent obtained by dissolving a special acrylic polymer in a solvent, and a vinyl defoaming agent obtained by dissolving a special vinyl polymer in a solvent. Specific product names of the defoaming agent include, for example, the following. Disparlon series manufactured by Kusumoto Chemical Industries, Ltd. (product names: OX-880EF, OX-881, OX-883, OX-77EF, OX-710, OX-8040, 1922, 1927, 1950, P-410EF, P-420, P-425, PD-7, 1970, 230, 230HF, 230EF, LF-1980, LF-1982, LF-1983, LF-1984, LF-1985, etc.) and BYK-052 and BYK-1752 manufactured by BYK Japan.

[0054] In order to improve storage stability, a polymerization inhibitor may be added to the curable resin raw material composition of the present embodiment. Specific examples of the polymerization inhibitor include hydroquinone, 2-methylhydroquinone, hydroquinone monomethyl ether, and 2-6-di-t-butyl-4-methylphenol.

[0055] The amount of compound (1) is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total amount of compound (1) and other polymerizable compounds. It may be 100% by mass. When the amount is equal to or more than the lower limit of the above range, the refractive index tends to be sufficiently high. The radical polymerization initiator is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 20 parts by mass, relative to 100 parts by mass of the total of the compound (1) and the other polymerizable compounds. When it is equal to or more than the lower limit of the above range, an appropriate polymerization rate is easily obtained. When it is equal to or less than the upper limit, coloring is unlikely to occur. In addition, recombination of the generated radicals and non-uniformity are unlikely to occur, and a sufficient molecular weight is easily obtained.

[0056] The curable resin raw material composition of the present embodiment is preferably liquid. As the other polymerizable compound, it is preferable to use one that is liquid at room temperature, and to prepare the curable resin raw material composition by dissolving the compound (1) in the other polymerizable compound. A solvent may be used as necessary. Examples of the solvent include propylene glycol monomethyl ether acetate, cyclohexane, and toluene. A polymer having a predetermined shape can be obtained by polymerizing the curable resin raw material composition in a predetermined shape. Methods for forming a predetermined shape include coating, potting, casting, printing, liquid resin injection molding (LIM), and transfer molding. When polymerizing the curable resin raw material composition, it is preferable to polymerize the curable resin raw material composition in a sealed state in order to suppress curing inhibition due to oxygen. Examples of a method for sealing include a method of sandwiching the curable resin raw material composition between glass or a PET film.

[0057] <Curable resin (polymer)> The polymer (curable resin) of the curable resin raw material composition of this embodiment is transparent and suitable for optical members. The curable resin of the present embodiment is obtained by polymerizing the curable resin raw material composition of the present embodiment. As a method for curing the curable resin raw material composition, any of photopolymerization, thermal polymerization, and redox polymerization can be adopted depending on the type of polymerization initiator contained in the curable resin raw material composition.

[0058] When the curable resin raw material composition is cured by photopolymerization to obtain a curable resin, the wavelength of the light irradiated to the curable resin raw material composition is not particularly limited, but it is preferable to irradiate ultraviolet light having a wavelength of 200 to 400 nm. Specific examples of the light source of ultraviolet light include ultra-high pressure mercury lamps, high pressure mercury lamps, metal halide lamps, high power metal halide lamps, UV-LED lamps, chemical lamps, black lights, etc. After photopolymerization of the curable resin raw material composition, after-curing may be further performed. This can reduce the amount of unreacted (meth)acryloyl groups remaining in the curable resin, and can further increase the strength of the curable resin. The after-curing conditions are preferably 70 to 150°C for 0.01 to 24 hours, more preferably 80 to 130°C for 0.1 to 10 hours.

[0059] When the curable resin raw material composition is polymerized by thermal polymerization to obtain a curable resin, the polymerization conditions are not particularly limited, but from the viewpoint of easily obtaining a resin for optical components with suppressed coloration, the polymerization temperature is preferably 40 to 200° C., more preferably 60 to 150° C. The polymerization time (heating time) varies depending on the polymerization temperature, but is preferably 1 to 120 minutes, more preferably 1 to 60 minutes. After the curable resin raw material composition is thermally polymerized, it is preferable to further perform after-curing, preferably at 50 to 150° C. for 0.1 to 10 hours, more preferably at 70 to 130° C. for 0.2 to 5 hours.

[0060] When the curable resin raw material composition is polymerized by redox polymerization to obtain a curable resin, the use of a redox-based polymerization initiator allows polymerization at room temperature of 5 to 40° C. The polymerization temperature is preferably 15 to 40° C., since the amount of unreacted (meth)acryloyl groups remaining in the obtained resin for optical members can be reduced and the strength of the resin for optical members can be further increased. In addition, from the viewpoint of preventing gelation of the curable resin raw material composition and enabling stable handling, a method of carrying out polymerization by dissolving a reducing agent in the curable resin raw material composition in advance and then adding a peroxide thereto is preferred.

[0061] For example, when the curable resin of this embodiment has a thickness of 1 mm, the total light transmittance is preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more. The haze is preferably 20% or less, more preferably 15% or less, and even more preferably 10% or less. The total light transmittance and haze are values ​​measured by the method described below.

[0062] The refractive index of the curable resin of this embodiment is preferably 1.55 or more, more preferably 1.58 or more, and even more preferably 1.60 or more, measured at 23°C with helium lamp d-line (587.6 nm). If the refractive index of the curable resin is 1.60 or more, when applied to a transparent optical component, various optical designs become possible, and the curable resin can be applied to various uses. The refractive index is a value measured by the method described below.

[0063] The curable resin of the present embodiment is suitable as a member constituting a part or the whole of a transparent optical member. Examples of the transparent optical member include films, sheets, lenses, optical waveguides, sealing materials, fillers, adhesives, reflective materials, pressure sensitive adhesives, and wavelength conversion materials used in light emitting diode modules, mobile phones, smartphones, tablet terminals, personal computers, cameras, organic electroluminescence (organic EL) devices, flat panel displays, touch panels, electronic paper, photodiodes, phototransistors, solar cells, projectors, etc.; anti-reflection materials used in photolithography processes; etc.

[0064] The curable resin of the present embodiment is suitable as a component constituting a part or the whole of various lenses. The lens may be a molded product made of the curable resin of the present embodiment, or may be a hybrid lens made of a transparent substrate such as flat glass, curved glass, or a glass wafer and the curable resin of the present embodiment formed on one or both sides of the transparent substrate.

[0065] <Compound (2)> Compound (2) represented by the following formula (2) is used as a precursor in the production method of compound (1).

[0066] [ka]

[0067] In equation (2), Q 1 , Q 2 , Q 3 , Q 4 represents an alkylene group having 1 to 6 carbon atoms. It may be linear or branched. The number of carbon atoms is preferably 1 to 4. A methylene group, an ethylene group, a methylmethylene group, or an ethylmethylene group is more preferred, a methylene group or an ethylene group is even more preferred, and a methylene group is particularly preferred. Q in one molecule 1 , Q 2 , Q 3 , Q 4 may be the same as or different from each other. Q is advantageous in that raw materials are easily available and the stereoisomers of the products can be easily controlled. 1 , Q 2 , Q 3 , Q 4 are preferably the same as each other.

[0068] In formula (2), Cy 1 , Cy 2 represents a sulfur-containing aromatic heterocycle. The sulfur-containing aromatic heterocycle contributes to a high refractive index. The sulfur-containing aromatic heterocycle may have a substituent. Cy 1 and Cy 2 may be the same as or different from each other. In terms of facilitating raw material acquisition and synthesis, Cy 1 and Cy 2 It is preferable that Cy be the same as Cy. 1 and Cy 2 are preferably different. The sulfur-containing aromatic heterocycle has at least a sulfur atom as a heteroatom constituting the aromatic heterocycle. In addition to the sulfur atom, the heteroatom may have an oxygen atom, a nitrogen atom, or an oxygen atom and a nitrogen atom. From the viewpoint of avoiding coloration and ensuring solubility, the number of heteroatoms constituting the sulfur-containing aromatic heterocycle is preferably 1 to 3, more preferably 1 to 2.

[0069] In formula (2), X 1 , X 2 , X 3 , X 4 each independently represents an oxygen atom, a sulfur atom, or a nitrogen atom which may have an organic group bonded thereto. The organic group that may be bonded to the nitrogen atom is not particularly limited, but examples thereof include alkyl groups having 1 to 8 carbon atoms (e.g., methyl group, ethyl group), and aromatic hydrocarbon groups having 6 to 15 carbon atoms (e.g., phenyl group, naphthyl group), and it is preferable that such an organic group is bonded to the nitrogen atom. X 1 , X 2 From the viewpoints of facilitating synthesis and reducing viscosity, an oxygen atom or a sulfur atom is preferred. From the viewpoint of availability of raw materials, an oxygen atom is more preferred, and from the viewpoint of refractive index, a sulfur atom is more preferred. Among these, an oxygen atom is particularly preferred. 1 and X 2 are preferably the same. X 3 , X 4 In terms of the ease of keeping the water absorption rate low, an oxygen atom or a sulfur atom is preferred. In terms of availability of raw materials, an oxygen atom is more preferred, and in terms of refractive index, a sulfur atom is more preferred. Among these, an oxygen atom is particularly preferred. 3 and X 4 are preferably the same.

[0070] In formula (2), Z 1 , Z 2 , Z 3 , Z 4 Each independently represents a divalent organic group. 1 and Z 2 are preferably the same in terms of ease of synthesis. 3and Z 4 are preferably the same in terms of ease of synthesis. The divalent organic group may be linear, branched, or cyclic. A hydrocarbon group which may have a substituent is preferred. The number of carbon atoms in the hydrocarbon group (not including the number of carbon atoms in the substituent) is preferably 1 to 8. If the number of carbon atoms is 8 or less, the refractive index is unlikely to decrease, the viscosity is likely to decrease due to the small molecular weight, and processability is likely to improve. Specific examples include methylene, ethylene, 1,3-propylene, 1,2-propylene, butylene, 2-hydroxypropylene, oxopropylene, oxobutylene, oxohexylene, oxoheptylene, 3-oxapentylene, cyclohexylene, phenylene, xylylene, -CH2CH2NHC(O)-, -CH2CH2OCH2CH2NHC(O)-, etc. Methylene, ethylene, 1,3-propylene, 1,2-propylene, 2-hydroxypropylene, and -CH2CH2NHC(O)- are preferred. Examples of the substituent include a halogen atom (a chlorine atom, a bromine atom, an iodine atom), a hydroxyl group, a mercapto group, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a mesityl group, a tolyl group, a naphthyl group, a cyano group, an acetyloxy group, an alkylcarbonyloxy group having 2 to 9 carbon atoms, an alkoxycarbonyl group having 2 to 9 carbon atoms, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, an alkylcarbonyl group having 2 to 9 carbon atoms, a phenethyl group, a hydroxyethyl group, an acetylamide group, a dialkylaminoethyl group having an alkyl group having 1 to 4 carbon atoms bonded thereto, a trifluoromethyl group, an alkylthio group having 1 to 8 carbon atoms, and a nitro group. Among these, alkyl groups having 1 to 8 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, cyano groups, acetyloxy groups, alkylcarboxyl groups having 2 to 8 carbon atoms, sulfamoyl groups, alkylsulfamoyl groups having 2 to 9 carbon atoms, and nitro groups are preferred.

[0071] In formula (2), n1, n2, n3, and n4 each independently represent 0 or an integer of 1 to 3. When n1, n2, n3, and n4 are small, the refractive index tends to be high. When n1, n2, n3, and n4 are small, the compound tends to be solid at room temperature (23°C). When the compound is solid at room temperature, it can be purified by a recrystallization method, and a compound (1) that is nearly colorless and transparent (low coloring) can be obtained. By producing a polymer using the compound (1) with low coloring, it becomes easy to obtain a polymer with low coloring. On the other hand, when n1, n2, n3, and n4 are large, the material is easily liquefied and good processability is easily obtained. An embodiment in which n1, n2, n3 and n4 are all 0 is more preferable, in that a compact structure makes it easier to increase the aromatic ring density and thus the refractive index, and a compound with low coloration can be obtained. In terms of ease of improving processability by lowering the melting point of the compound or liquefying it, an embodiment in which n1, n2, n3 and n4 are each independently 1 to 3 is preferred.

[0072] Preferred embodiments of compound (2) include the following. Aspect (1): Cy 1 , Cy 2 are each independently a benzothiazole ring which may have a substituent, a dibenzothiophene ring which may have a substituent, or a benzothiophene ring which may have a substituent. Mode (2): Mode (1), in which n1, n2, n3, and n4 are all 0. Aspect (3): In aspect (1), Q 1 , Q 2 , Q 3 , Q 4 are all methylene groups. Mode (4): In mode (1), n1, n2, n3, and n4 are all 0, and Q 1 , Q 2 , Q 3 , Q 4 are all methylene groups. Specific examples of the embodiment (4) include the following compounds (2-1) to (2-3).

[0073] [ka]

[0074] <Method for producing compound (2)> In formula (2), when n1, n2, n3, and n4 are all 0, compound (2c) represented by the following compound (2c) can be produced by reacting compound (2a) represented by the following formula (2a) with thiol compound (2b) represented by the following formula (2b). In formula (2a), X is a halogen atom (bromine atom, iodine atom, chlorine atom), and is preferably a bromine atom or an iodine atom. Compound (2a) can be produced by a known method of halogenating a compound having a hydroxyl group.

[0075] [ka]

[0076] The reaction between the active hydrogen of compound (2b) and the halogen atom of compound (2a) can be carried out by a known method. For example, compound (2a) can be reacted with compound (2b) in the presence of a basic compound to give compound (2c). Examples of the basic compound include triethylamine, pyridine, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, and potassium tert-butoxide (t-BuOK). The basic compound may be used alone or in combination of two or more. It is preferable to use an organic solvent in the reaction between compound (2a) and compound (2b). Examples of the organic solvent include dimethoxyethane, tetrahydrofuran, methanol, ethanol, toluene, N,N-dimethylformamide, and acetone. One type of organic solvent may be used, or two or more types may be used in combination.

[0077] The reaction between compound (2a) and compound (2b) is preferably carried out in a reaction system that does not contain moisture. Specifically, the reaction is preferably carried out in an inert gas (argon gas, nitrogen gas) atmosphere. The organic solvent is preferably a dehydrated, dry organic solvent. The amount of compound (2b) used is preferably 1.0 mol or more, more preferably 1.5 mol or more, and even more preferably 2.0 mol or more per mol of compound (2a). From the viewpoint of suppressing side reactions and loads on post-reaction treatment steps, the amount is preferably 8 mol or less, more preferably 6 mol or less, and even more preferably 5 mol or less per mol of compound (2a). The amount of the basic compound used is preferably 1.0 mol or more, more preferably 1.5 mol or more, and even more preferably 2.0 mol or more per mol of compound (2a). From the viewpoint of suppressing side reactions and loads on post-reaction treatment steps, the amount is preferably 8 mol or less, more preferably 6 mol or less, and even more preferably 5 mol or less per mol of compound (2a).

[0078] In formula (2), when n1 and n2 are 1 and n3 and n4 are 0, the method described in paragraphs 0039 to 0040 of JP 2017-14213 A is applied to obtain Q 1 , Q 2 Between -OH and (X 1 -Z 1 ), (X 2 -Z 2 ) can be introduced to produce compound (2).

[0079] In formula (2), when n1 and n2 are 0 and n3 and n4 are 1, the method described in paragraphs 0041 to 0042 of JP 2017-14213 A is applied to obtain Q 3 , Q 4 Between and -S- (X 3 -Z 3 ), (X 4 -Z 4 ) can be introduced to produce compound (2).

[0080] In formula (2), when n1, n2, n3, and n4 are all 1, the method described in paragraphs 0043 to 0044 of JP 2017-14213 A is applied to obtain Q 1 , Q 2 Between -OH and (X 1 -Z 1 ), (X 2 -Z 2 ) and Q3 , Q 4 Between and -S- (X 3 -Z 3 ), (X 4 -Z 4 ) can be introduced to produce compound (2).

[0081] However, the method described in JP 2017-14213 A is a method for producing a monol, whereas the method for producing compound (2) of the present embodiment is a method for producing a diol.

[0082] <Thermoplastic resin raw material composition containing compound (2)> A second embodiment of the polymerizable composition is a thermoplastic raw material composition containing compound (2).The polymer of the thermoplastic resin raw material composition is a thermoplastic resin. The compound (2) is suitable as a raw material for thermoplastic resins such as polyester resins, polycarbonate resins, or polyestercarbonate resins. The structural unit derived from compound (2) has two molecular chains containing a sulfur-containing aromatic heterocycle per structural unit, and contributes to an increase in the refractive index of thermoplastic resins for optical materials (polyester resins, polycarbonate resins, polyester carbonate resins, etc.).

[0083] The thermoplastic resin raw material composition of the present embodiment contains compound (2), a dicarboxylic acid compound, a diester compound, or a carbonate ester compound, and a polymerization catalyst. Compound (2) may be used alone or in combination of two or more kinds. The polyester resin can be produced by subjecting the compound (2) to a polycondensation reaction with a dicarboxylic acid compound or a diester compound. A polycarbonate resin can be produced by polymerizing the compound (2) with a carbonate compound. A polyester carbonate resin can be produced by polymerizing the compound (2), a dicarboxylic acid compound or a diester compound, and a carbonate compound. In producing a thermoplastic resin such as a polyester resin, a polycarbonate resin, or a polyester carbonate resin, a known dicarboxylic acid compound, a diester compound, or a carbonate ester compound can be used. The thermoplastic resin raw material composition of the present embodiment may contain a diol compound other than the compound (2). The thermoplastic resin raw material composition of this embodiment may further contain tri- or higher functional alcohols such as trimethylolpropane, pentaerythritol, and dipentaerythritol, if necessary.

[0084] [Other diol compounds] Specific examples of diol compounds other than compound (2) include diol compounds of straight-chain aliphatic hydrocarbons such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-heptanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol; diol compounds of branched aliphatic hydrocarbons such as 1,2-propanediol, 1,3-butanediol, 1,2-butanediol, neopentyl glycol, and hexylene glycol; 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,3-adamantanediol, hydrogenated bisphenol A, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol. diol compounds of alicyclic hydrocarbons and primary alcohols, such as diol compounds derived from terpene compounds, such as 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 2,6-decalin dimethanol, 1,5-decalin dimethanol, 2,3-decalin dimethanol, 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, 1,3-adamantanedimethanol, spiroglycol, and limonene.

[0085] In addition to the diol compounds listed above, diol compounds containing an aromatic component may be used. Specifically, resorcinol, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4-hydroxy-(3-phenyl)phenyl)propane, 2,2-bis(4-hydroxy-(3,5-diphenyl)phenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, bis( 4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, 1,1-bis(4-hydroxyphenyl)-2-ethylhexane, 1,1-bis(4-hydroxyphenyl)decane, bis(4-hydroxy-3-nitrophenyl)methane, 3,3-bis(4-hydroxyphenyl)pentane benzene, 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenyl sulfone, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxy-3-methylphenyl)sulfide, bis(4-hydroxyphenyl)disulfide aromatic bisphenol compounds such as 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether; diol compounds having an ether group bonded to an aromatic group such as 2,2-bis(4-(2-hydroxyethoxy)phenyl)propane, 2,2-bis(4-(2-hydroxypropoxy)phenyl)propane, 1,3-bis(2-hydroxyethoxy)benzene, 4,4'-bis(2-hydroxyethoxy)biphenyl, bis(4-(2-hydroxyethoxy)phenyl)sulfone;9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxypropoxy)phenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxypropoxy)-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxypropoxy)-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isopropylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isobutylphenyl)fluorene, 9 ,9-bis(4-(2-hydroxyethoxy)-3-tert-butylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-cyclohexylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3,5-dimethylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butyl-6-methylphenyl)fluorene, 9,9-bis(4-(3-hydroxy-2,2-dimethylpropoxy)phenyl)fluorene and other diol compounds having a fluorene ring;

[0086] In addition, the oligofluorene-diols described in paragraph 0279 of WO 2014 / 061677 are preferred in that they have a low photoelastic coefficient, and while having the desired optical properties, they also have various physical properties such as heat resistance. Among these, bis(9-hydroxymethylfluoren-9-yl)methane and 1,2-bis(9-hydroxymethylfluoren-9-yl)ethane can be mentioned.

[0087] The diol compound other than the compound (2) preferably contains a diol compound containing an aromatic component from the viewpoint of obtaining a high refractive index, whereas it preferably contains a diol compound not containing an aromatic component from the viewpoint of imparting flexibility and improving mechanical properties and melt processability. The diol compounds other than the compound (2) may be used alone or in combination of two or more.

[0088] [Dicarboxylic acid compounds / diester compounds] Examples of the dicarboxylic acid compound used in the thermoplastic resin raw material composition of this embodiment include aromatic dicarboxylic acids such as terephthalic acid, phthalic acid, isophthalic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-benzophenonedicarboxylic acid, 4,4'-diphenoxyethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid; and aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. Aromatic dicarboxylic acid compounds are preferred because they provide a high refractive index, but if they are contained in a large amount, they are undesirable because they deteriorate moldability. Aliphatic dicarboxylic acid compounds are preferred because they can adjust the glass transition temperature and improve moldability.

[0089] The dicarboxylic acid component may be a diester compound such as a methyl ester, an ethyl ester, or a phenyl ester, or a dicarboxylic acid derivative such as a dicarboxylic acid halide, depending on the production method. When a polyester resin is produced by a transesterification method, a methyl ester or an ethyl ester is preferable. When a polyester carbonate resin is produced, a phenyl ester that can be polymerized in the presence of diphenyl carbonate, which is a preferable carbonate ester, is preferable.

[0090] The oligofluorene diaryl esters described in paragraph 0284 of WO 2014 / 061677 are preferred in that they have a low photoelastic coefficient, have desired optical properties, and have various physical properties such as heat resistance. Among them, bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]methane, 1,2-bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]ethane, bis[9-(2-methoxycarbonylethyl)fluoren-9-yl]methane, 1,2-bis[9-(2-methoxycarbonylethyl)fluoren-9-yl]ethane, bis[9-(2-ethoxycarbonylethyl)fluoren-9-yl]methane, and 1,2-bis[9-(2-ethoxycarbonylethyl)fluoren-9-yl]ethane have negative birefringence, and are preferred in that they can be adjusted to near zero when made into a thermoplastic resin. These dicarboxylic acid compounds or diester compounds may be used alone or in combination of two or more.

[0091] [Carbonate compounds] Examples of the carbonate ester compound used in the thermoplastic resin raw material composition of this embodiment include phosgenes such as phosgene, diphosgene, and triphosgene; aromatic carbonate ester compounds such as diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, and bis(biphenyl) carbonate; and aliphatic carbonate ester compounds such as dimethyl carbonate, diethyl carbonate, and ethylene carbonate. When producing a high molecular weight resin, aromatic carbonate ester compounds having high reactivity are preferred, and among them, diphenyl carbonate, which is inexpensive and industrially available, is preferred. When producing a high molecular weight resin, aliphatic carbonate ester compounds having a small molecular weight and high production efficiency as a carbonate source are preferred, and dimethyl carbonate and ethylene carbonate, which have smaller molecular weights, are more preferred. These carbonate ester compounds may be used alone or in combination of two or more.

[0092] [Polymerization catalyst] As a polymerization catalyst for producing a polyester resin or a polyester carbonate resin using the thermoplastic resin raw material composition of this embodiment, for example, one or more selected from the group consisting of compounds (metal compounds) of Group 1 elements and Group 2 elements in the long periodic table are suitably used. Examples of the compounds of Group 1 elements include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride, sodium phenyl borohydride, and phenyl borohydride. Examples of the boron nitrate include potassium boron nitrate, lithium boron phenylate, cesium boron phenylate, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, dicesium hydrogen phosphate, disodium phenylphosphate, dipotassium phenylphosphate, dilithium phenylphosphate, dicesium phenylphosphate, sodium, potassium, lithium, and cesium alcoholates, phenolates, and disodium, dipotassium, dilithium, and dicesium salts of bisphenol A. Among these, lithium compounds are preferred from the viewpoint of polymerization activity and the hue of the resulting thermoplastic resin.

[0093] Examples of the compound of the Group 2 element include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, and strontium stearate, etc. Among these, magnesium compounds, calcium compounds, or barium compounds are preferred, and from the viewpoint of polymerization activity and the hue of the obtained thermoplastic resin, magnesium compounds and / or calcium compounds are more preferred, and calcium compounds are most preferred.

[0094] A basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, an amine compound, etc. may be used in combination with one or more of the compounds of Group 1 and Group 2 elements as an auxiliary. It is particularly preferable to use only one or more of the compounds of Group 1 and Group 2 elements.

[0095] Examples of the basic phosphorus compound include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts.

[0096] Examples of the basic ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, and butyltriphenylammonium hydroxide.

[0097] Examples of the amine compounds include 4-aminopyridine, 2-aminopyridine, N,N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline, and guanidine.

[0098] When one or more selected from the compounds of Group 1 and Group 2 elements are used, the amount of the polymerization catalyst is usually within the range of 0.1 μmol to 100 μmol, preferably within the range of 0.5 μmol to 50 μmol, and more preferably within the range of 1 μmol to 25 μmol, calculated as a metal amount relative to 1 mole of the total diol compounds used in the reaction. If the amount of the polymerization catalyst used is too small, the polymerization activity required to produce a thermoplastic resin with a desired molecular weight may not be obtained. On the other hand, if the amount of the polymerization catalyst used is too large, the color of the obtained thermoplastic resin may deteriorate. In addition, by-products are likely to be generated, fluidity may decrease, and gel may be generated frequently, making it difficult to produce a thermoplastic resin with the desired quality.

[0099] Among them, when a compound containing at least one metal selected from the group consisting of Group 2 elements and lithium in the long periodic table is used, particularly when at least one of a magnesium compound and a calcium compound is used, the metal equivalent amount is preferably 0.1 μmol or more, more preferably 0.3 μmol or more, and particularly preferably 0.5 μmol or more per mole of the total diol compounds. The upper limit is preferably 20 μmol or less, more preferably 10 μmol or less, even more preferably 5 μmol or less, and particularly preferably 3 μmol or less. If the amount of these catalysts used is too small, the polymerization rate will be slow, and the polymerization temperature will have to be increased accordingly to obtain a thermoplastic resin with a desired molecular weight. This may increase the possibility that the color of the resulting thermoplastic resin will deteriorate, or that the desired molecular weight will not be achieved. On the other hand, if the amount of polymerization catalyst used is too large, undesirable side reactions may occur, causing deterioration in the color of the resulting thermoplastic resin, or coloring of the resin during molding.

[0100] When a polycarbonate resin is produced using the thermoplastic resin raw material composition of the present embodiment, for example, an ester exchange reaction catalyst is used. Examples of the transesterification catalyst include titanium compounds such as tetrabutoxytitanium, tetraisobutoxytitanium, tetramethoxytitanium, tetraisopropoxytitanium, tetraethoxytitanium, tetrakis(2-ethylhexyloxy)titanium, tetrastearyloxytitanium, tetraphenoxytitanium, titanium(IV) acetylacetonate, and titanium(IV) diisopropoxide bis(acetylacetonate); alkali metal compounds such as lithium carbonate, dibutylaminolithium, lithium acetylacetonate, sodium phenoxide, and potassium phenoxide; cadmium compounds such as cadmium acetylacetonate and cadmium carbonate; zirconium compounds such as zirconium acetylacetonate and zirconocene; lead compounds such as lead sulfide, lead hydroxide, lead salts, zinc salts, lead carbonate, lead acetate, tetrabutyl lead, tetraphenyl lead, triphenyl lead, dimethoxy lead, and diphenoxy lead; copper acetate, copper bisacetylacetonate, and olein. copper compounds such as copper hydroxide, butyl copper, dimethoxy copper, and copper chloride; iron compounds such as iron hydroxide, iron carbonate, triacetoxy iron, trimethoxy iron, and triphenoxy iron; zinc compounds such as zinc bisacetylacetonate, diacetoxy zinc, dimethoxy zinc, diethoxy zinc, and diphenoxy zinc; organic tin compounds such as di-n-butyltin oxide, diphenyltin oxide, di-n-ocrylyl tin oxide, di-n-butyltin dimethoxide, di-n-butyltin diacrylate, di-n-butyltin dimethacrylate, di-n-butyltin dilaurate, tetramethoxytin, tetraphenoxytin, and tetrabutyl-1,3-diacetoxydistannoxane; aluminum compounds such as aluminum acetate, aluminum methoxide, aluminum ethoxide, and aluminum phenoxide; vanadium compounds such as vanadium dichloride, vanadium trichloride, vanadium tetrachloride, and vanadium sulfate; and phosphonium salts such as tetraphenylphosphonium phenoxide. These may be used alone or in combination of two or more. Among these, it is preferable to use phosphonium salts, lithium compounds, zirconium compounds, organotin compounds, titanium compounds, and the like, because they are industrially inexpensive and have advantages in terms of reaction operation, and among these, organotin compounds and titanium compounds are particularly preferable.

[0101] The amount of the transesterification catalyst used is not particularly limited, but if the amount is too large, the burden of purification after the reaction increases. The amount of the transesterification catalyst used is usually 20 mol % or less, preferably 10 mol % or less, and more preferably 5 mol % or less based on the total of the raw material compound (2) and diol compounds other than compound (2) (total diol compounds). On the other hand, if the amount of the transesterification catalyst used is too small, the reaction time may become too long. The lower limit is usually 0.1 mol% or more, preferably 0.5 mol% or more, and more preferably 1 mol% or more, based on the total diol compounds in the raw materials.

[0102] In the thermoplastic resin raw material composition of this embodiment, the content ratio of compound (2) can be any ratio that gives the desired physical properties. In terms of being easy to obtain a sufficient refractive index, when the total of the constituent units derived from compound (2), dicarboxylic acid compounds, diester compounds, carbonate ester compounds, and diol compounds other than compound (2) is taken as 100 mol%, the constituent units derived from compound (2) are preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more. In addition, it is preferably 60 mol% or less, more preferably 50 mol% or less, and even more preferably 40 mol% or less.

[0103] In the thermoplastic resin raw material composition for producing a polyester resin, when the polyester resin is used as a high molecular weight resin for lenses, etc., the dicarboxylic acid compound is preferably used at a molar fraction of 0.90 or more, more preferably 0.96 or more, and even more preferably 0.98 or more, based on the mole number of all diol compounds. The upper limit is preferably 1.10 or less, more preferably 1.05 or less, and even more preferably 1.03 or less. In addition, when the polyester resin is used for adjusting the refractive index of the adhesive, it is preferable to make the polyester resin alcohol-terminated or carboxylic acid-terminated after making the molecular weight relatively low. When the diol compound is alcohol-terminated, it is preferable to use 0.60 times or more of the dicarboxylic acid compound in moles relative to the total number of moles of the diol compound, more preferably 0.70 times or more, and even more preferably 0.80 times or more. The upper limit is preferably 0.98 times or less, more preferably 0.95 times or less, and even more preferably 0.90 times or less. When the diol compound is carboxylic acid-terminated, it is preferable to use 1.02 times or more of the dicarboxylic acid compound in moles relative to the total number of moles of the diol compound, more preferably 1.05 times or more, and even more preferably 1.10 times or more. The upper limit is preferably 1.60 times or less, more preferably 1.40 times or less, and even more preferably 1.20 times or less. Here, when a diol compound that can be removed by distillation, such as ethylene glycol, is used, it is preferable to remove it by using an excess diol.

[0104] In the thermoplastic resin raw material composition for polycarbonate resin production or polyester carbonate resin production, the amount of carbonate ester compound used is not particularly limited, but if it is too much with respect to the total diol compounds, the purification load after the reaction tends to be large. Therefore, the total mole number of the carbonate ester compound and the dicarboxylic acid compound with respect to the total diol compounds is usually 1.10 times mol or less, preferably 1.05 times mol or less, more preferably 1.03 times mol or less. On the other hand, if the amount of the carbonate ester compound used is too small, unreacted diol compounds may remain, so the lower limit is usually 0.90 times mol or more, preferably 0.96 times mol or more, more preferably 0.98 times mol or more with respect to the total diol compounds. If this ratio is equal to or greater than the lower limit, the produced thermoplastic resin is likely to have good thermal stability, and the desired high molecular weight material is likely to be obtained. Also, if this ratio is equal to or less than the upper limit, an appropriate polymerization rate is likely to be obtained. When a carbonate compound that can be removed by distillation, such as dimethyl carbonate or ethylene carbonate, is used, it is preferable to remove the carbonate using 1.10 times or more molar amount.

[0105] <Thermoplastic resin (polymer)> The polymer (thermoplastic resin) of the thermoplastic resin raw material composition of this embodiment is suitable for producing transparent optical members such as lenses, or for adjusting the refractive index of adhesives. The polymerization reaction of the thermoplastic resin raw material composition can be carried out by a known method for producing a thermoplastic resin.

[0106] The preferred molecular weight of the thermoplastic resin of this embodiment varies depending on the application. When used for lenses, etc., sufficient strength is required, so the weight average molecular weight is preferably 10,000 or more, more preferably 20,000 or more, and even more preferably 30,000 or more. In addition, if the molecular weight is too large, the fluidity decreases, so the weight average molecular weight is preferably 300,000 or less, more preferably 200,000 or less, and even more preferably 100,000 or less. When used for adjusting the refractive index of a tackifier, etc., a certain level of fluidity is required, so the number average molecular weight is preferably 500 or more, more preferably 800 or more, and even more preferably 1,000 or more, and preferably 5,000 or less, more preferably 3,000 or less, and even more preferably 2,000 or less.

[0107] The polymerization reaction of the polymerizable composition of the present embodiment can be carried out by a known method for producing a curable resin or a thermoplastic resin. The polymerizable composition of the present embodiment can be suitably used for producing a transparent optical member similar to the polymerizable composition containing the compound (1) or compound (2). EXAMPLES

[0108] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples.

[0109] <Measurement method> [Method for measuring the refractive index of a compound] The test solutions were prepared by dissolving the sample in 1-methyl-2-pyrrolidone to a predetermined concentration. The test solutions had three sample concentrations of 10 mass %, 20 mass %, and 30 mass %. The refractive index of each test solution was measured using a Kalnew precision refractometer (Shimadzu Corporation product name: KPR-2000). The temperature of the test solution was 23°C, and the measurement wavelength was helium lamp d-line (587.6 nm). Based on the measurement results, a calibration curve was created showing the correlation between the sample concentration and the refractive index. From the obtained calibration curve, the refractive index when the sample concentration was 100% by mass was determined and used as the refractive index of the sample. [Method of measuring the melting point of a compound] The melting point of each sample was measured using a thermogravimetric differential thermal analyzer (Seiko Instruments Inc. product name: EXSTAR6000).

[0110] [Method of measuring refractive index, total light transmittance and haze of curable resin] (Preparation of Curable Resin Raw Material Composition) Four types of curable resin raw material compositions a to d were prepared by mixing a sample, a photopolymerization initiator (Irgacure 184, a BASF product name), 3-phenoxybenzyl acrylate, and trimethylolpropane trimethacrylate according to the formulations shown in Table 1. (Production of hardening resin (polymer)) For each of the obtained curable resin raw material compositions a to d, a 1 mm thick silicone sheet was used as a gasket, the composition was sandwiched between two glass plates, and a high-pressure mercury lamp was used to illuminate the composition with an integrated light intensity of 3000 mJ / cm. 2 After being irradiated with ultraviolet light, the plate was heated for 30 minutes at 100° C. After cooling, the plate glass was removed to obtain curable resins a to d having a diameter of about 35 mm and a thickness of about 1 mm.

[0111] [Table 1]

[0112] (Refractive index measurement) The refractive indexes of the four curable resins obtained in the above (Production of Curable Resin (Polymer)) were measured using the refractometer. Based on the measurement results, a calibration curve showing the correlation between the amount of sample and the refractive index was created. From the resulting calibration curve, the refractive index when the sample was 100 mass % curable resin (homopolymer) was determined. The refractive index of a curable resin having a thickness of about 1 mm was measured in the same manner using the above refractometer. (Measurement of total light transmittance and haze) The total light transmittance and haze of the curable resin with a diameter of about 35 mm and a thickness of about 1 mm were measured using a haze meter (product name: HZ-2 type, manufactured by Suga Test Instruments Co., Ltd.).

[0113] (Example 1: Production of compound (2-1)) Compound (2-1) was produced by reacting compound (2a-1) with compound (2b-1).

[0114] [ka]

[0115] First, 587.2 g (3.511 mol, 2.20 equivalents) of 2-mercaptobenzothiazole (compound (2b-1)) was charged into a 20 L four-neck flask under an argon atmosphere, dissolved in dry DMF (5 L), and cooled to an internal temperature of 4 ° C. with stirring. Next, 393.9 g (3.511 mol, 2.2 equivalents) of potassium tert-butoxide was added in portions over 2 hours so that the internal temperature did not exceed 10 ° C., and then the internal temperature was raised to 85 ° C. A solution of 418.0 g (1.596 mol, 1.00 equivalents) of 2,2-bis(bromomethyl)-1,3-propanediol (compound (2a-1)) dissolved in dry DMF (1.3 L) was added dropwise over 1 hour and 20 minutes so that the internal temperature was kept at 90 ± 5 ° C. Next, the mixture was aged for 6 hours while maintaining the internal temperature at 90±5° C., and then left to stand overnight at room temperature. Purified water (3 L) was added dropwise to the obtained reaction solution, and the mixture was extracted with toluene (8.5 L). The obtained organic phase was washed twice with 50 mM NaOH aqueous solution (2.5 L) and six times with purified water (2.5 L). The washed organic phase was concentrated to obtain a crude product. The obtained crude product was purified by silica gel chromatography, concentrated, and the obtained crude crystals were suspended and washed in methanol, and filtered to obtain the target compound (357.8 g) as a powder (solid). The yield was 51.6%. 1 H-NMR analysis confirmed that the target compound was compound (2-1). 1 H-NMR(400MHz,CDCl3)δ7.81(d,J=8.2Hz,2H),7.75(d,J=8.0Hz,2H),7.45-7.42(m ,2H),7.34-7.26(m,2H),5.46(t,J=7.4Hz,2H),3.63(s,4H),3.58(d,J=8.0Hz,4H). The refractive index of the compound (2-1) obtained as a sample using the obtained powder was measured by the above-mentioned method, and was found to be 1.650. The melting point of the compound (2-1) was measured by the above-mentioned method using the obtained powder as a sample, and was found to be 161°C.

[0116] (Example 2: Production of compound (1A-1)) The compound (2-1) obtained in Example 1 was reacted with acrylic acid chloride to produce the compound (1A-1).

[0117] [ka]

[0118] First, in an argon atmosphere, 126.0 g (0.2899 mol) of compound (2-1), dry THF (2.5 L), and 114 mL (2.82 mol per mol of compound (2-1)) of triethylamine (Et3N) were charged into a 5 L four-neck flask, and the flask was cooled to an internal temperature of -5°C while stirring. Next, 74.0 g (2.82 mol per mol of compound (2-1)) of acrylic acid chloride was added dropwise over 40 minutes so that the internal temperature was kept in the range of -5 to 6°C, and then the internal temperature was raised to 30°C over 1 hour and 20 minutes. Next, the mixture was aged until the raw materials and intermediates were almost completely consumed while maintaining the internal temperature at 30 to 33°C. After cooling the resulting reaction solution to an internal temperature of 5°C, 2M aqueous potassium carbonate solution (450mL) was poured into the solution, and the solution was extracted twice with ethyl acetate (1.5L). The organic phase was washed three times with purified water (2L), dried over sodium sulfate, filtered, and concentrated to obtain a crude product. The crude product was purified by silica gel chromatography to obtain a pale yellow viscous oil (136.6g). The yield was 43.4%. The obtained pale yellow viscous oil was purified by recrystallization. Specifically, in a nitrogen atmosphere, the obtained pale yellow viscous oil (48.3 g) and ethanol (720 mL) were added to a 1 L four-neck flask, and the internal temperature was raised to 40° C. with stirring for 1 hour and 30 minutes. After this, it was left overnight at room temperature, cooled to an internal temperature of 2° C., filtered, and dried under reduced pressure to obtain a powder. The obtained powder was washed with isopropanol (380 mL) and dried under reduced pressure to obtain the target compound (37.1 g) in powder form. 1 H-NMR analysis confirmed that the target compound was compound (1A-1). 1 H-NMR(400MHz,CDCl3)δ7.80(d,J=10.2Hz,2H),7.70(d,J=10.0Hz,2H),7.40-7.36(m,2H),7.29-7.25(m,2H),6.38(dd,J1=2 1.7Hz,J2=1.6Hz,2H),6.06(dd,J1=21.9Hz,J2=12.9Hz,2H),5.81(dd,J1=13.1Hz,J2=1.6Hz,2H),4.37(s,4H),3.84(s,4H).

[0119] The compound (1A-1) obtained in this example was a white powder, and no coloring was observed. The refractive index of the compound (1A-1) obtained as a sample of the powder was measured by the above-mentioned method and was found to be 1.651. Using the obtained powder as a sample, the melting point of compound (1A-1) was measured by the above-mentioned method and found to be 66°C. The obtained powder was used as a sample to produce a curable resin by the above method, and the refractive index, total light transmittance, and haze were measured. The curable resin produced from the curable resin raw material composition had good curability and was colorless and transparent. The polymer (curable resin) of compound (1A-1) had a refractive index of 1.677, a total light transmittance of 90.1%, and a haze of 1.2%.

[0120] (Example 3: Production of compound (2-2)) Compound (2-2) was produced by reacting compound (2a-1) with compound (2b-2).

[0121] [ka]

[0122] Under a nitrogen atmosphere, compound (2b-2) (20 g, 92.45 mmol), 2,2-bis(bromomethyl)-1,3-propanediol (compound (2a-1), 12.11 g, 46.23 mmol), and DMF (150 mL) were mixed. A solution of potassium tert-butoxide (10.37 g, 92.45 mmol) in DMF (50 mL) was added dropwise to the mixture at 75° C., followed by stirring for 30 minutes. After the reaction was completed, the reaction solution was poured into water (1 L), extracted twice with ethyl acetate (500 mL), washed with saturated saline (1 L), dried over sodium sulfate, filtered, and concentrated. The crude product was purified by silica gel column chromatography to obtain 9.7 g of powdered compound (2-2) in a yield of 97.0%. 1 H-NMR analysis confirmed that the target compound was compound (2-2). 1 H-NMR(400MHz,CDCl3)δ8.31-8.29(m,2H),8.15(d,J=9.5Hz,2H),7.99-7.97(m,2H),7.53-7 .50(m,6H),7.39(t,J=3.5Hz,2H),4.78(t,J=4.8Hz,2H),3.51(d,J=4.8Hz,4H),3.27(s,4H). The refractive index of the compound (2-2) obtained as a sample using the obtained powder was measured by the above-mentioned method and was found to be 1.688. The melting point of the compound (2-1) was measured by the above-mentioned method using the obtained powder as a sample, and was found to be 137°C.

[0123] (Example 4: Production of compound (1A-2)) The compound (2-2) obtained in Example 3 was reacted with acrylic acid chloride to produce the compound (1A-2).

[0124] [ka]

[0125] Under a nitrogen atmosphere, compound (2-2) (12 g, 22.52 mmol), triethylamine (11.40 g, 112.62 mmol), and dichloromethane (80 mL) were cooled to 0°C and mixed. Acryloyl chloride (7.14 g, 78.83 mmol) dissolved in dichloromethane (80 mL) was added dropwise at 0-7°C, and the mixture was stirred for 2 hours. After the reaction was completed, the reaction solution was poured into water (300 mL), extracted three times with dichloromethane (300 mL), dried with sodium sulfate, filtered, and concentrated. The obtained crude product was purified by silica gel column chromatography and dried under reduced pressure to obtain 5.24 g of powdered compound (1A-2) in a yield of 36.0%. 1 H-NMR analysis confirmed that the target compound was compound (1A-2). 1 H-NMR(400MHz,CDCl3)δ8.07(d,J=8.8Hz,2H),7.95(d,J=7.6Hz,2H),7.82(d,J=7.6Hz,2H),7.50-7.46 (m,6H),7.30(t,J=7.6Hz,2H),6.17(d,J=17.2Hz,2H),5.87-5.80(dd,J1= 17.2Hz,J2=10.4Hz,2H),5.63(d,J=10.8Hz,2H),4.25(s,4H),3.37(s,4H).

[0126] The compound (1A-2) obtained in this example was a white powder, and no coloring was observed. The refractive index of the compound (1A-2) obtained as a sample using the obtained powder was measured by the above-mentioned method and was found to be 1.651. Using the obtained powder as a sample, the melting point of compound (1A-2) was measured by the above-mentioned method and found to be 52°C. The obtained powder was used as a sample to produce a curable resin by the above method, and the refractive index, total light transmittance, and haze were measured. The curable resin produced from the curable resin raw material composition had good curability and was colorless and transparent. The polymer (curable resin) of compound (1A-2) had a refractive index of 1.702, a total light transmittance of 90.6%, and a haze of 6.0%.

[0127] (Example 5: Production of polymer of curable resin raw material composition) A reaction vessel equipped with a cooler was charged with 20 parts by mass of compound (1A-1), 58 parts by mass of 9,9-bis(4-acryloyloxyethoxyphenyl)fluorene (product name of Shin-Nakamura Chemical Co., Ltd.: NK Ester A-BPEF), 2 parts by mass of benzyl methacrylate (product name of Mitsubishi Chemical Co., Ltd.: Acryester BZ), 20 parts by mass of trimethylolpropane trimethacrylate, 0.5 parts by mass of IRGANOX1076 (product name of BASF Co., Ltd.) as an antioxidant, 0.05 parts by mass of BHT (product name of Honshu Chemical Co., Ltd.: H-BHT) as a polymerization inhibitor, and 2 parts by mass of Irgacure 184 (product name of BASF Co., Ltd.) as a photopolymerization initiator, and the mixture was stirred at 70°C for 2 hours to obtain a curable resin raw material composition. The obtained curable resin raw material composition was sealed between two glass plates using a 1 mm thick silicone sheet as a gasket, and then exposed to a high-pressure mercury lamp (accumulated light amount: 3,000 mJ / cm 2 After heating at 130°C for 30 minutes, the glass plate was removed to obtain a polymerized product having a thickness of 1 mm. As a result of measurement using the above-mentioned haze meter, the total light transmittance of the obtained polymer was 90.4%, and the haze was 1.1%. The refractive index of the resulting polymer was measured using the above refractometer and was found to be 1.6077.

Claims

1. A compound represented by the following formula (1A'): 【Chemistry 1】 [In the formula, A ３ , A ４ each independently represents a (meth)acryloyl group, Cy 11 and Cy 12 each independently represent a benzothiazole ring which may have a substituent, Q １ , Q ２ , Q ３ , Q ４ each independently represents an alkylene group having 1 to 6 carbon atoms.

2. A polymerizable composition comprising the compound according to claim 1 and a polymerization initiator.

3. The polymerizable composition according to claim 2 , which is for use in a member constituting a part or the whole of a transparent optical member.

4. The polymerizable composition according to claim 3, for use as a component constituting all or part of a transparent optical component (excluding hard coats).

5. The polymerizable composition according to claim 3 , which is for use as a member constituting all or a part of a lens.

6. A polymerizable product of the polymerizable composition according to any one of claims 2 to 5.

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