Thermoplastic resin and optical lens containing the same

Abstract

According to the present application, there is provided a thermoplastic resin containing a structural unit (A) derived from a monomer represented by the following general formula (1). In the general formula (1), R1and R 11 respectively independently represent a hydrogen atom, an aryl group having 6 to 12 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms, and X represents any one of the following general formulae (a) to (d). In the general formulae (a) to (d), R 21 ~R 57 respectively independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy group having 1 to 7 carbon atoms.

Description

TECHNICAL FIELD

[0001] The present application relates to a thermoplastic resin and an optical lens containing the same. More specifically, the present application relates to a polycarbonate resin or a polyester carbonate resin, and an optical lens containing the same. BACKGROUND

[0002] As a material of an optical lens used in an optical system of various cameras such as a camera, a camera-integrated film, and a video camera, an optical glass or an optical resin is used. The optical glass is excellent in heat resistance, transparency, dimensional stability, chemical resistance, and the like, but has problems of high material cost, poor molding processability, and low productivity.

[0003] On the other hand, an optical lens composed of an optical resin has an advantage that it can be mass-produced by injection molding, and as a high refractive index material for a camera lens, polycarbonate, polyester carbonate, polyester resin, and the like are used.

[0004] In the case where an optical resin is used for an optical lens, in addition to optical properties such as refractive index and Abbe number, heat resistance, transparency, low water absorption, chemical resistance, low birefringence, and humidity resistance are required. In particular, in recent years, optical lenses having high refractive index and high heat resistance are in demand, and various resins are being developed (Patent Documents 1 to 5).

[0005] On the other hand, based on environmental considerations, resins having a large amount of aliphatic components are expected in all fields such as optical resins. However, aliphatic resins generally have a low glass transition temperature compared to aromatic resins, and have problems in terms of heat resistance. Therefore, it is desirable to develop a resin having a large amount of aliphatic components, which can maintain excellent optical properties and has a high glass transition temperature and excellent heat resistance compared to existing aliphatic resins.

[0006] PRIOR ART DOCUMENTS

[0007] PATENT DOCUMENTS

[0008] Patent Document 1: Japanese Patent Application Laid-Open (JP-A) No. 2018-2893

[0009] Patent Document 2: Japanese Patent Application Laid-Open (JP-A) No. 2018-2894

[0010] Patent Document 3: Japanese Patent Application Laid-Open (JP-A) No. 2018-2895

[0011] Patent Document 4: Japanese Patent Application Laid-Open (JP-A) No. 2018-59074

[0012] Patent Document 5: WO 2017 / 078073 SUMMARY

[0013] Technical problem to be solved by the invention

[0014] The technical problem to be solved by the present invention is to provide a resin having a high aliphatic component, excellent optical properties such as refractive index and Abbe number, and excellent heat resistance, and an optical lens using the resin.

[0015] Technical means for solving the technical problem

[0016] In order to solve the problems of the related art, the inventors of the present invention conducted intensive studies, and as a result, found that a resin having a high aliphatic component, excellent optical properties such as refractive index and Abbe number, and excellent heat resistance can be obtained by using an aliphatic monomer having a specific structure as a raw material, thereby completing the present invention.

[0017] That is, the present invention includes the following modes.

[0018] <1> A thermoplastic resin comprising a structural unit (A) derived from a monomer represented by the following general formula (1).

[0019]

[0020] (In the general formula (1), R1and R 11 each independently represent a hydrogen atom, an aryl group having 6 to 12 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms, and X represents any one of the following general formulae (a) to (d).

[0021]

[0022] (In the general formulae (a) to (d), an asterisk represents a bonding site, and R 21 to R 57 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy group having 1 to 7 carbon atoms.

[0023] <2> The thermoplastic resin according to <1> described above, wherein it is a polycarbonate resin or a polyester carbonate resin.

[0024] <3> The thermoplastic resin according to <1> or <2> described above, wherein R1and R 11 each independently are a linear or branched alkyl group having 1 to 4 carbon atoms.

[0025] <4> The thermoplastic resin according to any one of <1> to <3> described above, wherein X in the general formula (1) is selected from a phenyl group, a biphenyl group, a 1-naphthyl group, and a 2-naphthyl group.

[0026] The thermoplastic resin according to any one of the above <1> to <4>, wherein the monomer represented by General Formula (1) consists only of Isomer B represented by the following formula, or consists of a mixture of Isomer B and Isomer A represented by the following formula.

[0027]

[0028] (In the above formula, R1, R 11 and X have the same meanings as in General Formula (1).

[0029] The thermoplastic resin according to the above <5>, wherein an isomer ratio of the Isomer A to the Isomer B is A:B = 0:100 to 99:1.

[0030] The thermoplastic resin according to any one of the above <1> to <6>, wherein the thermoplastic resin contains a structural unit (B) from a monomer represented by the following General Formula (2) and / or a structural unit (C) from a monomer represented by the following General Formula (3).

[0031]

[0032] (In General Formula (2),

[0033] R a and R b are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which can have a substituent, an alkoxy group having 1 to 20 carbon atoms which can have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which can have a substituent, a cycloalkoxy group having 5 to 20 carbon atoms which can have a substituent, an aryl group having 6 to 20 carbon atoms which can have a substituent, a heteroaryl group having 6 to 20 carbon atoms which can have a substituent and contains 1 or more hetero ring atoms selected from the group consisting of O, N and S, an aryloxy group having 6 to 20 carbon atoms which can have a substituent, and -C≡C-Rh,

[0034] R h represents an aryl group having 6 to 20 carbon atoms which can have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which can have a substituent and contains 1 or more hetero ring atoms selected from the group consisting of O, N and S,

[0035] X represents a single bond, or represents a fluorenyl group which can have a substituent,

[0036] A and B each independently represent an alkylene group having 1 to 5 carbon atoms which can have a substituent,

[0037] m and n each independently represent an integer of 0 to 6,

[0038] a and b each independently represent an integer of 0 to 10.

[0039]

[0040] (in General Formula (3),

[0041] R c and R d are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which can have a substituent, an alkoxy group having 1 to 20 carbon atoms which can have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which can have a substituent, a cycloalkoxy group having 5 to 20 carbon atoms which can have a substituent, and an aryl group having 6 to 20 carbon atoms which can have a substituent,

[0042] Y1is a single bond, a fluorenyl group which can have a substituent, or any one of the structural formulas shown in the following Formulae (4) to (10),

[0043]

[0044] (in Formulae (4) to (10),

[0045] R 61 , R 62 , R 71 and R 72 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which can have a substituent, or an aryl group having 6 to 30 carbon atoms which can have a substituent, or represent a carbon ring or a heterocyclic ring having 1 to 20 carbon atoms which can have a substituent formed by R 61 and R 62 , or by R 71 and R 72 bonding to each other,

[0046] r and s each independently represent an integer of 0 to 5000,

[0047] A and B each independently represent an alkylene group having 1 to 5 carbon atoms which can have a substituent,

[0048] p and q each independently represent an integer of 0 to 4,

[0049] a and b each independently represent an integer of 0 to 10.

[0050] <8> The thermoplastic resin according to the above <7>, wherein, in the General Formula (2) and General Formula (3), A and B each independently represent an alkylene group having 2 or 3 carbon atoms.

[0051] <9> The thermoplastic resin according to the above <7> or <8>, wherein the thermoplastic resin contains at least a structural unit derived from any one of BPEF, BNE, BNEF, and DPBHBNA.

[0052] <10> The thermoplastic resin as described in any one of <1> to <9> above, wherein the thermoplastic resin further comprises a structural unit from at least one monomer from the group consisting of monomers.

[0053]

[0054] (In the above formula, R1 and R2 independently represent hydrogen atoms, methyl or ethyl groups, and R3 and R4 independently represent hydrogen atoms, methyl groups, ethyl groups, or alkylene glycols with 2 to 5 carbon atoms.)

[0055] <11> The thermoplastic resin as described in any one of <1> to <10> above, wherein the weight-average molecular weight (Mw) of the thermoplastic resin converted from polystyrene is 10,000 to 200,000.

[0056] <12> The thermoplastic resin as described in any one of <1> to <11> above, wherein the refractive index (nD) of the thermoplastic resin is 1.599 to 1.750.

[0057] <13> The thermoplastic resin as described in any one of <1> to <12> above, wherein the Abbe number (ν) of the thermoplastic resin is 25.0 to 33.0.

[0058] <14> The thermoplastic resin as described in any one of <1> to <13> above, wherein the glass transition temperature of the thermoplastic resin is 135 to 200°C.

[0059] <15> A thermoplastic resin composition comprising a modifier and a thermoplastic resin as shown in the following general formula (1).

[0060]

[0061] (In general formula (1), R1 and R 11 Each of the following can independently represent a hydrogen atom, an aryl group having 6 to 12 carbon atoms, or a straight-chain or branched alkyl group having 1 to 4 carbon atoms, where X represents any of the following general formulas (a) to (d).

[0062]

[0063] (In general formulas (a) to (d), the asterisk indicates the bonding site, R) 21 ~R 57 Each of the following can be independently represented: a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a straight-chain or branched alkyl group having 1 to 4 carbon atoms, or a straight-chain or branched alkoxy group having 1 to 7 carbon atoms.

[0064] An optical member containing the thermoplastic resin described in any one of the above <1> to <14> or the thermoplastic resin composition described in the above <15>.

[0065] An optical lens containing the thermoplastic resin described in any one of the above <1> to <14> or the thermoplastic resin composition described in the above <15>.

[0066] An optical film containing the thermoplastic resin described in any one of the above <1> to <14> or the thermoplastic resin composition described in the above <15>

[0067] Effects of the Invention

[0068] According to the present application, a resin having a high content of an aliphatic component, which has excellent optical properties such as refractive index and Abbe number, and also has excellent heat resistance, and an optical lens containing the resin can be provided. DETAILED DESCRIPTION

[0069] The present application is described in detail below using synthesis examples and examples, but the present application is not limited to the synthesis examples and examples, and can be changed to any method as long as the scope of the present application is not largely deviated.

[0070] Thermoplastic Resin

[0071] One embodiment of the present application is a thermoplastic resin containing a structural unit (A) derived from a monomer represented by the following general formula (1).

[0072]

[0073] In the general formula (1), R1and R 11 independently represent a hydrogen atom, an aryl group having 6 to 12 carbon atoms (preferably 6 to 10 carbon atoms, more preferably 6 carbon atoms), or a linear or branched alkyl group having 1 to 4 carbon atoms, and X represents any one of the following general formulas (a) to (d).

[0074]

[0075] In the general formulas (a) to (d), the asterisk represents a bonding site. R 21 to R 57 independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy group having 1 to 7 carbon atoms.

[0076] In the structure represented by the general formula (a), the following structures are preferable.

[0077] independently represent a hydrogen atom, an aryl group having 6 to 12 carbon atoms (preferably 6 to 10 carbon atoms, more preferably 6 carbon atoms), or a linear or branched alkyl group having 1 to 4 carbon atoms, and X represents any one of the following general formulas (a) to (d).

[0078] Among the structures represented by general formula (d), the following structures are preferable.

[0079]

[0080] In general formula (1), R1and R 11 The linear or branched alkyl group having 1 to 4 carbon atoms represented by R1and R

[0081] In general formula (1), R1and R 11 The aryl group having 6 to 12 carbon atoms represented by R1and R

[0082] In general formula (1), X is represented by any one of general formulae (a) to (d), and R 21 R1and R 57 The linear or branched alkyl group having 1 to 4 carbon atoms represented by R1and R

[0083] In general formulae (a) to (d), R 21 R1and R 57 is preferably a hydrogen atom. Specifically, X is preferably phenyl (general formula (a)), biphenyl (general formula (b)), 1-naphthyl (general formula (c)), and 2-naphthyl (general formula (d)). Among them, phenyl is more preferable.

[0084] The cyclic dihydroxy compound represented by general formula (1), as a specific preferable structural formula, for example, the following substances can be listed.

[0085]

[0086] As specific examples of the cyclic dihydroxy compound represented by General Formula (1), 5-phenyl-l,3-cyclohexanedione trihydroxymethylpropane dioxime, 5-(4-methylphenyl)-l,3-cyclohexanedione trihydroxymethylpropane dioxime, 5-(4-ethylphenyl)-l,3-cyclohexanedione trihydroxymethylpropane dioxime, 5-(3,4-dimethylphenyl)-l,3-cyclohexanedione trihydroxymethylpropane dioxime, 5-(2,4-dimethylphenyl)-l,3-cyclohexanedione trihydroxymethylpropane dioxime, 5-(3-fluoro-4-methylphenyl)-l,3-cyclohexanedione trihydroxymethylpropane dioxime, 5-(4-isopropylphenyl)-l,3-cyclohexanedione trihydroxymethylpropane dioxime, 5-(2,4,6-trimethylphenyl)-l,3-cyclohexanedione trihydroxymethylpropane dioxime, 5-(2,4,5-trimethylphenyl)-l,3-cyclohexanedione trihydroxymethylpropane dioxime, 5-(3-chloro-4-methylphenyl)-l,3-cyclohexanedione trihydroxymethylpropane dioxime, 5-(4-butylphenyl)-l,3-cyclohexanedione trihydroxymethylpropane dioxime, 5-(4-tert-butylphenyl)-l,3-cyclohexanedione trihydroxymethylpropane dioxime, 5-(4-isobutylphenyl)-l,3-cyclohexanedione trihydroxymethylpropane dioxime, 5-(penta-methylphenyl)-l,3-cyclohexanedione trihydroxymethylpropane dioxime, 5-(4-biphenyl)-l,3-cyclohexanedione trihydroxymethylpropane dioxime, 5-(3-bromo-4-methylphenyl)-l,3-cyclohexanedione trihydroxymethylpropane dioxime, 5-(4-chlorobiphenyl)-l,3-cyclohexanedione trihydroxymethylpropane dioxime, 5-(3-methylphenyl)-l,3-cyclohexanedione trihydroxymethylpropane dioxime, 5-(3,5-dimethylphenyl)-l,3-cyclohexanedione trihydroxymethylpropane dioxime, 5-(4-fluoro-3-methylphenyl)-l,3-cyclohexanedione trihydroxymethylpropane dioxime, 5-(4-methoxy-2,3,6-trimethylphenyl)-l,3-cyclohexanedione trihydroxymethylpropane dioxime, 5-(3-biphenyl)-l,3-cyclohexanedione trihydroxymethylpropane dioxime, 5-(2-bromo-5-methylphenyl)-l,3-cyclohexanedione trihydroxymethylpropane dioxime, 5-(3,5-di-tert-butylphenyl)-l,3-cyclohexanedione trihydroxymethylpropane dioxime, 5-(2-methylphenyl)-l,3-cyclohexanedione trihydroxymethylpropane dioxime, 5-(2,3-dimethylphenyl)-l,3-cyclohexanedione trihydroxymethylpropane dioxime, 5-(2,6-dimethylphenyl)-l,3-cyclohexanedione trihydroxymethylpropane dioxime, 5-(5-fluoro-2-methylphenyl)-l,3-cyclohexanedione trihydroxymethylpropane dioxime, 5-(4-fluoro-2-methylphenyl)-l,3-cyclohexanedione trihydroxymethylpropane dioxime, 5-(3-fluoro-2-methylphenyl)-l,3-cyclohexanedione trihydroxymethylpropane dioxime, 5-(5-bromo-2-methylphenyl)-l,3-cyclohexanedione trihydroxymethylpropane dioxime,3-cyclohexanedione trimethylolpropane bisacetal, 5-(1-naphthyl)-1,3-cyclohexanedione trimethylolpropane bisacetal, 5-(2-naphthyl)-1,3-cyclohexanedione trimethylolpropane bisacetal, 5-(4-methoxyphenyl)-1,3-cyclohexanedione trimethylolpropane bisacetal, 5-(4-ethoxyphenyl)-1,3-cyclohexanedione trimethylolpropane bisacetal, 5-(3-fluoro-4-methoxyphenyl)-1,3-cyclohexanedione trimethylolpropane bisacetal, 5-(2-fluoro-4-methoxyphenyl)-1,3-cyclohexanedione trimethylolpropane bisacetal, 5-(4-isopropoxyphenyl)-1,3-cyclohexanedione trimethylolpropane bisacetal, 5-(4-propoxyphenyl)-1,3-cyclohexanedione trimethylolpropane bisacetal, 5-(2,4-dimethoxyphenyl)-1,3-cyclohexanedione trimethylolpropane bisacetal, 5-(3,4-dimethoxyphenyl)-1,3-cyclohexanedione trimethylolpropane bisacetal, 5-(3-chloro-4-methoxyphenyl)-1,3-cyclohexanedione trimethylolpropane bisacetal, 5-(4-methoxy-2,3,6-trimethylphenyl)-1,3-cyclohexanedione trimethylolpropane bisacetal, 5-(4-tert-butoxyphenyl)-1,3-cyclohexanedione trimethylolpropane bisacetal, 5-(2,4-dimethoxy-3-methylphenyl)-1,3-cyclohexanedione trimethylolpropane bisacetal, 5-(3-ethoxy-4-methoxyphenyl)-1,3-cyclohexanedione trimethylolpropane bisacetal, 5-(4-ethoxy-3-methoxyphenyl)-1,3-cyclohexanedione trimethylolpropane bisacetal, 5-(2-fluoro-4,5-dimethoxyphenyl)-1,3-cyclohexanedione trimethylolpropane bisacetal, 5-(4-pentoxyphenyl)-1,3-cyclohexanedione trimethylolpropane bisacetal, 5-(2,4-diethoxyphenyl)-1,3-cyclohexanedione trimethylolpropane bisacetal, 5-(3,4-diethoxyphenyl)-1,3-cyclohexanedione trimethylolpropane bisacetal, 5-(2,4,5-trimethoxyphenyl)-1,3-cyclohexanedione trimethylolpropane bisacetal, 5-(3,4,5-trimethoxyphenyl)-1,3-cyclohexanedione trimethylolpropane bisacetal, 5-(2,3,4-trimethoxyphenyl)-1,3-cyclohexanedione trimethylolpropane bisacetal, 5-(2,4,6-trimethoxyphenyl)-1,3-cyclohexanedione trimethylolpropane bisacetal, 5-(2-chloro-3,4-dimethoxyphenyl)-1,3-cyclohexanedione trimethylolpropane bisacetal, 5-(4-hexoxyphenyl)-1,3-cyclohexanedione trimethylolpropane bisacetal, 5-(3-bromo-4-methoxyphenyl)-1,3-cyclohexanedione trimethylolpropane bisacetal, 5-(4-heptoxyphenyl)-1,3-cyclohexanedione trimethylolpropane bisacetal, 5-(2-bromo-4,5-dimethoxyphenyl)-1,3-cyclohexanedione trimethylolpropane bisacetal, 5-(3-bromo-4,5-dimethoxyphenyl)-1,3-cyclohexanedione trimethylolpropane bisacetal,3-cyclohexanedione trimethylolpropane bisacetal, 5-(2-naphthyl)-l,3-cyclohexanedione trimethylolpropane bisacetal, 5-(4-methoxy-l-naphthyl)-l,3-cyclohexanedione trimethylolpropane bisacetal, 5-(2-methoxy-l-naphthyl)-l,3-cyclohexanedione trimethylolpropane bisacetal, 5-(2-ethoxy-l-naphthyl)-l,3-cyclohexanedione trimethylolpropane bisacetal, 5-(6-methoxy-2-naphthyl)-l,3-cyclohexanedione trimethylolpropane bisacetal, 5-phenyl-l,3-cyclohexanedione trimethylolethane bisacetal, 5-(4-methylphenyl)-l,3-cyclohexanedione trimethylolethane bisacetal, 5-(4-ethylphenyl)-l,3-cyclohexanedione trimethylolethane bisacetal, 5-(3,4-dimethylphenyl)-l,3-cyclohexanedione trimethylolethane bisacetal, 5-(2,4-dimethylphenyl)-l,3-cyclohexanedione trimethylolethane bisacetal, 5-(3-fluoro-4-methylphenyl)-l,3-cyclohexanedione trimethylolethane bisacetal, 5-(4-isopropylphenyl)-l,3-cyclohexanedione trimethylolethane bisacetal, 5-(2,4,6-trimethylphenyl)-l,3-cyclohexanedione trimethylolethane bisacetal, 5-(2,4,5-trimethylphenyl)-l,3-cyclohexanedione trimethylolethane bisacetal, 5-(3-chloro-4-methylphenyl)-l,3-cyclohexanedione trimethylolethane bisacetal, 5-(4-butylphenyl)-l,3-cyclohexanedione trimethylolethane bisacetal, 5-(4-tert-butylphenyl)-l,3-cyclohexanedione trimethylolethane bisacetal, 5-(4-isobutylphenyl)-l,3-cyclohexanedione trimethylolethane bisacetal, 5-(penta-methylphenyl)-l,3-cyclohexanedione trimethylolethane bisacetal, 5-(4-biphenyl)-l,3-cyclohexanedione trimethylolethane bisacetal, 5-(3-bromo-4-methylphenyl)-l,3-cyclohexanedione trimethylolethane bisacetal, 5-(4-chlorobiphenyl)-l,3-cyclohexanedione trimethylolethane bisacetal, 5-(3-methylphenyl)-l,3-cyclohexanedione trimethylolethane bisacetal, 5-(3,5-dimethylphenyl)-l,3-cyclohexanedione trimethylolethane bisacetal, 5-(4-fluoro-3-methylphenyl)-l,3-cyclohexanedione trimethylolethane bisacetal, 5-(4-methoxy-2,3,6-trimethylphenyl)-l,3-cyclohexanedione trimethylolethane bisacetal, 5-(3-biphenyl)-l,3-cyclohexanedione trimethylolethane bisacetal, 5-(2-bromo-5-methylphenyl)-l,3-cyclohexanedione trimethylolethane bisacetal, 5-(3,5-di-tert-butylphenyl)-l,3-cyclohexanedione trimethylolethane bisacetal, 5-(2-methylphenyl)-l,3-cyclohexanedione trimethylolethane bisacetal, 5-(2,3-dimethylphenyl)-l,3-cyclohexanedione trimethylolethane bisacetal, 5-(2,6-dimethylphenyl)-l,3-cyclohexanedione trimethylolethane bisacetal,3-Cyclohexanedione tris(hydroxymethyl)ethane diacetate, 5-(5-fluoro-2-methylphenyl)-1,3-cyclohexanedione tris(hydroxymethyl)ethane diacetate, 5-(4-fluoro-2-methylphenyl)-1,3-cyclohexanedione tris(hydroxymethyl)ethane diacetate, 5-(3-fluoro-2-methylphenyl)-1,3-cyclohexanedione tris(hydroxymethyl)ethane diacetate, 5-(5-bromo-2-methylphenyl)-1,3-cyclohexanedione tris(hydroxymethyl)ethane diacetate, 5-(1-naphthyl)-1,3-cyclohexanedione tris(hydroxymethyl)ethane diacetate, 5-(2-naphthyl)-1,3-cyclohexanedione tris(hydroxymethyl)ethane diacetate, 5-(4-methoxyphenyl)-1,3-cyclohexanedione tris(hydroxymethyl)ethane diacetate, 5-(4-eth ...cyclohexanedione tris(hydroxymethyl)ethane diacetate, 5-cyclohexanedi Hexanedione trimethylolpropane diacetate, 5-(3-fluoro-4-methoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetate, 5-(2-fluoro-4-methoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetate, 5-(4-isopropoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetate, 5-(4-propoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetate, 5-(2,4-dimethoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetate, 5-(3,4-dimethoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetate, 5-(3-chloro-4-methoxyphenyl)-1,3-cyclohexanedione trimethylolpropane diacetate, 5-( ... 5-(4-tert-butoxyphenyl)-1,3-cyclohexanedione tris(hydroxymethyl)ethane diacetate, 5-(2,4-dimethoxy-3-methylphenyl)-1,3-cyclohexanedione tris(hydroxymethyl)ethane diacetate, 5-(3-ethoxy-4-methoxyphenyl)-1,3-cyclohexanedione tris(hydroxymethyl)ethane diacetate, 5-(4-ethoxy-3-methoxyphenyl)-1,3-cyclohexanedione tris(hydroxymethyl)ethane diacetate, 5-(2-fluoro-4,5-dimethoxyphenyl)-1,3-cyclohexanedione tris(hydroxymethyl)ethane diacetate, 5-(4-pentoxyphenyl)-1,3-cyclohexanedione tris(hydroxymethyl)ethane diacetate, 5-(2,4-di-... 5-(3,4-diethoxyphenyl)-1,3-cyclohexanedione tris(hydroxymethyl)ethane diacetate, 5-(2,4,5-trimethoxyphenyl)-1,3-cyclohexanedione tris(hydroxymethyl)ethane diacetate, 5-(3,4,5-trimethoxyphenyl)-1,3-cyclohexanedione tris(hydroxymethyl)ethane diacetate, 5-(2,3,4-trimethoxyphenyl)-1,3-cyclohexanedione tris(hydroxymethyl)ethane diacetate, 5-(2,4,6-trimethoxyphenyl)-1,3-cyclohexanedione tris(hydroxymethyl)ethane diacetate, 5-(2-chloro-3,4-dimethoxyphenyl)-1,3-cyclohexanedione tris(hydroxymethyl)ethane diacetate, 5-(4-hexyloxyphenyl)-1,3-cyclohexanedione tris(hydroxymethyl)ethane diacetate,3-cyclohexanedione trihydroxymethyl ethane diacetal, 5-(3-bromo-4-methoxyphenyl)- 1,3-cyclohexanedione trihydroxymethyl ethane diacetal, 5-(4-heptyloxyphenyl)- 1,3-cyclohexanedione trihydroxymethyl ethane diacetal, 5-(2-bromo-4,5- dimethoxyphenyl)-l,3-cyclohexanedione trihydroxymethyl ethane diacetal, 5-(3-bromo- 4,5-dimethoxyphenyl)-l,3-cyclohexanedione trihydroxymethyl ethane diacetal, 5-(4- methoxy-l-naphthyl)-l,3-cyclohexanedione trihydroxymethyl ethane diacetal, 5-(2- methoxy-l-naphthyl)-l,3-cyclohexanedione trihydroxymethyl ethane diacetal, 5-(2- ethoxy-l-naphthyl)-l,3-cyclohexanedione trihydroxymethyl ethane diacetal, 5-(6- methoxy-2-naphthyl)-l,3-cyclohexanedione trihydroxymethyl ethane diacetal, and the like.

[0087] Among these, preferred compounds are 5-phenyl-l,3-cyclohexanedione trihydroxymethyl propane diacetal, 5-phenyl-l,3-cyclohexanedione trihydroxymethyl ethane diacetal, 5-(4-tert-butylphenyl)-l,3-cyclohexanedione trihydroxymethyl propane diacetal, 5-(2,4,6- trimethylphenyl)-l,3-cyclohexanedione trihydroxymethyl propane diacetal, 5-(2,4- dimethylphenyl)-l,3-cyclohexanedione trihydroxymethyl propane diacetal, 5-(4- methylphenyl)-l,3-cyclohexanedione trihydroxymethyl propane diacetal, 5-(3,4- dimethylphenyl)-l,3-cyclohexanedione trihydroxymethyl propane diacetal, 5-(4- methoxyphenyl)-l,3-cyclohexanedione trihydroxymethyl propane diacetal, 5-(4- isopropylphenyl)-l,3-cyclohexanedione trihydroxymethyl propane diacetal, 5-(4- isobutylphenyl)-l,3-cyclohexanedione trihydroxymethyl propane diacetal, 5-(4- tert-butylphenyl)-l,3-cyclohexanedione trihydroxymethyl ethane diacetal, 5-(4- biphenyl)-l,3-cyclohexanedione trihydroxymethyl propane diacetal, 5-(4-biphenyl)- 1,3-cyclohexanedione trihydroxymethyl ethane diacetal, 5-(l-naphthyl)-l,3- cyclohexanedione trihydroxymethyl propane diacetal, 5-(l-naphthyl)-l,3- cyclohexanedione trihydroxymethyl ethane diacetal, 5-(2-naphthyl)-l,3- cyclohexanedione trihydroxymethyl propane diacetal, 5-(2-naphthyl)-l,3- cyclohexanedione trihydroxymethyl ethane diacetal. More preferred compounds are 5- phenyl-l,3-cyclohexanedione trihydroxymethyl propane diacetal and 5-phenyl-l,3- cyclohexanedione trihydroxymethyl ethane diacetal.

[0088] Preferably, the cyclic dihydroxy compound represented by General Formula (1) is composed of Isomer B represented by the following formula, or is composed of a mixture of Isomer B and Isomer A represented by the following formula. In addition, as other isomers, Isomer C represented by the following formula can be exemplified.

[0089]

[0090] In the above formula, R1, R 11 and X have the same meanings as in the general formula (1).

[0091] In one embodiment of the present application, the isomer ratio of the above isomer A to the above isomer B is preferably A:B = 0:100 to 99:1, more preferably 0:100 to 50:50, and particularly preferably 20:80 to 50:50. The isomer ratio can be determined by gas chromatography (GC) analysis by area percentage method.

[0092] The novel cyclic dihydroxy compound represented by the general formula (1) can be produced, for example, as shown in the following Reaction Scheme (I).

[0093] <Reaction Scheme (I)>

[0094]

[0095] [In the formula, R1, R 11 and X have the same meanings as in the above general formula (1).]

[0096] As the production method of the novel cyclic dihydroxy compound represented by the general formula (1), as shown in the above Reaction Scheme (I), a production method in which a 1,3-cyclohexanedione compound having a substituent X at the 5-position is subjected to an acetalization reaction with a 2-hydroxymethyl-l,3-propanediol compound having a substituent R1or R 11 at the 2-position in the presence of an acidic catalyst in a toluene solvent can be exemplified.

[0097] The above 1,3-cyclohexanedione compound having a substituent X at the 5-position (compound of the following formula (3)) can be produced as shown in the following Reaction Scheme (II) by reacting a compound represented by the general formula (5) with a compound represented by the general formula (6) in the presence of a base, followed by treatment with an acid.

[0098] <Reaction Scheme (II)>

[0099]

[0100] [In the formula, R 3 are the same or different and each represents an alkyl group having 1 to 3 carbon atoms. X is the same as above.]

[0101] As the alkyl group having 1 to 3 carbon atoms represented by R 3 , for example, a methyl group, an ethyl group, an isopropyl group, and the like can be exemplified.

[0102] The present reaction can be carried out according to or based on a publicly known method, for example, a method described in Chemistry-A Eurpean Journal (2017), 23(49), 11757-11760, Zhurnal Obshchei Khimii (1957), 27.3087-92, and the like.

[0103] The thermoplastic resin of one embodiment of the present application can be a polyester resin, a polycarbonate resin, a polyester carbonate resin, an epoxy resin, a polyurethane resin, a polyacrylate resin, a polymethacrylate resin, or the like, and is not particularly limited, and is preferably a polycarbonate resin or a polyester carbonate resin, and more preferably contains a structural unit (A) represented by the following formula.

[0104]

[0105] [In the formula, R1, R 11 and X have the same meanings as in the above general formula (1).

[0106] In the thermoplastic resin of one embodiment of the present application, the proportion of the structural unit (A) represented by the above formula in all the structural units is not particularly limited, and is preferably 1 to 80 mol%, more preferably 1 to 60 mol%, and further preferably 5 to 50 mol% in all the structural units.

[0107] That is, the thermoplastic resin of one embodiment of the present application can contain, in addition to the structural unit (A) represented by the above formula, a structural unit derived from an aliphatic dihydroxy compound or a structural unit derived from an aromatic dihydroxy compound, which is usually used as a structural unit of a polycarbonate resin or a polyester carbonate resin.

[0108] Specifically, as the aliphatic dihydroxy compound, various substances can be listed, and specifically, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, 1,3-adamantanedimethanol, 2,2-bis(4-hydroxycyclohexyl)-propane, 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 2-(5-ethyl-5-hydroxymethyl-1,3-dioxan-2-yl)-2-methylpropan-1-ol, isosorbide, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and the like can be listed.

[0109] As the aromatic dihydroxy compound, various substances can be exemplified, and specifically, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)cycloalkane, bis(4-hydroxyphenyl) oxide, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) sulfone, bis(4-hydroxyphenyl) sulfoxide, and bis(4-hydroxyphenyl) ketone, diphenyloxyethanol fluorene, and the like can be exemplified.

[0110] Further, it is preferable that the thermoplastic resin of one embodiment of the present application contain a structural unit (B) derived from a monomer represented by the following general formula (2).

[0111]

[0112] In the general formula (2), R a and R b are each independently selected from a halogen atom, an alkyl group having 1 to 20 carbon atoms which can have a substituent, an alkoxy group having 1 to 20 carbon atoms which can have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which can have a substituent, a cycloalkoxy group having 5 to 20 carbon atoms which can have a substituent, an aryl group having 6 to 20 carbon atoms which can have a substituent, a heteroaryl group having 6 to 20 carbon atoms which can have a substituent and contains one or more hetero ring atoms selected from O, N, and S, an aryloxy group having 6 to 20 carbon atoms which can have a substituent, and -C≡C-R h . R h represents an aryl group having 6 to 20 carbon atoms which can have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which can have a substituent and contains one or more hetero ring atoms selected from O, N, and S.

[0113] R a and R b are each independently selected from a halogen atom, an alkyl group having 1 to 20 carbon atoms which can have a substituent, an alkoxy group having 1 to 20 carbon atoms which can have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which can have a substituent, a cycloalkoxy group having 5 to 20 carbon atoms which can have a substituent, an aryl group having 6 to 20 carbon atoms which can have a substituent, a heteroaryl group having 6 to 20 carbon atoms which can have a substituent and contains one or more hetero ring atoms selected from O, N, and S, an aryloxy group having 6 to 20 carbon atoms which can have a substituent, and -C≡C-R

[0114] In the general formula (2), X represents a single bond, or a fluorenyl group which can have a substituent. X is preferably a single bond, or a fluorenyl group which can have a substituent and has a total of 12 to 20 carbon atoms.

[0115] In the general formula (2), A and B are each independently an alkylene group having 1 to 5 carbon atoms which can have a substituent, and are preferably an alkylene group having 2 or 3 carbon atoms.

[0116] In General Formula (2), m and n are each independently an integer of 0 to 6, preferably an integer of 0 to 3, and more preferably 0 or 1.

[0117] In General Formula (2), a and b are each independently an integer of 0 to 10, preferably an integer of 1 to 3, and more preferably 1 or 2.

[0118] As specific examples of the structural unit (B), there can be mentioned structural units derived from 2,2'-bis(2-hydroxyethoxy)-l,l'-binaphthyl (BNE), DPBHBNA, and the like.

[0119]

[0120] Further, it is preferable that the thermoplastic resin of one embodiment of the present application have a structural unit (C) derived from a monomer represented by General Formula (3) below.

[0121]

[0122] In General Formula (3), R c and R d are each independently selected from a halogen atom, an alkyl group having a carbon atom number of 1 to 20 which can have a substituent, an alkoxy group having a carbon atom number of 1 to 20 which can have a substituent, a cycloalkyl group having a carbon atom number of 5 to 20 which can have a substituent, a cycloalkoxy group having a carbon atom number of 5 to 20 which can have a substituent, and an aryl group having a carbon atom number of 6 to 20 which can have a substituent.

[0123] R c and R d are each independently selected from a halogen atom, an alkyl group having a carbon atom number of 1 to 20 which can have a substituent, an alkoxy group having a carbon atom number of 1 to 20 which can have a substituent, a cycloalkyl group having a carbon atom number of 5 to 20 which can have a substituent, a cycloalkoxy group having a carbon atom number of 5 to 20 which can have a substituent, and an aryl group having a carbon atom number of 6 to 20 which can have a substituent.

[0124] In General Formula (3), Y1is a single bond, a fluorenyl group which can have a substituent, or any one of the structural formulas represented by Formulae (4) to (10) below, and is preferably a single bond or the structural formula represented by Formula (4) below.

[0125]

[0126] In Formulae (4) to (10), R 61 , R 62 , R 71 , and R 72respectively independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which can have a substituent, or an aryl group having 6 to 30 carbon atoms which can have a substituent, or represent a carbon ring or a heterocycle having 1 to 20 carbon atoms which can have a substituent formed by bonding R 61 and R 62 , or R 71 and R 72 to each other.

[0127] In formulae (4) to (10), r and s are respectively an integer of 0 to 5000.

[0128] In the above general formula (3), A and B are respectively an alkylene group having 1 to 5 carbon atoms which can have a substituent, preferably an alkylene group having 2 or 3 carbon atoms. In the above general formula (3), p and q are respectively an integer of 0 to 4, preferably 0 or 1. Further, in the above general formula (3), a and b are respectively an integer of 0 to 10, preferably an integer of 0 to 5, more preferably an integer of 0 to 2, for example, 0 or 1.

[0129] As specific examples of the structural unit (C), there can be mentioned structural units from BPEF (9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene), BPPEF (9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene), 9,9-bis[6-(2-hydroxyethoxy)naphthalen-2-yl]fluorene (BNEF), bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bis(4-hydroxyphenyl)-2,2-dichloroethylene, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol P-AP (4,4'-(1-phenylethylidene)bisphenol), bisphenol P-CDE (4,4'-(cyclo-dodecylidene)bisphenol), bisphenol P-HTG (4,4'-(3,3,5-trimethylcyclohexylidene)bisphenol), bisphenol P-MIBK (4,4'-(1,3-dimethylbutylidene)bisphenol), bisphenol PEO-FL (bisphenoxyethanol fluorene), bisphenol P-3MZ (4-[1-(4-hydroxyphenyl)-3-methylcyclohexyl]phenol), bisphenol OC-FL (4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol), bisphenol Z, BP-2EO (2,2'-[[1,1'-biphenyl]-4,4'-diylbis(oxy)bis(ethanol), S-BOC (4,4'-(1-methylethylidene)bis(2-methylphenol), TrisP-HAP (4,4',4"-ethylidene triphenol), and the like. Among these, as the structural unit (C), there are preferably mentioned structural units from BPEF or BNEF.

[0130]

[0131] The thermoplastic resin of one embodiment of the present application is a polymer containing structural unit (A) as a necessary element, and can be a polymer containing structural unit (B) and not containing structural unit (C), a copolymer having structural unit (B) and structural unit (C), a mixture of a polymer having structural unit (B) and a polymer having structural unit (C), or a combination thereof, in addition to a polymer containing structural unit (C) and not containing structural unit (B). As the polymer containing structural unit (C) and not containing structural unit (B), for example, a polymer having a structural unit of the following formula (I-1) to (I-3) can be given, and as the copolymer having structural unit (B) and structural unit (C), for example, a copolymer having a structural unit of the following formula (II-1) to (II-4) can be given.

[0132]

[0133] (In formula (I-1), m and n are each an integer of 1 to 10, preferably an integer of 1 to 5, more preferably 1,

[0134] The number of repeating units of formula (I-3) is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably 1.

[0135] In addition, as the polymer having a plurality of structural units, a block copolymer and a random copolymer in which m and n have a value as high as, for example, 100 or more can be used, and a random copolymer is preferable, and a random copolymer in which m and n have a value of 1 is more preferable.

[0136]

[0137] (In formula (II-1) to (II-4), m and n are each independently an integer of 1 to 10, preferably an integer of 1 to 5, more preferably 1.)

[0138] In addition, as the polymer having a plurality of structural units, a block copolymer and a random copolymer in which m and n have a value as high as, for example, 100 or more can be used, and a random copolymer is preferable, and a random copolymer in which m and n have a value of 1 is more preferable.

[0139] In the copolymer, the molar ratio of structural unit (B) to structural unit (C) is preferably 1 : 99 to 99 : 1, more preferably 10 : 90 to 90 : 10, further preferably 15 : 85 to 85 : 15, and particularly preferably 30 : 70 to 70 : 30. In the mixture, the mass ratio of the polymer having structural unit (B) to the polymer having structural unit (C) is preferably 1 : 99 to 99 : 1, more preferably 10 : 90 to 90 : 10, further preferably 15 : 85 to 85 : 15, and particularly preferably 30 : 70 to 70 : 30.

[0140] The thermoplastic resin of one embodiment of the present application also preferably further contains structural units derived from at least one monomer selected from the following monomer groups.

[0141]

[0142] (In the above formula, R1and R2each independently represent a hydrogen atom, a methyl group, or an ethyl group, and R3and R4each independently represent a hydrogen atom, a methyl group, an ethyl group, or an alkylene glycol having 2 to 5 carbon atoms.)

[0143] In the polycarbonate resin of one preferred embodiment of the present application, an alcohol compound such as a phenol compound generated as a by-product at the time of production, or a dihydroxy component or a carbonate diester which remains unreacted as an impurity can sometimes be present.

[0144] An alcohol compound such as a phenol compound or a carbonate diester as an impurity can cause a decrease in strength or generation of odor at the time of production of a molded body, and thus it is preferable that the content thereof be as little as possible.

[0145] The content of the remaining phenol compound is preferably 3000 parts by mass or less, more preferably 1000 parts by mass or less, and particularly preferably 300 parts by mass or less, relative to 100 parts by mass of the polycarbonate resin.

[0146] The content of the remaining dihydroxy component is preferably 1000 parts by mass or less, more preferably 100 parts by mass or less, and particularly preferably 10 parts by mass or less, relative to 100 parts by mass of the polycarbonate resin.

[0147] The content of the remaining carbonate diester is preferably 1000 parts by mass or less, more preferably 100 parts by mass or less, and particularly preferably 10 parts by mass or less, relative to 100 parts by mass of the polycarbonate resin.

[0148] It is particularly preferable that the content of a compound such as phenol or t-butylphenol be small, and it is preferable that these compounds be within the above range.

[0149] The content of the remaining phenol compound in the polycarbonate resin can be determined by a method in which a phenol compound extracted from the polycarbonate resin is analyzed by gas chromatography.

[0150] The content of the remaining alcohol compound in the polycarbonate resin can also be determined by a method in which an alcohol compound extracted from the polycarbonate resin is analyzed by gas chromatography.

[0151] The content of the dihydroxy component and the carbonic acid diester remaining in the polycarbonate resin can also be determined by extracting these compounds from the polycarbonate resin and analyzing them using gas chromatography.

[0152] The content of the alcohol compound, the dihydroxy component, and the carbonic acid diester as by-products of the phenolic compound and the like can be reduced to an undetectable level, but from the viewpoint of productivity, it can also be contained in a trace amount within a range that does not impair the effects. Also, if it is a trace amount, it is possible to make the plasticity at the time of resin melting good.

[0153] The content of each of the phenolic compound, the dihydroxy component, or the carbonic acid diester remaining can be, for example, 0.01 mass ppm or more, 0.1 mass ppm or more, or 1 mass ppm or more, with respect to 100 mass% of the polycarbonate resin.

[0154] The content of the alcohol compound remaining can be, for example, 0.01 mass ppm or more, 0.1 mass ppm or more, or 1 mass ppm or more, with respect to 100 mass% of the polycarbonate resin.

[0155] Among these, the content of the alcohol compound, the dihydroxy component, and the carbonic acid diester as by-products of the phenolic compound and the like in the polycarbonate resin can be adjusted to the above range by appropriately adjusting the conditions and device settings of the polycondensation. Also, it can be adjusted by the conditions of the extrusion process after the polycondensation.

[0156] For example, the residual amount of the alcohol compound as a by-product of the phenolic compound and the like is related to the kind of the carbonic acid diester used for the polymerization of the polycarbonate resin, or the polymerization temperature and the polymerization pressure, and the like. The residual amount of the alcohol compound as a by-product of the phenolic compound and the like can be reduced by adjusting these factors.

[0157] For example, in the case of producing a polycarbonate resin using a carbonic acid dialkyl ester such as diethyl carbonate, there is a tendency that the molecular weight is difficult to increase, that a low-molecular-weight polycarbonate is formed, and that the content of the alkyl alcohol compound as a by-product increases. Such an alkyl alcohol has high volatility, and once it remains in the polycarbonate resin, there is a tendency that the moldability of the resin deteriorates. In addition, when the residual amount of the alcohol compound as a by-product of the phenolic compound and the like is large, there is a possibility that there is a problem of odor generation at the time of resin molding, and that there is a possibility that a cracking reaction of the resin skeleton occurs at the time of blending and the molecular weight decreases. Therefore, the content of the alcohol compound as a by-product remaining in the obtained polycarbonate resin is preferably 3000 mass ppm or less with respect to the polycarbonate resin (100 mass%). The content of the alcohol compound remaining is preferably 3000 mass ppm or less, more preferably 1000 mass ppm or less, and particularly preferably 300 mass ppm or less, with respect to 100 mass% of the polycarbonate resin.

[0158] <Physical properties of thermoplastic resin>

[0159] (1) Refractive index (nD)

[0160] In one embodiment of the present application, it is a feature that the thermoplastic resin has a high refractive index, and the refractive index is preferably 1.500 to 1.750, more preferably 1.599 to 1.750, further preferably 1.599 to 1.650, particularly preferably 1.600 to 1.650. In the present application, the refractive index can be measured by the method described in the Examples below.

[0161] (2) Abbe number (v)

[0162] In one embodiment of the present application, the Abbe number of the thermoplastic resin is preferably 20.0 to 55.0, more preferably 25.0 to 33.0, further preferably 25.5 to 32.0, particularly preferably 26.0 to 30.0. In the present application, the Abbe number can be measured by the method described in the Examples below.

[0163] (3) Glass transition temperature (Tg)

[0164] In one embodiment of the present application, it is a feature that the thermoplastic resin has a high heat resistance, and the glass transition temperature (Tg) is preferably 135 to 200°C, more preferably 140 to 180°C, particularly preferably 140 to 170°C. In the present application, the glass transition temperature can be measured by the method described in the Examples below.

[0165] (4) Polystyrene-equivalent weight average molecular weight (Mw)

[0166] In one embodiment of the present application, the polystyrene-equivalent weight average molecular weight of the thermoplastic resin is preferably 10,000 to 200,000, more preferably 10,000 to 100,000, particularly preferably 10,000 to 80,000.

[0167] <Thermoplastic resin composition>

[0168] Another embodiment of the present application is a thermoplastic resin composition containing the above-described thermoplastic resin and additives. In the thermoplastic resin composition of the present embodiment, a resin other than the above-described thermoplastic resin of the present application containing structural unit (A) can be used in combination within a range not impairing the intended effects of the present embodiment. As such a resin, there is no particular limitation, and for example, a resin selected from at least one of polycarbonate resin, polyester resin, polyester carbonate resin, (meth)acrylic resin, polyamide resin, polystyrene resin, cyclic olefin resin, acrylonitrile-butadiene-styrene copolymer resin, vinyl chloride resin, polyphenylene ether resin, polysulfone resin, polyacetal resin, and methyl methacrylate-styrene copolymer resin can be exemplified. They can use various known substances, and one kind alone or two or more kinds in combination can be used in the thermoplastic resin composition.

[0169] [Antioxidant]

[0170] An antioxidant is preferably contained as the above-described additive in the thermoplastic resin composition.

[0171] As the antioxidant, at least one of a phenol-based antioxidant and a phosphite-based antioxidant is preferably contained.

[0172] As the phenol-based antioxidant, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine e-2,4,6(1H,3H,5H)-trione, 4,4',4"- (1-methylpropyl-3-ylidene)tris(6-tert-butyl-m-cresol), 6,6'-di-tert-butyl-4,4'-butylidene di-m-cresol, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritol-tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane, pentaerythritol-tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and the like can be exemplified, and pentaerythritol-tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] is preferred.

[0173] As the phosphite-based antioxidant, 2-ethylhexyldiphenyl phosphite, isodecyldiphenyl phosphite, triisodecyl phosphite, triphenyl phosphite, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diazaspiro[5.5]undecane, 3,9-bis(2,6-di-t-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diazaspiro[5.5]undecane, 2,2'-methylolbis(4,6-di-t-butylphenyl)2-ethylhexyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, tris(nonylphenyl) phosphite, tetra-C12-15-alkyl(propane-2,2-diylbis(4,1-phenylenoxy))bis(phosphite), 3,9-bis(2,6-di-t-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diazaspiro[5.5]undecane, and the like can be exemplified, and 3,9-bis(2,6-di-t-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diazaspiro[5.5]undecane is preferred.

[0174] As the antioxidant, only one of the above-mentioned compounds can be used, or a mixture of two or more of them can be used.

[0175] In the thermoplastic resin composition, the antioxidant is preferably contained at 1 to 3000 ppm by weight, based on the total weight of the resin composition. The content of the antioxidant in the thermoplastic resin composition is more preferably 50 to 2500 ppm by weight, more preferably 100 to 2000 ppm by weight, particularly preferably 150 to 1500 ppm by weight, and further more preferably 200 to 1200 ppm by weight.

[0176] [Release agent]

[0177] The thermoplastic resin composition preferably contains a release agent as the above-mentioned additive.

[0178] As the release agent, ester compounds can be exemplified, such as glycerin fatty acid esters such as mono- and diglycerides of glycerin fatty acids, glycol fatty acid esters such as propylene glycol fatty acid esters, sorbitan fatty acid esters, higher alcohol fatty acid esters, and total esters or mono fatty acid esters of aliphatic polyols and aliphatic carboxylic acids. In the case where an ester of an aliphatic polyol and an aliphatic carboxylic acid is used as the release agent, monoesters, total esters, and the like can be used, such as esters other than total esters of monoesters and the like.

[0179] As specific examples of the release agent, the following can be exemplified.

[0180] That is, examples include: sorbitan fatty acid esters such as sorbitan stearate, sorbitan laurate, sorbitan oleate, sorbitan trioleate, sorbitan trihexylenate, sorbitan stearate, sorbitan tristearate, and sorbitan caprylate.

[0181] Propylene glycol fatty acid esters such as propylene glycol monostearate, propylene glycol monooleate, propylene glycol monobehenate, propylene glycol monolaurate, and propylene glycol monopalmitate;

[0182] Higher alcohol fatty acid esters such as stearyl stearate;

[0183] Monoglycerides of glycerol monostearate, glycerol mono-12-hydroxystearate, glycerol monooleate, glycerol mono-behenate, glycerol monocaprylate, glycerol monodecanoate, glycerol monolaurate, etc., including mono- and diglycerides of glycerol fatty acid esters such as glycerol mono-distearate, glycerol mono-distearate, glycerol mono-dibehenate, glycerol mono-dioleate, etc.

[0184] Glyceryl fatty acid esters such as diacetyl monolaurate are acetylated monoglycerides;

[0185] Glycerol fatty acid monoglycerides such as citric acid fatty acid monoglycerides, succinic acid fatty acid monoglycerides, and diacetyl tartaric acid fatty acid monoglycerides are organic acid monoglycerides.

[0186] Polyglycerol fatty acid esters such as diglycerol stearate, diglycerol laurate, diglycerol oleate, diglycerol monostearate, diglycerol monolaurate, diglycerol monomyristate, diglycerol monooleate, tetraglycerol stearate, decaglycerol laurate, decaglycerol oleate, and polyglycerol polyricinoleate.

[0187] In the thermoplastic resin composition, the release agent preferably contains 1 ppm to 5000 ppm by weight, based on the total weight of the resin composition. More preferably, the content of the release agent in the thermoplastic resin composition is 50 ppm to 4000 ppm by weight, further preferably 100 ppm to 3500 ppm by weight, particularly preferably 500 ppm to 13000 ppm by weight, and even more particularly preferably 1000 ppm to 2500 ppm by weight.

[0188] [Other additives]

[0189] In addition to the antioxidants and release agents mentioned above, other additives can also be added to thermoplastic resin compositions. Examples of additives that can be included in thermoplastic resin compositions include, for instance, compounding agents, catalyst deactivators, heat stabilizers, plasticizers, fillers, UV absorbers, rust inhibitors, dispersants, defoamers, leveling agents, flame retardants, lubricants, dyes, pigments, bluing agents, nucleating agents, and transparentizing agents.

[0190] The content of additives other than antioxidants and release agents in the thermoplastic resin composition is preferably 10 ppm to 5.0 wt%, more preferably 100 ppm to 2.0 wt%, and even more preferably 1000 ppm to 1.0 wt%, but is not limited thereto.

[0191] The aforementioned additives may adversely affect transmittance, and it is preferable not to add them in excess, for example, the total amount added should be within the range mentioned above.

[0192] In the method for manufacturing the thermoplastic resin composition of the present invention, in order to maintain thermal stability and hydrolytic stability after the polymerization reaction, the catalyst may be removed or deactivated, but deactivation is not necessary. In the case of deactivation, it is suitable to deactivate the catalyst by adding a known acidic substance. Specifically, suitable acidic substances include: esters such as butyl benzoate; aromatic sulfonic acids such as p-toluenesulfonic acid; aromatic sulfonates such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate; phosphoric acids such as phosphorous acid, phosphoric acid, and phosphonic acid; phosphites such as triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, di-n-hexyl phosphite, dioctyl phosphite, and monooctyl phosphite; and phosphites such as triphenyl phosphate, diphenyl phosphate, and phosphoric acid. Phosphate esters such as monophenyl phosphate, dibutyl phosphate, dioctyl phosphate, and monooctyl phosphate; phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid, and dibutylphosphonic acid; phosphonate esters such as diethyl phenylphosphonate; phosphine derivatives such as triphenylphosphine and bis(diphenylphosphino)ethane; boric acids such as boric acid and phenylboronic acid; aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonate; organohalides such as stearoyl chloride, benzoyl chloride, and p-toluenesulfonyl chloride; alkyl sulfuric acids such as dimethyl sulfuric acid; and organohalides such as benzyl chloride. From the viewpoint of the effectiveness of the deactivator and the stability to the resin, p-toluene or butyl sulfonate is particularly preferred. These deactivators are preferably used at 0.01 to 50 moles, more preferably 0.3 to 20 moles, relative to the catalyst amount. When the amount is less than 0.01 moles relative to the catalyst amount, the deactivation effect becomes insufficient and is not preferred. In addition, when the amount of catalyst is greater than 50 times the molar amount, the heat resistance of the resin decreases and the molded body is prone to coloring, which is not preferred.

[0193] The deactivating agent can be compounded immediately after the polymerization reaction is complete, or it can be compounded after the polymerized resin has been granulated. In addition to the deactivating agent, other additives can also be added using the same method.

[0194] Another embodiment of the present invention is a thermoplastic resin composition containing a modifier and a thermoplastic resin as shown in the following general formula (1).

[0195]

[0196] In general formula (1), R1 and R 11 The meanings of X and X are the same as in the general formula (1) above. That is, the cyclic dihydroxy compound shown in general formula (1) can also be used as a modifier.

[0197] In one embodiment of the present invention, the modifier is formulated in a thermoplastic resin to modifier mass ratio of 99.9:0.1 to 70:30. The mass ratio is preferably 99:1 to 70:30, more preferably 98:2 to 70:30, and for example, 99:1, 98:2, 97:3, 96:4, 95:5, 94:6, 93:7, 92:8, 91:9, 90:10, 85:15, 80:20, 75:25, 70:30, etc. In the present invention, if the mass ratio of thermoplastic resin to modifier is within the above range, a resin composition with high flowability and good moldability can be provided.

[0198] <Optical Components>

[0199] The thermoplastic resin or thermoplastic resin composition of the present invention (hereinafter referred to as "resin composition") is suitable for optical components. In one embodiment of the present invention, an optical component containing the resin composition of the present invention is provided. In one embodiment of the present invention, the optical component includes, but is not limited to, optical discs, transparent conductive substrates, optical memory cards, sheets, films, optical fibers, lenses, prisms, optical films, substrates, filters, hard coatings, etc. The resin composition of the present invention has high fluidity and can be molded by casting, and is therefore particularly suitable for manufacturing thin optical components. In a preferred embodiment of the present invention, the optical component manufactured using the resin composition of the present invention can be an optical lens. In addition to lenses for smartphones, examples of optical lenses include lenses for automotive cameras, lenses for VR (virtual reality) or MR (mixed reality) glasses, lenses for surveillance cameras, etc. In another preferred embodiment of the present invention, the optical component manufactured using the resin composition of the present invention can be an optical film.

[0200] When manufacturing optical components containing the resin composition of the present invention by injection molding, molding is preferably performed at a barrel temperature of 260–350°C and a mold temperature of 90–170°C. Molding is more preferably performed at a barrel temperature of 270–320°C and a mold temperature of 100–160°C. When the barrel temperature is above 350°C, the resin composition decomposes and colors; when the temperature is below 260°C, the melt viscosity increases, making molding difficult. In addition, when the mold temperature is above 170°C, it is difficult to remove the molded sheet formed from the resin composition from the mold; and when the mold temperature is below 90°C, the resin rapidly over-cures within the mold during molding, making it difficult to control the shape of the molded sheet or to fully transfer the molded material.

[0201] <Optical Lenses>

[0202] In one embodiment of the invention, the resin composition is suitable for use in optical lenses. Optical lenses manufactured using the resin composition of the present invention have a high refractive index and excellent heat resistance, and are therefore extremely useful in fields such as telescopes, binoculars, and television projectors, where expensive high-refractive-index glass lenses have historically been used.

[0203] For example, in the lens of a smartphone, a lens unit is formed by overlapping a lens molded from a thermoplastic resin containing structural unit (A) and a lens molded from a resin containing any structural unit of formulas (II-1) to (II-4) or a resin containing any monomer from the above formulas.

[0204]

[0205] (In the above formula, R1 and R2 independently represent hydrogen atoms, methyl or ethyl groups, and R3 and R4 independently represent hydrogen atoms, methyl groups, ethyl groups, or alkylene glycols with 2 to 5 carbon atoms.)

[0206] The optical lens of this invention is suitable for implementation as an aspherical lens as needed. An aspherical lens can achieve substantially zero spherical aberration using a single lens, thus eliminating the need for a combination of multiple spherical lenses to eliminate spherical aberration, enabling weight reduction and lower manufacturing costs. Therefore, aspherical lenses are particularly useful as camera lenses in optical applications.

[0207] Furthermore, the optical lens of the present invention exhibits high molding fluidity, making it particularly useful as a material for thin-walled, small, and complex-shaped optical lenses. Specifically, the thickness of the central portion is preferably 0.05–3.0 mm, more preferably 0.05–2.0 mm, and even more preferably 0.1–2.0 mm. The diameter is preferably 1.0 mm–20.0 mm, more preferably 1.0–10.0 mm, and even more preferably 3.0–10.0 mm. Furthermore, a meniscus lens with one convex and one concave side is preferred in terms of shape.

[0208] The optical lens of the present invention can be formed by any method such as mold forming, cutting, grinding, laser processing, electrical discharge machining, etching, etc. Among these methods, mold forming is preferred from the perspective of manufacturing cost.

[0209] <Optical film>

[0210] In one embodiment of the invention, the resin composition is suitable for use in optical films. In particular, optical films made using the polycarbonate resin of the present invention are suitable for use in liquid crystal substrate films, optical memory cards, etc., due to their excellent transparency and heat resistance.

[0211] To minimize the ingress of foreign matter into the optical film, the molding environment must be a low-dust environment, preferably below level 6, and more preferably below level 5.

[0212] [Example]

[0213] The following examples and comparative examples of the present invention are shown together to illustrate the invention in detail, but the present invention is not limited to these examples.

[0214] 1) refractive index (nD)

[0215] Polycarbonate resin was molded according to JIS B 7071-2:2018 to obtain V-shaped blocks, which served as test pieces. The refractive index was measured at 23°C using a Shimadzu KPR-3000 instrument.

[0216] 2) Abbe number (v)

[0217] Using the same test piece (V-block) as used in the refractive index measurement, the refractive indices at wavelengths of 486 nm, 589 nm, and 656 nm were measured at 23 °C using a refractometer, and the Abbe number was calculated using the following formula.

[0218] ν=(nD-1) / (nF-nC)

[0219] nD: Refractive index at a wavelength of 589nm

[0220] nC: Refractive index at a wavelength of 656nm

[0221] nF: Refractive index at a wavelength of 486nm

[0222] 3) glass transition temperature (Tg)

[0223] According to JIS K7121-1987, the measurements were performed using a differential thermal scanning calorimeter (Hitachi High Technology Corporation X-DSC7000) with a temperature ramping program of 10°C / minute.

[0224] 4) weight average molecular weight (Mw)

[0225] The weight-average molecular weight of the resin was determined by gel permeation chromatography (GPC) and calculated using standard polystyrene. The apparatus, column, and measurement conditions are as follows.

[0226] ·GPC device: Made by Tosoh Corporation, HLC-8420GPC

[0227] ·Pillar: Made by Tosoh Corporation, TSKgel SuperHM-M×3 pieces

[0228] Made by Tosoh Co., Ltd., TSKgel guardcolumn SuperH-H×1 piece

[0229] Made by Tosoh Co., Ltd., TSKgel SuperH-RC×1 piece

[0230] • Detector: RI detector

[0231] • Standard polystyrene: Tosoh Corporation, standard polystyrene reagent kit PStQuick C

[0232] • Sample solution: 0.2% by mass tetrahydrofuran solution

[0233] • Eluent: Tetrahydrofuran

[0234] • Elution buffer flow rate: 0.6 mL / min

[0235] Column temperature: 40℃

[0236] [Synthesis example 1]

[0237] In a 300 ml pear-shaped flask equipped with a Dean-Stark apparatus with a cooling tube, 12.5 g (66.4 mmol) of 5-phenyl-1,3-cyclohexanedione, 625 mg of phosphotungstic acid, 21.3 g (159 mmol) of trimethylolpropane, and 125 ml of toluene were added, and a stir bar was added. The mixture was stirred with a magnetic stirrer while the temperature was increased. Under reflux of toluene, the water produced (aimed at the theoretical amount of water produced, 132 mmol, 2.3 g) was removed using a Dean-Stark apparatus, and the reaction proceeded for 2 hours to produce an acetal. The reaction mixture was allowed to return to room temperature, neutralized with 125 ml of saturated sodium bicarbonate solution, and then 125 ml of toluene was added, separating the aqueous and organic layers. The separated organic layer was washed with 125 ml of warm water at 40 °C. The organic layer was then set to 40 °C and 50 mmHg, and the solvent was removed using a rotary evaporator. The remaining 125 g of the organic layer was stirred at room temperature, and the crystals were collected. Toluene was used as the washing solution, and the precipitated crystals were separated by filtration. The wet crystals were dried at 5 mmHg and 100 °C to obtain 11.8 g (28 mmol) of 5-phenyl-1,3-cyclohexanedione trimethylolpropane diacetal (hereinafter referred to as "Compound 1") with a GC area of ​​99.6%. The melting point of the crystals was 135 °C.

[0238] The IR spectrum of the obtained 5-phenyl-1,3-cyclohexanedione trimethylolpropane diacetal was determined and 1 The H-NMR spectrum, based on the following characteristic peaks, confirmed that it was 5-phenyl-1,3-cyclohexanedione trimethylolpropane diacetal.

[0239] IR (cm) －1 ): 3365, 2965, 2948, 1474, 1463, 1358, 1263, 1253, 1191, 1162, 1087, 1061, 1031, 1000, 969, 820, 756, 699

[0240] 1 H-NMR (500MHz, ppm): 0.80 (t, 3H), 0.87 (t, 3H), 1.24 (m, 2H), 1.33 (m, 2H), 1.39 (t, 1H), 1.49 (d, 1H), 1.67 (t, 1H), 1.96(d, 2H), 2.18(d, 1H), 2.76(d, 1H), 2.94(m, 2H), 3.70(m, 10H), 3.82(m, 2H), 7.20(m, 3H), 7.31(m, 2H)

[0241] The peak near 7.26 ppm is from the solvent deuterated chloroform.

[0242] In addition, LC analysis of compound 1 showed that the LC area of ​​isomer A (shown in the following structural formula) was 26.6%, and the LC area of ​​isomer B (shown in the following structural formula) was 73.1%, i.e., the isomer ratio (isomer A: isomer B = 27:73).

[0243] Isomer A:

[0244]

[0245] Isomer B:

[0246]

[0247] [Synthesis example 2]

[0248] Compound 1 obtained in Synthesis Example 1 was repeatedly recrystallized in the same manner as in Synthesis Example 1 until the area value of isomer A was no longer detected by LC analysis, thus obtaining compound 2. LC analysis of compound 2 showed that the LC area value of isomer B was 97.0%, while the LC area value of isomer A was not detected, i.e., the isomer ratio was isomer A: isomer B = 0:100.

[0249] [Synthesis example 3]

[0250] Add 42.8 g (264 mmol) of 4-tert-butylbenzaldehyde and 396 ml of acetone to a 1 L beaker. While stirring at room temperature, add 264 g of 10% sodium hydroxide aqueous solution dropwise at a temperature below 30 °C. Then, stir at room temperature for 2.5 hours, neutralize with 44 g of acetic acid, and remove the acetone by distillation.

[0251] Add 264 ml of ethyl acetate to separate and extract the organic phase. The obtained organic phase was washed successively with saturated sodium bicarbonate aqueous solution and saturated sodium chloride aqueous solution, and concentrated under reduced pressure to obtain 65.1 g of a pale yellow liquid with a purity of 90.7 GC area%. The crude product was subjected to single distillation under reduced pressure at 141–145 °C and 0.1–0.2 kPa to obtain 35.4 g of a pale yellow liquid with a purity of 98.8 GC area.

[0252] In a 500 ml four-necked flask equipped with a thermometer, nitrogen inlet tube, and cooling tube, 30 ml of ethanol, 17.4 g (110 mmol) of diethyl malonate, and 37.4 g (110 mmol) of 20% sodium ethoxide ethanol solution were added, and the mixture was stirred at room temperature for 30 minutes. Then, the temperature was raised to 70 °C, and a solution of 20.2 g (100 mmol) of 4-tert-butylbenzylacetone dissolved in 30 ml of ethanol was added dropwise over 25 minutes at the same temperature. Afterward, 80 ml of ethanol was added, the temperature was raised, and the mixture was stirred under reflux for 2 hours.

[0253] Next, hydrolysis was performed under reflux for 2 hours using a 10% (w / w) sodium hydroxide aqueous solution. Then, 150 ml of ethanol was removed by distillation under reduced pressure, starting at atmospheric pressure. After cooling to room temperature, 80 g of a 20% (w / w) hydrogen chloride aqueous solution was added, and a decarbonation reaction was carried out under reflux for 4 hours. The precipitated crystals were washed four times with 50 ml of water and dried under reduced pressure to obtain 25.6 g of crude crystals with a GC purity of 91.3%. Next, 200 ml of ethyl acetate was added, and the mixture was stirred at 70°C for 1 hour. To separate the precipitated crystals by filtration, the mixture was washed with 50 ml of ethyl acetate and dried under reduced pressure at 100°C for 2 hours to obtain 19.7 g of a light-colored solid with a GC area percentage of 98.9%.

[0254] In a 500 mL four-necked flask equipped with a thermometer, a nitrogen inlet tube, and a water separator cooling tube, 12.4 g (50 mmol) of 5-(4-tert-butylphenyl)-1,3-cyclohexanedione, 16.8 g (125 mmol) of trimethylolpropane, 625 mmol of phosphotungstic acid, and 120 mL of toluene were added. The mixture was heated and stirred at reflux for 2.5 hours. After the reaction was complete, the mixture was cooled to room temperature, and 50 mL of saturated sodium bicarbonate aqueous solution was added. The mixture was stirred for 0.5 hours. Then, 50 mL of ethyl acetate was added. The resulting organic phase was washed with warm water and concentrated under reduced pressure to obtain 23.5 g of crude diacetate. Regarding the purification of the crude product, recrystallization was performed using 90 g of toluene, followed by filtration, filter cake washing (using 40 ml of cold toluene), and vacuum drying at 100 °C for 2 hours to obtain 14.8 g of 5-(4-tert-butylphenyl)-1,3-cyclohexanedione trimethylolpropane diacetal (hereinafter referred to as "compound 3") with a purity of 98.5 GC area%.

[0255]

[0256] (Example 1)

[0257] As raw materials, 23.5810 g (0.0538 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (BPEF), as shown in the following structural formula, 9.6899 g (0.0230 mol) of 5-phenyl-1,3-cyclohexanedione trimethylolpropane diacetal obtained in Synthesis Example 1, 16.9474 g (0.0791 mol) of diphenyl carbonate (DPC), and 1.29071 × 10⁻⁶ sodium bicarbonate were added to a 300 mL reactor equipped with a stirrer and a distillation device. －4 g(1.53638×10 －6The system was set to a nitrogen atmosphere of 101.3 kPa. The reactor was immersed in an oil bath heated to 200°C to begin the transesterification reaction. Stirring was started 5 minutes after the start of the reaction. After 20 minutes, the pressure was reduced from 101.3 kPa to 26.66 kPa over 10 minutes. The temperature was increased to 210°C while the pressure was reduced, and then increased to 220°C after 70 minutes. After 80 minutes, the pressure was reduced to 20.00 kPa over 30 minutes, and then increased to 240°C and reduced to 0.133 kPa. After holding this temperature for 10 minutes, nitrogen gas was introduced into the reaction system to restore the pressure to 101.3 kPa, yielding polycarbonate resin.

[0258] The obtained polycarbonate resin has a refractive index of 1.6076, an Abbe number of 27.46, a Tg of 144℃, and a polystyrene equivalent weight-average molecular weight (Mw) of 37,000. The content of dihydroxy compounds in the raw materials and the physical properties of the obtained resin are shown in Table 1 below.

[0259] (Example 2)

[0260] In addition to using BPEF 25.4506 g (0.0580 mol) as raw materials, 6.0881 g (0.0145 mol) of 5-phenyl-1,3-cyclohexanedione trimethylolpropane diacetal obtained in Synthesis Example 2, 16.0044 g (0.0747 mol) of DPC, and 4.25154 × 10⁻⁶ sodium bicarbonate, the following other ingredients were also used: －7 g(3.65573×10 －5 Except for the molar amount, the polycarbonate resin was obtained by the same procedure as in Example 1.

[0261] The obtained polycarbonate resin has a refractive index of 1.6125, an Abbe number of 26.02, a Tg of 148℃, and a polystyrene equivalent weight-average molecular weight (Mw) of 40,000. The content of dihydroxy compounds in the raw materials and the physical properties of the obtained resin are shown in Table 1 below.

[0262] (Example 3)

[0263] In addition to using BPEF 23.3726 g (0.0533 mol) as raw materials, 6.5309 g (0.0129 mol) of 5-(4-tert-butyl)-phenyl-1,3-cyclohexanedione trimethylolpropane diacetal obtained in Synthesis Example 3, 14.6156 g (0.0682 mol) of DPC, and 4.25154 × 10⁻⁶ sodium bicarbonate, the following other ingredients were also used: －7 g(3.65573×10 －5 Except for the molar amount, the polycarbonate resin was obtained by the same procedure as in Example 1.

[0264] The obtained polycarbonate resin has a refractive index of 1.6119, an Abbe number of 26.35, a Tg of 146℃, and a polystyrene equivalent weight-average molecular weight (Mw) of 37,000. The content of dihydroxy compounds in the raw materials and the physical properties of the obtained resin are shown in Table 1 below.

[0265] (Comparative Example 1)

[0266] In addition to using BPEF 42.5953g (0.0971 mol) as raw materials, spirodiol (3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane) (SPG) 12.6658g (0.0416 mol), DPC 30.6188g (0.1429 mol), and sodium bicarbonate 1.1656×10 －4 g(1.3874×10 －6 Except for the molar amount, the polycarbonate resin was obtained by the same procedure as in Example 1.

[0267] The obtained polycarbonate resin has a refractive index of 1.5998, an Abbe number of 26.53, a Tg of 134℃, and a polystyrene equivalent weight-average molecular weight (Mw) of 39,000. The content of dihydroxy compounds in the raw materials and the physical properties of the obtained resin are shown in Table 1 below.

[0268] BPEF

[0269]

[0270] Spirodiol (SPG)

[0271]

[0272] [Table 1]

[0273]

[0274] As can be seen from the results in Table 1, Examples 1 to 3, which used the novel cyclic dihydroxy compound represented by general formula (1), compared with Comparative Example 1, which used spirodiol as an existing cyclic dihydroxy compound, were able to obtain resins with high refractive index (nD) and glass transition temperature, excellent optical properties, and excellent heat resistance, and a high aliphatic content.

Claims

1. A thermoplastic resin, characterized by, comprises a structural unit (A) from a monomer represented by the following general formula (1), In General Formula (1), R1and R 11 respectively independently represent a hydrogen atom, an aryl group having 6 to 12 carbon atoms, or a linear or branched alkyl group having 1 to 4 carbon atoms, and X represents any one of the following General Formulae (a) to (d), In General Formulae (a) to (d), an asterisk indicates a bonding site, R 21 ~R 57 respectively independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy group having 1 to 7 carbon atoms, the thermoplastic resin is a polycarbonate resin, a polyester resin, or a polyester carbonate resin, the structural unit (A) accounts for 1 to 80 mol% of the total structural units.

2. The thermoplastic resin according to claim 1, wherein it is a polycarbonate resin or a polyester carbonate resin.

3. The thermoplastic resin according to claim 1 or 2, wherein R1and R2in the general formula (1) are each independently a linear or branched alkyl group having 1 to 4 carbon atoms. 11 R1and R2in the general formula (1) are each independently a linear or branched alkyl group having 1 to 4 carbon atoms.

4. The thermoplastic resin according to claim 1 or 2, wherein X in the general formula (1) is selected from the group consisting of a phenyl group, a biphenyl group, a 1-naphthyl group, and a 2-naphthyl group.

5. The thermoplastic resin according to claim 1 or 2, wherein the monomer represented by the general formula (1) consists of only an isomer B represented by the following formula, or consists of a mixture of the isomer B and an isomer A represented by the following formula, In the above formula, R1, R 11 and X have the same meanings as in general formula (1).

6. The thermoplastic resin according to claim 5, wherein the isomer ratio of the isomer A to the isomer B is A:B = 0:100 to 99:

1.

7. The thermoplastic resin according to claim 1 or 2, wherein the thermoplastic resin comprises a structural unit (B) from a monomer represented by the following general formula (2) and / or a structural unit (C) from a monomer represented by the following general formula (3), in the general formula (2), R a and R b are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms with or without a substituent, an alkoxy group having 1 to 20 carbon atoms with or without a substituent, a cycloalkyl group having 5 to 20 carbon atoms with or without a substituent, a cycloalkoxy group having 5 to 20 carbon atoms with or without a substituent, an aryl group having 6 to 20 carbon atoms with or without a substituent, a heteroaryl group having 6 to 20 carbon atoms with or without a substituent, containing 1 or more hetero ring atoms selected from the group consisting of O, N and S, an aryloxy group having 6 to 20 carbon atoms with or without a substituent, and -C≡C-Rh, R h represents an aryl group having 6 to 20 carbon atoms with or without a substituent, or a heteroaryl group having 6 to 20 carbon atoms with or without a substituent containing 1 or more hetero ring atoms selected from O, N and S, X represents a single bond, or a fluorene group with or without a substituent, A and B each independently represent an alkylene group having 1 to 5 carbon atoms with or without a substituent, m and n each independently represent an integer of 0 to 6, a and b each independently represent an integer of 0 to 10, in the general formula (3), R c and R d are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms with or without a substituent, an alkoxy group having 1 to 20 carbon atoms with or without a substituent, a cycloalkyl group having 5 to 20 carbon atoms with or without a substituent, a cycloalkoxy group having 5 to 20 carbon atoms with or without a substituent, and an aryl group having 6 to 20 carbon atoms with or without a substituent, Y1 is a single bond, a fluorene group with or without a substituent, or any one of the structural formulas represented by the following formulas (4) to (10), in the formulas (4) to (10), R 61 , R 62 , R 71 and R 72 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms with or without a substituent, or an aryl group having 6 to 30 carbon atoms with or without a substituent, or represent a carbocyclic ring or a heterocyclic ring having 1 to 20 carbon atoms with or without a substituent formed by bonding each other of R 61 and R 62 , or R 71 and R 72 , r and s each independently represent an integer of 0 to 5000, A and B each independently represent an alkylene group having 1 to 5 carbon atoms with or without a substituent, p and q each independently represent an integer of 0 to 4, a and b each independently represent an integer of 0 to 10.

8. The thermoplastic resin according to claim 7, wherein in the general formula (2) and the general formula (3), A and B each independently represent an alkylene group having 2 or 3 carbon atoms.

9. The thermoplastic resin according to claim 8, wherein the thermoplastic resin comprises at least a structural unit from any one of BPEF, BNE, BNEF, and DPBHBNA.

10. The thermoplastic resin according to claim 1 or 2, wherein the thermoplastic resin further comprises a structural unit from at least one monomer from the following monomer group, in the above formulae, R1 and R2 each independently represent a hydrogen atom, a methyl group, or an ethyl group, and R3 and R4 each independently represent a hydrogen atom, a methyl group, an ethyl group, or an alkylene glycol having 2 to 5 carbon atoms.

11. The thermoplastic resin according to claim 1 or 2, wherein the thermoplastic resin has a weight average molecular weight (Mw) in terms of polystyrene of 10,000 to 200,000.

12. The thermoplastic resin according to claim 1 or 2, wherein the thermoplastic resin has a refractive index (nD) of 1.599 to 1.

750.

13. The thermoplastic resin according to claim 1 or 2, wherein the thermoplastic resin has an Abbe number (v) of 25.0 to 33.

0.

14. The thermoplastic resin according to claim 1 or 2, wherein the thermoplastic resin has a glass transition temperature of 135 to 200°C.

15. An optical member, comprising the thermoplastic resin according to any one of claims 1 to 14.

16. An optical lens, comprising the thermoplastic resin according to any one of claims 1 to 14.

17. An optical film, comprising the thermoplastic resin according to any one of claims 1 to 14. ​ ​ ​ ​ ​ ​

Images