Thermoplastic resin and optical lens including same

Abstract

The present invention makes it possible to provide a thermoplastic resin including a constituent unit (A) derived from a monomer represented by general formula (1). (In general formula (1), R1-R12, Rk, and Rp each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a C5-20 cycloalkyl group, a C5-20 cycloalkoxyl group, a C6-20 aryl group, a C1-10 linear or branched alkyl group, a C2-10 alkenyl group, a C1-10 alkoxy group, a C6-20 heteroaryl group including one or more hetero atoms selected from O, N, and S, or a C7-20 aralkyl group, X and Y represent a single bond or a C1-5 alkylene group, i and ii each independently represent an integer of 0-4, K1 and K2 each independently represent -OH, -COOH, or -COORq, and Rq represents a C1-5 alkyl group.)

Description

Thermoplastic resin and optical lens containing same

[0001] The present invention relates to a thermoplastic resin and an optical lens containing the same. More particularly, the present invention relates to a polycarbonate resin, a polyester resin, or a polyestercarbonate resin and an optical lens containing the same.

[0002] Optical glass or optical resin is used as a material for optical lenses used in the optical systems of various cameras, such as cameras with integrated film, video cameras, etc. Optical glass is excellent in heat resistance, transparency, dimensional stability, chemical resistance, etc., but has problems such as high material costs, poor moldability, and low productivity.

[0003] On the other hand, optical lenses made of optical resins have the advantage that they can be mass-produced by injection molding, and polycarbonate, polyester carbonate, polyester resin, etc. are used as high refractive index materials for camera lenses.

[0004] When an optical resin is used as an optical lens, in addition to optical properties such as refractive index and Abbe number, it is required to have heat resistance, transparency, low water absorption, chemical resistance, low birefringence, moist heat resistance, etc. In particular, in recent years, there has been a demand for optical lenses with high refractive index and high heat resistance, and various resins have been developed (Patent Documents 1 to 5).

[0005] Furthermore, thermoplastic resins made from 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene have excellent optical properties and are useful as various optical materials (Patent Document 6). However, due to the wide range of molding processes and usage environments, there has been a demand for further improvement in heat resistance without impairing optical properties.

[0006] JP 2018-2893 A JP 2018-2894 A JP 2018-2895 A JP 2018-59074 A WO2017 / 078073 WO2014 / 073496

[0007] An object of the present invention is to provide a thermoplastic resin that has excellent optical properties such as refractive index and Abbe number, and also has excellent heat resistance, and an optical lens using the same.

[0008] As a result of extensive research aimed at solving the problems of the past, the present inventors have found that by using a raw material in which an aromatic ring is introduced into a diol compound having a binaphthalene structure, a thermoplastic resin excellent in optical properties such as refractive index and Abbe number, as well as in heat resistance, can be obtained, and have completed the present invention.

[0009] That is, the present invention includes the following aspects: <1> A thermoplastic resin containing a structural unit (A) derived from a monomer represented by the following general formula (1). (In general formula (1), R １ ~R １２ Rk and Rp each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms containing one or more hetero ring atoms selected from O, N, and S, or an aralkyl group having 7 to 20 carbon atoms; X and Y each independently represent a single bond or an alkylene group having 1 to 5 carbon atoms; i and ii each independently represent an integer of 0 to 4; K １ and K. ２ each independently represents —OH, —COOH, or —COORq, and Rq represents an alkyl group having 1 to 5 carbon atoms.) <2> The thermoplastic resin according to <1> above, which is a polycarbonate resin, a polyester resin, or a polyester carbonate resin. <3> R in the general formula (1) １ ~R １２ , Rk and Rp represent a hydrogen atom, X and Y represent a methylene group, K １ and K. ２ <4> The thermoplastic resin according to the above <1> or <2>, wherein R in the general formula (1) represents —OH. １ ~R １２ , Rk and Rp represent a hydrogen atom, X and Y represent a single bond, K １ and K. ２represents —COOH or —COORq, and Rq represents an alkyl group having 1 to 5 carbon atoms. <5> The thermoplastic resin according to any one of <1> to <4> above, wherein the thermoplastic resin contains a structural unit (B) derived from a monomer represented by the following general formula (2) and / or a structural unit (C) derived from a monomer represented by the following general formula (3): (In general formula (2), R ａ and R ｂ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and -C≡C-R ｈ R is selected from the group consisting of ｈ represents an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N, and S and which may have a substituent; X represents a single bond or an optionally substituted fluorene group; A and B each independently represent an optionally substituted alkylene group having 1 to 5 carbon atoms; m and n each independently represent an integer of 0 to 6; and a and b each independently represent an integer of 0 to 10. (In 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 which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, and an aryl group having 6 to 20 carbon atoms which may have a substituent; １represents a single bond, a fluorene group which may have a substituent, or any of the structural formulae represented by the following formulae (4) to (11): (In formulas (4) to (11), R ６１ , R ６２ , R ７１ and R ７２ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent, or R ６１ and R ６２ , or R ７１ and R ７２ are bonded to each other to form a carbon ring or hetero ring having 1 to 20 carbon atoms, which may have a substituent; R ａａ and R ｂｂ represents R in the above general formula (2). ａ and R ｂ and r and s each independently represent an integer of 0 to 5,000.) A and B each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent, p and q each independently represent an integer of 0 to 4, and a and b each independently represent an integer of 0 to 10.) <6> The thermoplastic resin according to <5> above, wherein the thermoplastic resin contains at least a structural unit derived from any one of BPEF, BNE, BNEF, and DPBHBNA. <7> The thermoplastic resin according to any one of <1> to <6> above, wherein the thermoplastic resin further contains a structural unit derived from at least one monomer selected from the group of monomers below: (In the above formula, R １ and R ２ each independently represents a hydrogen atom, a methyl group, or an ethyl group; R ３ and R ４each independently represents a hydrogen atom, a methyl group, an ethyl group, or an alkylene glycol having 2 to 5 carbon atoms. Raaa and Rbbb each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N, and S and which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and -C≡C-R ｈ wherein mm and nn each independently represent an integer of 0 to 6.) <8> The thermoplastic resin according to any one of <1> to <7> above, wherein the polystyrene-equivalent weight average molecular weight (Mw) of the thermoplastic resin is 10,000 to 200,000. <9> The thermoplastic resin according to any one of <1> to <8> above, wherein the refractive index (nD) of the thermoplastic resin is 1.64 to 1.70. <10> The thermoplastic resin according to any one of <1> to <9> above, wherein the Abbe number (ν) of the thermoplastic resin is 15.0 to 24.0. <11> The thermoplastic resin according to any one of <1> to <10> above, wherein the glass transition temperature of the thermoplastic resin is 130 to 180°C. <12> A thermoplastic resin composition comprising a modifier represented by the following general formula (1) and a thermoplastic resin: (In general formula (1), R １ ~R １２ Rk and Rp each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms containing one or more hetero ring atoms selected from O, N, and S, or an aralkyl group having 7 to 20 carbon atoms; X and Y each independently represent a single bond or an alkylene group having 1 to 5 carbon atoms; i and ii each independently represent an integer of 0 to 4; K１ and K. ２ each independently represents -OH, -COOH, or -COORq, and Rq represents an alkyl group having 1 to 5 carbon atoms.) <13> An optical member comprising the thermoplastic resin according to any one of the above <1> to <11> or the thermoplastic resin composition according to the above <12>. <14> An optical lens comprising the thermoplastic resin according to any one of the above <1> to <11> or the thermoplastic resin composition according to the above <12>. <15> An optical film comprising the thermoplastic resin according to any one of the above <1> to <11> or the thermoplastic resin composition according to the above <12>.

[0010] According to the present invention, it is possible to provide a thermoplastic resin that is excellent in optical properties such as refractive index and Abbe number, and also excellent in heat resistance, and an optical lens containing the same.

[0011] Hereinafter, the present invention will be described in detail by way of examples and synthesis examples. However, the present invention is not limited to the synthesis examples and examples exemplified, and can be carried out by any method as long as it does not significantly deviate from the content of the present invention.

[0012] <Thermoplastic Resin> One embodiment of the present invention is a thermoplastic resin containing a structural unit (A) derived from a monomer represented by the following general formula (1). In general formula (1), R １ ~R １２Rk and Rp each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cycloalkyl group having 5 to 20 carbon atoms (preferably 5 to 10, more preferably 6 to 8), a cycloalkoxyl group having 5 to 20 carbon atoms (preferably 5 to 10), an aryl group having 6 to 20 carbon atoms (preferably 6 to 12, more preferably 6 to 10), a linear or branched alkyl group having 1 to 10 carbon atoms (preferably 1 to 4, more preferably 1 to 3, particularly preferably 1 to 2), an alkenyl group having 2 to 10 carbon atoms (preferably 2 to 5), an alkoxy group having 1 to 10 carbon atoms (preferably 1 to 5), a heteroaryl group having 6 to 20 carbon atoms (preferably 6 to 15, more preferably 6 to 12, particularly preferably 6 to 10) containing one or more hetero ring atoms selected from O, N, and S, or an aralkyl group having 7 to 20 carbon atoms (preferably 7 to 10). R １ ~R １２ , Rk and Rp preferably each independently represent a hydrogen atom, a methyl group, or a phenyl group, and more preferably, R １ ~R １２ , Rk, and Rp all represent a hydrogen atom. X and Y each represent a single bond or an alkylene group having 1 to 5 carbon atoms (preferably 1 to 3), preferably a single bond, a methylene group, or an ethylene group, more preferably a single bond or a methylene group. i and ii each independently represent an integer of 0 to 4, preferably an integer of 0 to 2. K １ and K. ２ each independently represents —OH, —COOH, or —COORq, where Rq represents an alkyl group having 1 to 5 carbon atoms (preferably 1 to 3). Rq preferably represents a methyl group, an ethyl group, or a propyl group, and more preferably represents a methyl group.

[0013] In one embodiment of the present invention, R in general formula (1) １ ~R １２ , Rk and Rp represent a hydrogen atom, X and Y represent a methylene group, K １ and K. ２ In addition, an embodiment in which R in general formula (1) represents —OH is preferable. １ ~R １２ , Rk and Rp represent a hydrogen atom, X and Y represent a single bond, K１ and K. ２ Also preferred is an embodiment in which Rq represents an alkyl group having 1 to 5 carbon atoms (preferably 1 to 3 carbon atoms).

[0014] Specific particularly preferred compounds of the monomer represented by formula (1) are shown below, but the present invention is not limited to these compounds.

[0015] The monomer represented by general formula (1) can be produced according to the method described in Adv. Synth. Catal. 2004, 346, 195-198. For example, it can be produced as shown in the following reaction scheme.

[0016] As shown in the above reaction scheme, 2,2-binaphthol is reacted with p-bromobenzaldehyde in pyridine in the presence of copper, copper oxide, and potassium carbonate to produce 4,4'-([1,1'-binaphthalene]-2,2'-diylbis(oxy))dialdehyde, which is then reduced with a reducing agent such as lithium aluminum hydride (LiAlH4). By replacing p-bromobenzaldehyde with o-bromobenzaldehyde or m-bromobenzaldehyde, isomers can be obtained.

[0017] The thermoplastic resin according to one embodiment of the present invention is not particularly limited and may be a polyester resin, a polycarbonate resin, a polyester carbonate resin, an epoxy resin, a polyurethane resin, a polyacrylic acid ester resin, a polymethacrylic acid ester resin, or the like. However, it is preferably a polycarbonate resin, a polyester resin, or a polyester carbonate resin, and more preferably contains a structural unit (A) represented by the following formula: [Each symbol in the formula has the same meaning as in the general formula (1)]

[0018] In a thermoplastic resin according to one embodiment of the present invention, the proportion of the structural unit (A) represented by the above formula relative to all structural units is not particularly limited, but is preferably 1 to 90 mol %, more preferably 1 to 80 mol %, even more preferably 5 to 70 mol %, and particularly preferably 10 to 60 mol % of all structural units. In other words, in addition to the structural unit (A) represented by the above formula, a thermoplastic resin according to one embodiment of the present invention can contain structural units derived from aliphatic dihydroxy compounds or aromatic dihydroxy compounds, which are generally used as structural units in polycarbonate resins and polyester carbonate resins. Specific examples of aliphatic dihydroxy compounds include, but are not limited to, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, 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, and 1,6-hexanediol. Examples of aromatic dihydroxy compounds include various compounds, particularly 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, bis(4-hydroxyphenyl)ketone, bisphenoxyethanolfluorene, and the like.

[0019] Furthermore, the thermoplastic resin according to one embodiment of the present invention preferably contains a structural unit (B) derived from a monomer represented by the following general formula (2). In general formula (2), R ａ and R ｂ each independently represents a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and -C≡C-R ｈ R ｈ represents an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent. ａ and R ｂ is preferably a hydrogen atom, an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent, more preferably a hydrogen atom, or an aryl group having 6 to 20 carbon atoms which may have a substituent, and even more preferably a hydrogen atom, or an aryl group having 6 to 12 carbon atoms which may have a substituent.

[0020] In general formula (2), X represents a single bond or a fluorene group which may have a substituent. X is preferably a single bond or a fluorene group which may have a substituent and has a total of 12 to 20 carbon atoms. In general formula (2), A and B each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent, preferably an alkylene group having 2 or 3 carbon atoms. In general formula (2), m and n each independently represent an integer of 0 to 6, preferably an integer of 0 to 3, and more preferably 0 or 1. In general formula (2), a and b each independently represent an integer of 0 to 10, preferably an integer of 1 to 3, and more preferably 1 or 2.

[0021] Specific examples of the structural unit (B) include those derived from 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene (BNE), DPBHBNA, and the like.

[0022] Furthermore, the thermoplastic resin according to one embodiment of the present invention preferably contains a structural unit (C) derived from a monomer represented by the following general formula (3). In general formula (3), R ｃ and R ｄ are each independently selected from the group consisting of a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, and an aryl group having 6 to 20 carbon atoms which may have a substituent. ｃ and R ｄ is preferably a hydrogen atom, an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent, more preferably a hydrogen atom, or an aryl group having 6 to 20 carbon atoms which may have a substituent, and even more preferably a hydrogen atom, or an aryl group having 6 to 12 carbon atoms which may have a substituent.

[0023] In the general formula (3), Y １ represents a single bond, a fluorene group which may have a substituent, or any of the structural formulae represented by the following formulas (4) to (11), and is preferably a single bond or the structural formula represented by the following formula (4): In formulas (4) to (11), R ６１ , R ６２ , R ７１ and R ７２ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent, or R ６１ and R ６２ , or R ７１ and R ７２are bonded to each other to form a carbon ring or hetero ring having 1 to 20 carbon atoms, which may have a substituent; R ａａ and R ｂｂ represents R in the above general formula (2). ａ and R ｂ In formulas (4) to (11), r and s each independently represent an integer of 0 to 5,000.

[0024] In the general formula (3), A and B are each independently an alkylene group having 1 to 5 carbon atoms, which may have a substituent, and preferably an alkylene group having 2 or 3 carbon atoms. In the general formula (3), p and q are each independently an integer of 0 to 4, and preferably 0 or 1. In the general formula (3), a and b are each independently an integer of 0 to 10, preferably an integer of 0 to 5, and more preferably an integer of 0 to 2, for example, 0 or 1.

[0025] Specific examples of the structural unit (C) include 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'-cyclododecylidenebisphenol), bisphenol Bisphenol P-HTG (4,4'-(3,3,5-trimethylcyclohexylidene)bisphenol), bisphenol P-MIBK (4,4'-(1,3-dimethylbutylidene)bisphenol), bisphenol PEO-FL (bisphenoxyethanolfluorene), bisphenol P-3MZ (4-[1-(4-hydroxyphenyl)-3-methylcyclohexyl]phenol), bisphenol OC-FL (4,4'-[1-[ Examples of structural unit (C) include those derived from BPEF (4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol), bisphenol Z, BP-2EO (2,2'-[[1,1'-biphenyl]-4,4'-diylbis(oxy)bisethanol), S-BOC (4,4'-(1-methylethylidene)bis(2-methylphenol), TrisP-HAP (4,4',4''-ethylidene trisphenol), etc. Among these, preferred structural unit (C) is one derived from BPEF or BNEF.

[0026] The thermoplastic resin according to one embodiment of the present invention essentially contains the structural unit (A), but may also be a polymer containing the structural unit (B) but not the structural unit (C), a polymer containing the structural unit (C) but not the structural unit (B), a copolymer containing the structural unit (B) and the structural unit (C), a mixture of a polymer containing the structural unit (B) and a polymer containing the structural unit (C), or a combination thereof. Examples of polymers containing the structural unit (C) but not the structural unit (B) include those having structural units represented by the following formulas (I-1) to (I-3), and examples of copolymers having the structural unit (B) and the structural unit (C) include those having structural units represented by the following formulas (II-1) to (II-4). (In formula (I-1), m and n each represent an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably 1; the number of repeating units in formula (I-3) is an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably 1.) Furthermore, as the polymer having multiple types of structural units, either a block copolymer in which the values ​​of m and n are large, for example, 100 or more, or a random copolymer can be used, but a random copolymer is preferred, and more preferably a random copolymer in which the values ​​of m and n are 1 is used. (In formulas (II-1) to (II-4), m and n each independently represent an integer of 1 to 10, preferably an integer of 1 to 5, and more preferably 1.) Furthermore, as the polymer having multiple types of structural units, either a block copolymer in which the values ​​of m and n are large, for example, 100 or greater, or a random copolymer can be used, although a random copolymer is preferred, and more preferably a random copolymer in which the values ​​of m and n are 1. 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, even more preferably 15:85 to 85:15, and particularly preferably 30:70 to 70:30. Furthermore, in the mixture, the mass ratio of the polymer having the structural unit (B) to the polymer having the structural unit (C) is preferably 1:99 to 99:1, more preferably 10:90 to 90:10, even more preferably 15:85 to 85:15, and particularly preferably 30:70 to 70:30.

[0027] The thermoplastic resin according to one embodiment of the present invention preferably further contains a structural unit derived from at least one monomer selected from the following group of monomers: (In the above formula, R １ and R ２ each independently represents a hydrogen atom, a methyl group, or an ethyl group; R ３ and R ４ each independently represents a hydrogen atom, a methyl group, an ethyl group, or an alkylene glycol having 2 to 5 carbon atoms. Raaa and Rbbb each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N, and S and which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and -C≡C-R ｈwherein mm and nn each independently represent an integer of 0 to 6.

[0028] In a preferred embodiment of the polycarbonate resin or polyester carbonate resin of the present invention, impurities such as alcohol compounds such as phenolic compounds that may be produced as by-products during production, or diol components or carbonate diesters that remain unreacted, may be present. The impurities, such as alcohol compounds such as phenolic compounds and carbonate diesters, may cause a decrease in strength or the generation of odor when molded into a product, so it is preferable that the content of these impurities be as small as possible.

[0029] The content of residual phenolic compounds is preferably 3,000 ppm by mass or less, more preferably 1,000 ppm by mass or less, and particularly preferably 300 ppm by mass or less, based on 100% by mass of the polycarbonate resin. The content of residual diol components is preferably 1,000 ppm by mass or less, more preferably 100 ppm by mass or less, and particularly preferably 10 ppm by mass or less, based on 100% by mass of the polycarbonate resin. The content of residual carbonate diesters is preferably 1,000 ppm by mass or less, more preferably 100 ppm by mass or less, and particularly preferably 10 ppm by mass or less, based on 100% by mass of the polycarbonate resin. In particular, it is preferable that the contents of compounds such as phenol and t-butylphenol are low, and it is preferable that the contents of these compounds are within the above ranges.

[0030] The content of phenolic compounds remaining in the polycarbonate resin can be measured by a method of analyzing phenolic compounds extracted from the polycarbonate resin using gas chromatography. The content of alcoholic compounds remaining in the polycarbonate resin can also be measured by a method of analyzing alcoholic compounds extracted from the polycarbonate resin using gas chromatography. The content of diol components and carbonate diesters remaining in the polycarbonate resin can also be measured by a method of extracting these compounds from the polycarbonate resin and analyzing them using gas chromatography.

[0031] The contents of by-produced alcohol compounds such as phenolic compounds, diol components, and carbonate diesters may be reduced to an undetectable level, but from the viewpoint of productivity, they may be contained in small amounts within a range that does not impair the effects. Furthermore, small amounts can improve the plasticity of the resin when it is melted.

[0032] The content of each of the remaining phenolic compounds, diol components, and carbonate diesters may be, for example, 0.01 ppm by mass or more, 0.1 ppm by mass or more, or 1 ppm by mass or more, relative to 100% by mass of the polycarbonate resin. The content of the remaining alcoholic compounds may be, for example, 0.01 ppm by mass or more, 0.1 ppm by mass or more, or 1 ppm by mass or more, relative to 100% by mass of the polycarbonate resin.

[0033] The contents of by-produced alcohol compounds such as phenolic compounds, diol components, and carbonate diesters in the polycarbonate resin can be adjusted to fall within the above ranges by appropriately adjusting the polycondensation conditions and apparatus settings, and can also be adjusted by the conditions of the extrusion step after polycondensation.

[0034] For example, the amount of residual by-produced alcohol compounds such as phenolic compounds is related to the type of carbonate diester used in the polymerization of the polycarbonate resin, the polymerization reaction temperature, the polymerization pressure, etc. By adjusting these factors, the amount of residual by-produced alcohol compounds such as phenolic compounds can be reduced.

[0035] For example, when a polycarbonate resin is produced using a dialkyl carbonate such as diethyl carbonate, the molecular weight is difficult to increase, resulting in a low-molecular-weight polycarbonate, and the content of by-product alkyl alcohol compounds tends to be high. Such alkyl alcohols are highly volatile, and if they remain in the polycarbonate resin, the moldability of the resin tends to deteriorate. Furthermore, if a large amount of by-product alcohol compounds such as phenolic compounds remain, odor problems may occur during resin molding, or the cleavage reaction of the resin skeleton may progress during compounding, resulting in a decrease in molecular weight. Therefore, it is preferable that the content of by-product alcohol compounds remaining in the obtained polycarbonate resin be 3,000 ppm by mass or less relative to 100% by mass of the polycarbonate resin. The content of the remaining alcohol compounds is preferably 3,000 ppm by mass or less, more preferably 1,000 ppm by mass or less, and particularly preferably 300 ppm by mass or less, relative to 100% by mass of the polycarbonate resin.

[0036] <Physical Properties of Thermoplastic Resin> (1) Refractive Index (nD) In ​​one embodiment of the present invention, one of the characteristics of the thermoplastic resin is that it has a high refractive index, and the refractive index is preferably 1.64 to 1.70, more preferably 1.64 to 1.69, and particularly preferably 1.65 to 1.68. In the present invention, the refractive index can be measured by the method described in the examples below.

[0037] (2) Abbe number (ν) In one embodiment of the present invention, the Abbe number of the thermoplastic resin is preferably 15.0 to 26.0, more preferably 15.0 to 24.0, and particularly preferably 18.0 to 22.0. In the present invention, the Abbe number can be measured by the method described in the examples below.

[0038] (3) Glass Transition Temperature (Tg) In one embodiment of the present invention, one of the characteristics of the thermoplastic resin is high heat resistance, and the glass transition temperature (Tg) is preferably 130 to 180° C., more preferably 135 to 170° C., and particularly preferably 140 to 160° C. In the present invention, the glass transition temperature can be measured by the method described in the examples below.

[0039] (4) Weight Average Molecular Weight (Mw) in Polystyrene Equivalents In one embodiment of the present invention, the weight average molecular weight of the thermoplastic resin in polystyrene equivalents is preferably 10,000 to 200,000, more preferably 10,000 to 100,000, and particularly preferably 10,000 to 80,000.

[0040] <Thermoplastic Resin Composition> Another embodiment of the present invention is a thermoplastic resin composition containing the above-described thermoplastic resin and an additive. The thermoplastic resin composition of this embodiment can be used in combination with a resin other than the thermoplastic resin of the present invention containing the above-described structural unit (A), as long as the desired effects of this embodiment are not impaired. Examples of such resins include, but are not limited to, at least one resin selected from the group consisting of polycarbonate resins, polyester resins, polyestercarbonate resins, (meth)acrylic resins, polyamide resins, polystyrene resins, cycloolefin resins, acrylonitrile-butadiene-styrene copolymer resins, vinyl chloride resins, polyphenylene ether resins, polysulfone resins, polyacetal resins, and methyl methacrylate-styrene copolymer resins. Various known resins can be used, and one type can be added alone or two or more types can be added in combination to the thermoplastic resin composition.

[0041] [Antioxidant] The thermoplastic resin composition preferably contains an antioxidant as the additive. The antioxidant preferably contains at least one of a phenolic antioxidant and a phosphite-based antioxidant. Examples of phenolic antioxidants include 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-methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol), 6,6'-di-tert-butyl-4,4'-butylidene-m-cresol, ocladecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentane, methyl ... Examples of the hydroxybenzoate include pentaerythritol-tetrakis[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-tetraoxospiro[5.5]undecane, and pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and preferably pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].Phosphite antioxidants include 2-ethylhexyl diphenyl phosphite, isodecyl diphenyl phosphite, triisodecyl phosphite, triphenyl phosphite, 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxy-3,9-diphosphaspiro[5.5]undecane, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 2,2'-methylenebis(4,6-di-tert-butylphenyl)2-ethylhexyl phosphite, Examples of the antioxidant include tris(2,4-di-tert-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra-C12-15-alkyl(propane-2,2-diylbis(4,1-phenylene))bis(phosphite), and 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and preferably 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane. As the antioxidant, any one of the above may be used alone, or a mixture of two or more may be used.

[0042] The antioxidant content in the thermoplastic resin composition is preferably 1 ppm by weight to 3,000 ppm by weight based on the total weight of the resin composition, more preferably 50 ppm by weight to 2,500 ppm by weight, even more preferably 100 ppm by weight to 2,000 ppm by weight, particularly preferably 150 ppm by weight to 1,500 ppm by weight, and even more preferably 200 ppm by weight to 1,200 ppm by weight.

[0043] [Release Agent] The thermoplastic resin composition preferably contains a release agent as the additive. Examples of the release agent include ester compounds, such as glycerin fatty acid esters such as mono- and diglycerides of glycerin fatty acid, glycol fatty acid esters such as propylene glycol fatty acid esters and sorbitan fatty acid esters, higher alcohol fatty acid esters, and full esters or mono-fatty acid esters of aliphatic polyhydric alcohols and aliphatic carboxylic acids. When an ester of aliphatic polyhydric alcohols and aliphatic carboxylic acids is used as the release agent, either a monoester or a full ester can be used, but other than a full ester, such as a monoester, may also be used. Specific examples of the release agent include the following.That is, sorbitan fatty acid esters such as sorbitan stearate, sorbitan laurate, sorbitan oleate, sorbitan trioleate, sorbitan tribehenate, sorbitan stearate, sorbitan tristearate, and sorbitan caprylate; propylene glycol fatty acid esters such as propylene glycol monostearate, propylene glycol monooleate, propylene glycol monobehenate, propylene glycol monolaurate, and propylene glycol monopalmitate; higher alcohol fatty acid esters such as stearyl stearate; glycerin monohydroxystearates such as glycerin monostearate and glycerin mono-12-hydroxystearate, glycerin monooleate, glycerin monobehenate, glycerin monocaprylate, glycerin monocaprate, and glycerin Examples of the monoglycerides include monoglycerides such as monolaurate, and mono-diglycerides such as glycerin monodistearate, glycerin monodistearate, glycerin monodibehenate, and glycerin monodiolate; acetylated monoglycerides of glycerin fatty acid esters such as glycerin diacetomonolaurate; organic acid monoglycerides of glycerin fatty acid esters such as citric acid fatty acid monoglyceride, succinic acid fatty acid monoglyceride, and diacetyltartaric acid fatty acid monoglyceride; and polyglycerin fatty acid esters such as diglycerin stearate, diglycerin laurate, diglycerin oleate, diglycerin monostearate, diglycerin monolaurate, diglycerin monomyristate, diglycerin monooleate, tetraglycerin stearate, decaglycerin laurate, decaglycerin oleate, and polyglycerin polyricinoleate.

[0044] The thermoplastic resin composition preferably contains 1 ppm by weight to 5,000 ppm by weight of the release agent based on the total weight of the resin composition, more preferably 50 ppm by weight to 4,000 ppm by weight, even more preferably 100 ppm by weight to 3,500 ppm by weight, particularly preferably 500 ppm by weight to 13,000 ppm by weight, and even more preferably 1,000 ppm by weight to 2,500 ppm by weight.

[0045] [Other Additives] In addition to the antioxidant and mold release agent described above, other additives may be added to the thermoplastic resin composition. For example, additives that may be contained in the thermoplastic resin composition include compounding agents, catalyst deactivators, heat stabilizers, plasticizers, fillers, UV absorbers, rust inhibitors, dispersants, antifoaming agents, leveling agents, flame retardants, lubricants, dyes, pigments, bluing agents, nucleating agents, and clarifying agents. The content of other additives other than the antioxidant and mold release agent in the thermoplastic resin composition is preferably 10 ppm by weight to 5.0% by weight, more preferably 100 ppm by weight to 2.0% by weight, and even more preferably 1000 ppm by weight to 1.0% by weight, but is not limited thereto. The above-mentioned additives may adversely affect transmittance, so it is preferable not to add them in excess; for example, the total amount added is within the above-mentioned range.

[0046] Furthermore, another embodiment of the present invention is a thermoplastic resin composition containing a modifier represented by the following general formula (1) and a thermoplastic resin. Each symbol in the general formula (1) has the same meaning as in the above-mentioned general formula (1). That is, the monomer represented by the general formula (1) can also be used as a modifier.

[0047] In one embodiment of the present invention, the modifier can be blended so that the mass ratio of the thermoplastic resin to the modifier is 99.9:0.1 to 70:30. The mass ratio is preferably 99:1 to 70:30, more preferably 98:2 to 70:30, such as 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, or 70:30. In the present invention, if the mass ratio of the thermoplastic resin to the modifier is within the above range, a resin composition with high flowability and good moldability can be provided.

[0048] <Optical Members> The thermoplastic resin or thermoplastic resin composition of the present invention (hereinafter simply referred to as "resin composition") can be suitably used for optical members. In one embodiment of the present invention, an optical member comprising the resin composition of the present invention is provided. In one embodiment of the present invention, optical members include, but are not limited to, optical disks, transparent conductive substrates, optical cards, sheets, films, optical fibers, lenses, prisms, optical films, substrates, optical filters, hard coat films, and the like. The resin composition of the present invention can be molded by a casting method with high flowability, and is therefore particularly suitable for producing thin optical members. In a preferred embodiment of the present invention, the optical member produced using the resin composition of the present invention may be an optical lens. In another preferred embodiment of the present invention, the optical member produced using the resin composition of the present invention may be an optical film.

[0049] When an optical element containing the resin composition of the present invention is produced by injection molding, molding is preferably performed under conditions of a cylinder temperature of 260 to 350°C and a mold temperature of 90 to 170°C. More preferably, molding is performed under conditions of a cylinder temperature of 270 to 320°C and a mold temperature of 100 to 160°C. If the cylinder temperature is higher than 350°C, the resin composition will decompose and discolor, and if it is lower than 260°C, the melt viscosity will be high, making molding difficult. Furthermore, if the mold temperature is higher than 170°C, it will be difficult to remove a molded piece made of the resin composition from the mold. On the other hand, if the mold temperature is lower than 90°C, the resin will harden too quickly in the mold during molding, making it difficult to control the shape of the molded piece and making it difficult to sufficiently transfer the shape of the molded piece.

[0050] <Optical Lens> In one embodiment of the present invention, the resin composition can be suitably used for optical lenses. Optical lenses produced using the resin composition of the present invention have a high refractive index and excellent heat resistance, and are therefore extremely useful in fields where expensive high refractive index glass lenses have traditionally been used, such as telescopes, binoculars, and television projectors. For example, in smartphone lenses, a lens molded from a thermoplastic resin containing the structural unit (A) and a resin containing any one of the structural units of formulas (II-1) to (II-4), or (In the above formula, R １ and R ２ each independently represents a hydrogen atom, a methyl group, or an ethyl group; R ３ and R ４each independently represents a hydrogen atom, a methyl group, an ethyl group, or an alkylene glycol having 2 to 5 carbon atoms. Raaa and Rbbb each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N, and S and which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and -C≡C-R ｈ and mm and nn each independently represent an integer of 0 to 6.) A lens molded from a resin containing a structural unit derived from any one of the monomers of the above formulas can be superimposed on the resin to be used as a lens unit.

[0051] The optical lens of the present invention is preferably implemented as an aspherical lens, if necessary. Since an aspherical lens can substantially eliminate spherical aberration with a single lens, it is not necessary to eliminate spherical aberration by combining multiple spherical lenses, which allows for weight reduction and reduced molding costs. Therefore, aspherical lenses are particularly useful as camera lenses, among other optical lenses.

[0052] Furthermore, because the optical lens of the present invention has high molding fluidity, it is particularly useful as a material for optical lenses that are thin, small, and have complex shapes. Specifically, the lens size preferably has a central thickness of 0.05 to 3.0 mm, more preferably 0.05 to 2.0 mm, and even more preferably 0.1 to 2.0 mm. The diameter is preferably 1.0 to 20.0 mm, more preferably 1.0 to 10.0 mm, and even more preferably 3.0 to 10.0 mm. Furthermore, the lens preferably has a meniscus shape, with one side convex and the other concave. The optical lens of the present invention can be molded by any method, such as mold molding, cutting, polishing, laser machining, electrical discharge machining, or etching. Among these, mold molding is more preferred in terms of production costs.

[0053] <Optical Film> In one embodiment of the present invention, the resin composition can be suitably used for optical films. In particular, optical films produced using the polycarbonate resin of the present invention have excellent transparency and heat resistance, and are therefore suitable for use as films for liquid crystal substrates, optical memory cards, etc. In order to minimize the inclusion of foreign matter in the optical film, the molding environment must naturally be a low-dust environment, preferably class 6 or less, and more preferably class 5 or less.

[0054] Examples of the present invention will be shown below together with comparative examples to explain the details of the invention, but the present invention is not limited to these examples.

[0055] 1) Refractive index (nD): A test specimen was prepared by molding a polycarbonate resin into a V-shaped block according to JIS B 7071-2:2018. The refractive index was measured at 23°C using a refractometer (Shimadzu KPR-3000).

[0056] 2) Abbe number (ν) Using the same test piece (V-block) as used in the refractive index measurement, the refractive indexes at wavelengths of 486 nm, 589 nm, and 656 nm at 23°C were measured using a refractometer, and the Abbe number was calculated using the following formula: ν=(nD−1) / (nF−nC), where nD is the refractive index at a wavelength of 589 nm, nC is the refractive index at a wavelength of 656 nm, and nF is the refractive index at a wavelength of 486 nm.

[0057] 3) Glass transition temperature (Tg) Measured according to JIS K7121-1987 using a differential scanning calorimeter (X-DSC7000 manufactured by Hitachi High-Tech Science Corporation) with a temperature increase program of 10°C / min.

[0058] 4) Weight-average molecular weight (Mw) The weight-average molecular weight of the resin was measured by gel permeation chromatography (GPC) and calculated in terms of standard polystyrene. The apparatus, column, and measurement conditions used were as follows: GPC apparatus: HLC-8420GPC, manufactured by Tosoh Corporation Columns: TSKgel SuperHM-M x 3, manufactured by Tosoh Corporation TSKgel guard column SuperH-H x 1, manufactured by Tosoh Corporation TSKgel SuperH-RC x 1, manufactured by Tosoh Corporation Detector: RI detector Standard polystyrene: Standard polystyrene kit PStQuick C, manufactured by Tosoh Corporation Sample solution: 0.2% by mass tetrahydrofuran solution Eluent: tetrahydrofuran Eluent flow rate: 0.6 mL / min Column temperature: 40°C

[0059] Example 1 As raw materials, 7.50 kg (15.04 mol) of (([1,1′-binaphthalene]-2,2′-diylbis(oxy))bis(4,1-phenylene))dimethanol (hereinafter referred to as “BINOL-DBAL”) represented by the following structural formula, 6.60 kg (15.04 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (hereinafter referred to as “BPEF”) represented by the following structural formula, 6.64 kg (30.99 mol) of diphenyl carbonate (hereinafter referred to as “DPC”), and 2.5×10 －２ 12 ml (3.0 x 10 －４ mole, i.e., 10 × 10 per mole of the total of dihydroxy compounds －６(mol) was placed in a 50-liter reactor equipped with a stirrer and a distillation device, and after nitrogen substitution, the mixture was heated to 205°C over 1 hour under a nitrogen atmosphere of 760 Torr and stirred. After complete dissolution of the raw materials, the reduced pressure was adjusted to 150 Torr over 15 minutes, and the mixture was maintained at 205°C and 150 Torr for 20 minutes to carry out a transesterification reaction. The mixture was then heated to 240°C at a rate of 37.5°C / hr and maintained at 240°C and 150 Torr for 10 minutes. The mixture was then adjusted to 120 Torr over 10 minutes and maintained at 240°C and 120 Torr for 70 minutes. The mixture was then adjusted to 100 Torr over 10 minutes and maintained at 240°C and 100 Torr for 10 minutes. The mixture was then reduced to 1 Torr or less over 40 minutes, and the polymerization reaction was carried out with stirring for 10 minutes at 240°C and 1 Torr. After the reaction was completed, nitrogen was introduced into the reactor to pressurize the reaction system, and the resulting polycarbonate resin was pelletized and removed to obtain a polycarbonate resin. The physical properties of the obtained polycarbonate resin are shown in Table 1 below. The monomer represented by general formula (1), "BINOL-DBAL," was obtained by the method described in Adv. Synth. Catal. 2004, 346, 195-198.

[0060] Comparative Example 1 As raw materials, 6.00 kg (16.02 mol) of 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene (hereinafter referred to as “BINOL-2EO”) represented by the following structural formula, 7.03 kg (16.02 mol) of 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene (“BPEF”) represented by the above structural formula, 7.07 kg (33.01 mol) of diphenyl carbonate (“DPC”), and 2.5×10 －２ 13 ml (3.2 x 10 －４ mole, i.e., 10 × 10 per mole of the total of dihydroxy compounds －６ A polycarbonate resin was obtained in the same manner as in Example 1, except that a polycarbonate resin having a molecular weight of 1000 to 15000 (mol) was used. The physical properties of the obtained polycarbonate resin are shown in Table 1 below.

[0061] (Examples 2 to 6) Polycarbonate resins of Examples 2 to 6 were obtained in the same manner as in Example 1, except that the materials shown in Table 1 were used as raw materials in the amounts shown in Table 1. The physical properties of the obtained polycarbonate resins are shown in Table 1 below. BINOL-DBALo: (([1,1'-binaphthalene]-2,2'-diylbis(oxy))bis(3,1-phenylene))dimethanol DPBHBNA: 6,6'-diphenyl-2,2'-bis-(2-hydroxyethoxy)-1,1'-binaphthyl

[0062] (Example 7) As raw materials, 8.33 kg (16.71 mol) of BINOL-DBAL, 2.00 kg (3.71 mol) of 2,2'-(((9H-fluorene-9,9-diyl)bis(naphthalene-6,2-diyl))bis(oxy))bis(ethanol-1-ol) (hereinafter referred to as "NOLE" or "BNEF") represented by the following structural formula, 6.72 kg (16.71 mol) of 1,1'-binaphthalene-2,2'-diylbisoxybisacetic acid (hereinafter referred to as "BINOL-DC") represented by the following structural formula, 0.96 kg (4.47 mol) of DPC, 1.41 g of aluminum (III) acetylacetonate (the amount of Al relative to the amount of resin produced was 7 ppm) and 1.69 ml of diethyl (4-methylbenzyl)phosphonate as catalysts were used. (P content relative to the amount of resin produced was 14 ppm) was placed in a 50-liter reactor equipped with a stirrer and distillation device, and after nitrogen substitution, the mixture was heated to 205°C over 1 hour under a nitrogen atmosphere of 760 Torr and stirred. After complete dissolution of the raw materials, the vacuum was adjusted to 300 Torr over 15 minutes and maintained at 205°C and 300 Torr for 90 minutes to carry out an ester exchange reaction. The temperature was then increased to 240°C at a rate of 37.5°C / hr and maintained at 240°C and 300 Torr for 10 minutes. The pressure was then adjusted to 150 Torr over 10 minutes and maintained at 240°C and 150 Torr for 1 hour. The pressure was then adjusted to 100 Torr over 20 minutes and maintained at 240°C and 100 Torr for 10 minutes. The pressure was further reduced to 1 Torr or less over 40 minutes, and the polymerization reaction was carried out with stirring at 240°C and 1 Torr for 10 minutes. After the reaction was completed, nitrogen was blown into the reactor to increase the pressure, and the polyester carbonate resin produced was pelletized and removed to obtain a polyester carbonate resin. The physical properties of the resulting polyester carbonate resin are shown in Table 1 below.

[0063] (Example 8) A polyester carbonate resin of Example 8 was obtained in the same manner as in Example 7, except that the materials shown in Table 1 were used as raw materials in the amounts shown in Table 1. The physical properties of the obtained polycarbonate resin are shown in Table 1 below. The results in Table 1 show that Examples 1 to 8, which used the monomer represented by general formula (1), have higher glass transition temperatures than Comparative Example 1, which did not use this monomer, and thus thermoplastic resins excellent not only in optical properties but also in heat resistance can be obtained.

Claims

1. A thermoplastic resin comprising a structural unit (A) derived from a monomer represented by the following general formula (1): 【Chemistry 1】 (In general formula (1), R １ ~R １２ Rk and Rp each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms containing one or more heterocyclic atoms selected from O, N, and S, or an aralkyl group having 7 to 20 carbon atoms; X and Y each represent a single bond or an alkylene group having 1 to 5 carbon atoms, i and ii each independently represent an integer of 0 to 4, K １ and K. ２ each independently represents -OH, -COOH, or -COORq, and Rq represents an alkyl group having 1 to 5 carbon atoms.

2. The thermoplastic resin of claim 1 which is a polycarbonate resin, a polyester resin, or a polyestercarbonate resin.

3. R in the general formula (1) １ ~R １２ Rk and Rp represent a hydrogen atom, X and Y represent a methylene group, K １ and K. ２ The thermoplastic resin according to claim 1 , wherein represents —OH.

4. R in the general formula (1) １ ~R １２ Rk and Rp each represent a hydrogen atom, X and Y each represent a single bond, K １ and K. ２ The thermoplastic resin according to claim 1, wherein Rq represents an alkyl group having 1 to 5 carbon atoms.

5. The thermoplastic resin comprises a structural unit (B) derived from a monomer represented by the following general formula (2) and / or a structural unit (C) derived from a monomer represented by the following general formula (3). The thermoplastic resin according to claim 1. 【Chemistry 2】 (In general formula (2), R ａ and R ｂ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and -C≡C-R ｈ is selected from the group consisting of R ｈ represents an aryl group having 6 to 20 carbon atoms which may have a substituent, or a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N and S and which may have a substituent, X represents a single bond or an optionally substituted fluorene group; A and B each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent; m and n each independently represent an integer of 0 to 6; a and b each independently represent an integer from 0 to 10. 【Chemistry 3】 (In 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 which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, and an aryl group having 6 to 20 carbon atoms which may have a substituent; Y １ represents a single bond, a fluorene group which may have a substituent, or any one of the structural formulae represented by the following formulae (4) to (11), 【Chemistry 4】 (In formulas (4) to (11), R ６１ , R ６２ , R ７１ and R ７２ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 30 carbon atoms which may have a substituent, or R ６１ and R ６２ , or R ７１ and R ７２ R represents a carbon ring or hetero ring having 1 to 20 carbon atoms which may have a substituent, which are formed by bonding with each other; ａａ and R ｂｂ is R in the above general formula (2). ａ and R ｂ is synonymous with Each of r and s independently represents an integer of 0 to 5000. A and B each independently represent an alkylene group having 1 to 5 carbon atoms which may have a substituent; p and q each independently represent an integer of 0 to 4; a and b each independently represent an integer from 0 to 10.

6. The thermoplastic resin according to claim 5, wherein the thermoplastic resin contains at least a structural unit derived from any one of BPEF, BNE, BNEF, and DPBHBNA.

7. The thermoplastic resin according to claim 1, further comprising a structural unit derived from at least one monomer selected from the following monomer group: 【Chemistry 5】 (In the above formula, R １ and R ２ each independently represents a hydrogen atom, a methyl group, or an ethyl group; R ３ and R ４ Each of Raaa and Rbbb independently represents a hydrogen atom, a methyl group, an ethyl group, or an alkylene glycol having 2 to 5 carbon atoms. Each of Raaa and Rbbb independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 20 carbon atoms which may have a substituent, a cycloalkoxyl group having 5 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, a heteroaryl group having 6 to 20 carbon atoms which contains one or more hetero ring atoms selected from O, N, and S and which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and -C≡C-R ｈ wherein mm and nn each independently represent an integer from 0 to 6.

8. The thermoplastic resin according to claim 1, wherein the polystyrene-equivalent weight average molecular weight (Mw) of the thermoplastic resin is 10,000 to 200,000.

9. The thermoplastic resin according to claim 1, wherein the refractive index (nD) of the thermoplastic resin is 1.64 to 1.

70.

10. The thermoplastic resin according to claim 1, wherein the Abbe number (ν) of the thermoplastic resin is 15.0 to 26.

0.

11. The thermoplastic resin according to claim 1, wherein the glass transition temperature of the thermoplastic resin is 130 to 180°C.

12. A thermoplastic resin composition comprising a modifier represented by the following general formula (1) and a thermoplastic resin: 【Chemistry 6】 (In general formula (1), R １ ~R １２ Rk and Rp each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms containing one or more heterocyclic atoms selected from O, N, and S, or an aralkyl group having 7 to 20 carbon atoms; X and Y each represent a single bond or an alkylene group having 1 to 5 carbon atoms, i and ii each independently represent an integer of 0 to 4, K １ and K. ２ each independently represents -OH, -COOH, or -COORq, and Rq represents an alkyl group having 1 to 5 carbon atoms.

13. An optical member comprising the thermoplastic resin according to claim 1 or the thermoplastic resin composition according to claim 12.

14. 13. An optical lens comprising the thermoplastic resin of claim 1 or the thermoplastic resin composition of claim 12.

15. An optical film comprising the thermoplastic resin according to claim 1 or the thermoplastic resin composition according to claim 12.

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